Food Hydrocolloids 42 (2014) 5e41

Contents lists available at ScienceDirect

Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Review

Beverage emulsions: Recent developments in formulation, production,

and applications
Daniel T. Piorkowski, David Julian McClements*
Department of Food Science, University of Massachusetts, Amherst, MA 01003, USA

a r t i c l e i n f o a b s t r a c t

Article history: Soft drinks are one of the most widely consumed and profitable beverages in the world. This review
Received 13 May 2013 article focuses on the utilization of emulsion science and technology for the fabrication of soft drinks by
Accepted 9 July 2013 the beverage industry. A brief overview of the various high and low energy methods available for pre-
Available online 26 July 2013
paring this type of beverage emulsions is given, as well as a discussion of the functional ingredients used
to formulate these systems, including oil phases, emulsifiers, weighting agents, ripening inhibitors, and
Keywords:
thickening agents. The influence of droplet characteristics on the physicochemical and sensory proper-
Beverages
ties of beverage emulsions is reviewed, with special focus on their influence on product stability. Finally,
Soft drinks
Nutraceuticals
we discuss recent developments in the soft drinks area, including fortification with vitamins, reduced
Flavors calorie beverages, and “all-natural” products.
Emulsions Ó 2013 Elsevier Ltd. All rights reserved.
Nanoemulsions

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
2. Emulsion science and technology in the beverage industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7
3. Controlling droplet characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
3.1. Droplet composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2. Droplet concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3. Droplet size distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4. Droplet charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.5. Interfacial properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.6. Colloidal interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4. Physicochemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.1. Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2. Rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3. Molecular distribution and release characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5. Beverage emulsion shelf-life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13
5.1. Physical stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.1.1. Gravitational separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.1.2. Droplet aggregation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5.1.3. Ostwald ripening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
5.2. Chemical stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5.3. Defining the end of shelf life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
6. Beverage emulsion manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18
6.1. High-energy approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
6.1.1. High pressure valve homogenizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
6.1.2. Microfluidizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6.1.3. Ultrasonic homogenizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

* Corresponding author. Tel.: þ1 413 545 1019.

E-mail address: mcclements@foodsci.umass.edu (D.J. McClements).

0268-005X/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodhyd.2013.07.009
6 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41

6.2. Low-energy approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

6.2.1. Spontaneous emulsification methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6.2.2. Phase inversion methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
7. Beverage emulsion ingredients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7.1. Oil phase components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7.1.1. Flavor oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7.1.2. Cloud oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
7.1.3. Nutraceutical lipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
7.1.4. Fat soluble colorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
7.2. Emulsifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
7.2.1. Mechanism of action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
7.2.2. Factors influencing selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
7.2.3. Ingredient examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
7.3. Weighting agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
7.3.1. Mechanism of action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
7.3.2. Factors influencing selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
7.3.3. Ingredient examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
7.4. Ripening inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
7.5. Thickening agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7.5.1. Mechanism of action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7.5.2. Factors influencing selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7.5.3. Ingredient examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7.6. Sweeteners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7.6.1. Mechanism of action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7.6.2. Factors influencing selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
7.6.3. Ingredient examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
8. Commercial aspects of beverage emulsion formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
9. Recent developments in beverage emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
9.1. “All-natural” products and cleaner ingredient lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
9.2. Low-calorie and mid-calorie soft drinks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
9.3. Energy drinks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
9.4. Beverage concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
9.5. Fortification with vitamins, minerals, and nutraceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
9.6. Bottled water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
9.7. New product innovation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
10. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

1. Introduction particles suspended within an aqueous medium, e.g., a micro-

Globally, soft drinks are one of the most widely consumed and
profitable beverages (Table 1). Cola is the top soft drink flavor
currently consumed in the United States, with lemon-lime and or-
ange being the second and third. All three of these soft drink flavors
contain hydrophobic citrus compounds extracted from fruit peels.
Soft drinks may also contain a variety of other hydrophobic com-
ponents, such as clouding agents, weighting agents, nutraceuticals,
oil-soluble vitamins, and oil-soluble antimicrobials. The non-polar
character of flavor oils and other hydrophobic ingredients means
that these ingredients cannot simply be dispersed directly into an
aqueous phase e they would rapidly coalesce and separate through
gravitational forces leading to a layer of oil on top of the product
(Given, 2009). Instead they first have to be converted into a colloidal
dispersion consisting of flavor molecules encapsulated within small
Table 1
Global revenue from non-alcoholic beverage sales by major beverage manufacturing
companies in 2010 (Beverage Executive. October 2011, “Worldwide 100”, pages 44e
48).
Company
Coca-Cola Co.
PepsiCo
Kraft Foods
Dr. Pepper Snapple Group
emulsion, nanoemulsion, or emulsion (McClements, 2011;
McClements & Li, 2010). These colloidal delivery systems must be
carefully designed to provide desirable physicochemical, sensory,
and biological attributes to the final product. A number of desirable
attributes of colloidal delivery systems suitable for application in
beverage products are highlighted below (McClements, Decker, &
Weiss, 2007; McClements & Li, 2010):
 Composition: Ideally, the delivery systems should be fabricated
entirely from “label friendly” food-grade ingredients that are
economic and easy to handle.
 Fabrication: Ideally, the delivery systems should be fabricated
using robust, reliable and inexpensive manufacturing methods
that are easily implemented.
 Stability: The delivery systems should be designed to withstand
all of the stresses that a product may experience during its
production, storage, transport and utilization, such as tem-
perature fluctuations, exposure to light and oxygen, exposure
to mechanical forces (such as stirring, flow through a pipe, and
vibrations), variations in aqueous phase composition (such as
Annual sales (billions of dollars) pH, ionic strength, buffer type, ingredient interactions), and
35.1
exposure to microorganisms (such as yeasts, molds or
21.4 bacteria).
8.8  Physicochemical and sensory properties: The delivery system
5.6 should not adversely affect the optical properties, rheology, or
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41 7

variety of different colloidal delivery systems suitable for applica-

tion within beverage products (McClements, 2012; McClements &
• Thermodynamically unstable Rao, 2011), with the most common being microemulsions, nano-
Emulsion • d > 100 nm emulsions, and emulsions (Fig. 1). Each of these colloidal disper-
• Optically opaque sions has particular benefits and limitations for the encapsulation
of hydrophobic compounds. Microemulsions are thermodynami-
cally stable systems under a specific set of environmental condi-
tions (e.g., composition and temperature), and are therefore easy to
fabricate (often by simple mixing) and tend to have good long-term
stability. Microemulsions typically contain very small particles
• Thermodynamically unstable
• d < 100 nm (r < 25 nm) and therefore tend to be optically transparent, which is
Nanoemulsion desirable for soft drinks that should be clear. On the other hand, the
• Transparent or slightly turbid
formation of microemulsions usually requires relatively high levels
of synthetic surfactants and sometimes the use of cosurfactants/
cosolvents, which can be undesirable for cost, taste, and labeling
• Thermodynamically stable
reasons. Microemulsions may also become thermodynamically
Microemulsion • d < 100 nm unstable if environmental conditions are altered (such as temper-
• Transparent or slightly turbid ature or composition).
Conventional emulsions (r > 100 nm) and nanoemulsions
(r < 100 nm) are both thermodynamically unstable systems, and
therefore tend to breakdown during storage through a variety of
Fig. 1. Schematic representation of different kinds of colloidal dispersions that can be instability mechanisms (Fig. 2), such as gravitational separation,
used in the beverage industry: emulsions, nanoemulsions, and microemulsions. flocculation, coalescence and Ostwald ripening (McClements & Rao,
2011; McClements et al., 2007). Emulsion systems must therefore
be carefully designed to inhibit these instability mechanisms and
flavor profile (aroma, taste, and mouthfeel) of the beverage provide sufficient kinetic stability throughout the lifetime of the
product into which it is incorporated. product. Emulsions usually contain larger droplets than micro-
 Biological activity: The delivery system should not adversely emulsions and therefore they scatter light more strongly and
affect the biological activity of any encapsulated bioactive appear more turbid or cloudy. This is an advantage for soft drinks
components, such as antimicrobials, vitamins, or nutraceuticals. that are required to have a cloudy appearance, but a disadvantage
for products where optical clarity is required. Nevertheless,
This review article provides an overview of the current status of recently it has been shown that emulsions with ultrafine droplets,
the design, formulation, and production of emulsion-based de- often referred to as “nanoemulsions”, can be prepared that are
livery systems suitable for utilization within the beverage industry. optically transparent (McClements, 2012; McClements & Rao,
2011). A major advantage of emulsions and nanoemulsions is that
2. Emulsion science and technology in the beverage industry the emulsifier-to-oil ratio required to formulate them is often much
less than that required for microemulsions, and they can be
Hydrophobic components (such as flavor oils, clouding agents, formulated from all natural ingredients (such as proteins and
oil-soluble vitamins, and nutraceuticals) can be incorporated into a polysaccharides) rather than synthetic surfactants (such as

Fig. 2. Schematic diagram of most common instability mechanisms that occur in food emulsions: creaming, sedimentation, flocculation, coalescence, Ostwald ripening and phase
inversion.
8 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
Tweens). In this article, we focus primarily on the utilization of
emulsion systems (conventional emulsions and nanoemulsions) in
the preparation of soft drinks but much of the material is also
relevant to the formulation of microemulsions.
It should be noted that the emulsions used in the beverage in-
dustry are typically divided into two groups: flavor emulsions and
cloud emulsions. Flavor emulsions contain lipophilic compounds
that are primarily present to provide taste and aroma to a beverage
product (such as lemon, lime, or orange oils). On the other hand,
cloud emulsions are used to provide specific optical properties to
certain beverage products, i.e., to increase their turbidity (“cloudi-
ness”). Cloud emulsions are typically prepared using an oil phase
that is highly water-insoluble and that is not prone to chemical
degradation, such as flavorless vegetable oils. In addition, the size of
the droplets within cloud emulsions is designed so that they have
dimensions where strong light scattering occurs, but are not too
large to undergo gravitational separation (e.g., r ¼ 100e200 nm).
Cloud emulsions are often added to beverages that only contain a
relatively low percentage of juice and provide a desirable cloudy
appearance that hides sedimentation and ringing.
In this article, we will use the term “emulsion” to refer to both
nanoemulsions and conventional emulsions because they have
similar structures and properties. Generally, an emulsion consists
of at least two immiscible liquids (usually oil and water), with one
of the liquids being dispersed as small spherical droplets in the
other (Dickinson, 1992a; Dickinson & Stainsby, 1982; Friberg,
Larsson, & Sjoblom, 2004; McClements, 2005). In general, emul-
sions are classified according to the relative spatial organization of
the oil and water phases. A system that contains oil droplets
dispersed within water is called an oil-in-water (O/W) emulsion,
whereas a system that contains water droplets dispersed in oil is
called a water-in-oil (W/O) emulsion. It is possible to prepare more
complex emulsion structures, e.g., oil-in-water-in-oil (O/W/O),
water-in-oil-in-water (W/O/W) or oil-in-water-in-water (O/W/W)
emulsions (Benichou, Aserin, & Garti, 2004; Garti & Bisperink, 1998;
van der Graaf, Schroen, & Boom, 2005). Currently, almost all of the
emulsions used in the beverage industry are of the O/W type,
although there may be certain advantages to using other emulsion
types for certain applications. For example, in principle it is possible
to trap a hydrophilic bioactive component within the inner water
phase of a W/O/W emulsion to protect it from chemical degradation
or for taste masking. In practice, it is often difficult to formulate W/
O/W emulsions that have sufficient stability for commercial appli-
cations, although this is still an active area of research.
Emulsions are thermodynamically unfavorable systems that
tend to break down over time though a variety of physicochemical
mechanisms, including gravitational separation (creaming and
sedimentation), droplet aggregation (flocculation and coalescence)
and droplet growth (Ostwald ripening) (Dickinson, 1992a; Friberg
et al., 2004; McClements, 2005). It is possible to form emulsions
that are kinetically stable for a reasonable period of time by
including substances known as stabilizers, e.g., emulsifiers,
weighting agents, ripening inhibitors, or texture modifiers. It is
important to clearly distinguish the different physicochemical
mechanisms involved in promoting emulsion stability for these
different categories of stabilizers. Emulsifiers are surface-active
molecules that adsorb to the surface of freshly formed droplets
during homogenization, forming a protective layer that prevents
the droplets from aggregating. Weighting agents are dense hydro-
phobic components added to low-density oils to prevent gravita-
tional separation. Ripening inhibitors are water-insoluble
components added to polar oils to prevent Ostwald ripening.
Texture modifiers are substances used to increase the viscosity or gel
aqueous solutions, thereby retarding or preventing droplet move-
ment. A more detailed description of different types of stabilizers
that can be used in beverage emulsions is given in a later section.
Selecting the most appropriate stabilizer(s) for a particular appli-
cation is one of the most important factors determining the shelf-
life and physicochemical properties of beverage emulsions.
3. Controlling droplet characteristics
The bulk physicochemical properties of beverage emulsions
(such as optical properties, stability, rheology, molecular parti-
tioning, and release characteristics) are largely determined by the
properties of the droplets they contain (McClements, 2005), such as
composition, concentration, size, and charge (Fig. 3). In this section,
we discuss some of the most important droplet characteristics that
can be controlled by beverage manufacturers in order to create
products with specific desirable functional properties.
3.1. Droplet composition
The composition of the oil phase has a major influence on the
formation and stability of beverage emulsions, which has often been
overlooked in academic research. Beverage emulsions may contain a
variety of different hydrophobic components, including flavor oils,
essential oils, triacylglycerol oils, oil-soluble vitamins, nutraceuticals,
weighting agents, and ripening inhibitors. These components vary in
their molecular characteristics (such as molecular weight, molecular
conformation, and functional groups), which leads to changes in
their physicochemical properties (such as polarity, water-solubility,
density, viscosity, refractive index, physical state, and melting
point). Many of these molecular and physicochemical properties
have a major influence on the formation, stability, and functionality
of emulsions. For example, oil viscosity influences the efficiency of
droplet disruption during high energy homogenization e the closer
the ratio of dispersed phase viscosity to continuous phase viscosity
(hD/hC) is to unity, the more efficient is droplet disruption and the
smaller is the particle size produced (Walstra, 1993, 2003). Oil den-
sity determines the rate of particle creaming or sedimentation
within emulsions e the greater the density contrast between the
droplets and surrounding fluid, the faster the rate of gravitational
separation (McClements, 2005). Oil refractive index determines the
efficiency of light scattering by droplets in emulsions e the greater
the refractive index contrast between the droplets and surrounding
fluid, the stronger the degree of light scattering and the more turbid
the appearance (Chanamai & McClements, 2002). The water-
solubility of an oil phase determines the stability of an emulsion to
Ostwald ripening due to diffusion of oil molecules through the
Fig. 3. The particles in beverage emulsions can be designed to have different func-
tional performances by varying their physicochemical and structural properties, such
as size, composition, charge and interfacial properties.
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
aqueous phase (Kabalnov, 2001; McClements, Henson, Popplewell,
Decker, & Choi, 2012). Oil interfacial tension plays a number of
important roles in determining emulsion formation and stability.
First, the ease of droplet disruption during high energy homogeni-
zation decreases as the interfacial tension decreases (Walstra, 1993).
Second, the rate of droplet coalescence increases as the interfacial
tension decreases (Kabalnov & Wennerstrom, 1996). Third, the
ability of emulsifiers to adhere to droplet surfaces decreases as the
bare oil-water interfacial tension decreases (Chanamai, Horn, &
McClements, 2002). Finally, the rate of droplet growth due to Ost-
wald ripening depends on the interfacial tension at the oil-water
interface (Kabalnov, 2001).
For flavor emulsions, it is important to control the type and con-
centration of the flavor molecules initially present in the oil phase. It is
also important to be aware that the location of the flavor molecules
within an emulsion is governed by their oil-water partition, which
depends on carrier oil type (Choi, Decker, Henson, Popplewell, &
McClements, 2009; Choi, Decker, Henson, Popplewell, &
McClements, 2010b). The flavor profile of an emulsion may there-
fore change if the carrier oil type is altered, if the physical state of the
carrier oil changes, or if an emulsion is diluted, since this will change
the distribution of the flavor molecules in the oil, water and air (Choi
et al., 2009; Choi et al., 2010b; Mei et al., 2010).
It is important for beverage manufacturers to understand the
composition of the oil phases used to formulate commercial
products, and to understand how specific lipophilic components
influence the formation, stability, and properties of final products.
3.2. Droplet concentration
In general, the concentration of droplets in an emulsion in-
fluences its texture, stability, appearance, sensory attributes, and
nutritional quality (McClements, 2005; McClements & Rao, 2011).
Droplet concentration is usually characterized in terms of the
dispersed phase volume fraction (f), which is the volume of
emulsion droplets (VD) divided by the total volume of emulsion
(VE): f ¼ VD/VE. Practically, it is often more convenient to express
the droplet concentration in terms of the dispersed phase mass
fraction (fm), which is the mass of emulsion droplets (mD) divided
by the total mass of emulsion (mE): fm ¼ mD/mE. When the den-
sities of the two phases are equal, the mass fraction is equivalent to
the volume fraction. It is particularly important to convert the
droplet concentration to the appropriate units when comparing
experimental work with theoretical predictions.
In beverage emulsions, controlling the droplet concentration is
important for a number of reasons. Beverage emulsions are often
prepared in a concentrated form (>10% oil) because this facilitates
handling and transport, but they are highly diluted when they are
introduced into the final product (<0.1% oil). The amount to which
an emulsion concentrate is diluted influences the appearance of a
final product, since emulsion turbidity or cloudiness increases with
oil droplet concentration. Dilution also influences the total amount
of flavor molecules present in final products, as well as their par-
titioning between the oil and water phases (Choi et al., 2009). In the
concentrate, droplet concentration has a major impact on the
rheological properties of the system. From a practical point of view,
it may be important to have a high oil loading in the concentrate
emulsion so as to reduce transport and storage costs, but not have
the oil content so high that the product is unstable or cannot easily
be dispersed into the final product.
3.3. Droplet size distribution
The size distribution of the droplets in a beverage emulsion has a
strong impact on its physical stability (e.g., to gravitational separation,
9
flocculation, coalescence and Ostwald ripening) and its optical
properties (e.g., lightness and color) (McClements, 2005). Beverage
manufacturers must therefore specify the optimum droplet size dis-
tribution required for their particular product based on the properties
required, e.g., optical clarity and shelf-life. They must then develop a
formulation and manufacturing process that can reliably produce a
beverage with this droplet size distribution. Immediately after the
product has been manufactured it is usually important to measure the
droplet size distribution to ensure that it has met the specified quality
criteria, e.g., using light scattering instruments. It may also be
important to measure changes in the droplet size distribution of the
product during storage or after an accelerated storage test to predict
its long-term stability (McClements, 2007).
The particle size distribution (PSD) of an emulsion specifies the
concentration of droplets within different size classes, and can be
conveniently measured using various commercially available in-
struments (McClements, 2005). When presenting or interpreting PSD
data on a beverage emulsion it is important to pay particular attention
to the manner in which the particle concentration and particle size
are presented. The concentration of particles within a particular size
class is usually presented as either the volume or number percent,
whereas the size of the particles in a particular size class is usually
presented as either the mid-point particle radius or diameter. The
same PSD may look very different if it is plotted as volume versus
particle size or as number versus particle size. Typically, particle vol-
ume versus particle diameter is the most widespread and informative
way of presenting particle size data. Commercial beverage emulsions
are always polydisperse systems that can be characterized as being
“monomodal”, “bimodal” or “multimodal” depending on whether
there are one, two, or more peaks in the particle size distribution.
Typically, beverage manufacturers would like to produce a final
product that has a narrow monomodal distribution, as this usually
provides the best long-term stability.
In many practical situations it is important to have knowledge of
the full PSD of a beverage emulsion since this contains information
about the size characteristics of all of the particles present, as well
as providing insights into the possible origin and nature of any
instability mechanisms. For example, it may be possible to detect a
small population of large particles that may cause problems with
creaming during long-term storage (i.e., ringing). In addition, by
measuring changes in the PSD overtime it is sometimes possible to
distinguish between different instability mechanisms (e.g., coales-
cence versus Ostwald ripening). Nevertheless, in some situations it
is more convenient to represent the full particle size distribution by
a measure of its central tendency and spread. The mean, median, or
modal particle sizes are often used as measures of the central
tendency, whereas the relative standard deviation is often used as a
measure of spread (Walstra, 2003). The mean particle size is the
most widely used method of representing the central tendency of
emulsion particle size distributions in the beverage industry.
It is important to realize that a number of different mean par-
ticles sizes can be derived from a full PSD and each mean size can
have a different magnitude and physical meaning (McClements,
2007). The three most commonly used mean particle sizes are
the number-weighted mean diameter (dN or d10 ¼ Snidi/Sni), the
P P
surface-weighted mean diameter (dS or d32 ¼ ni d3i = ni d2i ) and
P P
the volume-weighted mean diameter (dV or d43 ¼ ni d4i = ni d3i ).
Generally, the volume-weighted mean diameter is more sensitive
to the presence of large particles than the number-weighted mean
diameter, and so it often provides the most rigorous test of the
physical stability of a beverage emulsion, i.e., if d43 is small then the
emulsion is more likely to remain stable. Appreciable differences
between the values of d10, d32 and d43 generally indicate that the
particle size distribution is broad or multimodal. One must there-
fore be very careful when interpreting or reporting particle size
10 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
data to identify which mean particle size value (and corresponding
relative standard deviation) is being used. It should also be noted
that mean values should be treated with caution when used to
represent highly polydisperse emulsions (e.g., aggregated systems),
and it is always useful to examine the full particle size distribution.
Commercial beverage manufacturers usually develop a set of
standardized particle size criteria that they use to determine
whether a particular batch of product has the desired physico-
chemical characteristics, e.g., long-term stability and optical prop-
erties. For example, a manufacturer might specify that the mean
droplet diameter (d43) of a particular class of products should
be < 500 nm, and that > 90% of the droplets should be smaller than
800 nm. The precise criteria used will depend on the product being
manufactured (especially whether it should be clear or opaque).
3.4. Droplet charge
The droplets in most beverage emulsions have an electrical
charge because of adsorption of ionic species to their surfaces, e.g.,
proteins, ionic polysaccharides, ionic surfactants, phospholipids,
fatty acids, and some small ions (McClements, 2005). The electrical
characteristics of a droplet surface depend on the type, concen-
tration and organization of the ionized species present, as well as
the ionic composition and physical properties of the surrounding
aqueous phase. The electrical charge on the oil droplets in a
beverage may be important for a number of reasons: it determines
the stability of the droplets to aggregation due to its influence of the
magnitude, range and sign of electrostatic interactions; it de-
termines the interactions of droplets with other charged species in
an emulsion e.g., ions (such as calcium or iron), or polyelectrolytes
(such as proteins or polysaccharides); it influences how the drop-
lets interact with electrically charged surfaces, such as storage
vessels, bottles, cups, and the mouth; it influences the behavior of
the droplets in an electrical field, which is important for measuring
their charge using electrophoresis.
The electrical characteristics of a droplet in an emulsion are
usually characterized in terms of its surface charge density (s),
electrical potential (J0), and/or z-potential (z) (Hunter, 1986). The
surface charge density is the amount of electrical charge per unit
surface area, which depends on the net number of ionized groups
per unit interfacial area. The electrical potential is the amount of
energy required to increase the surface charge density from zero to s.
The electrical potential depends on the surface charge density, but
also on the ionic composition of the surrounding medium due to
electrostatic screening effects. At a fixed surface charge density, the
electrical potential decreases with increasing ionic strength due to
these effects. The zeta-potential (z) is the electrical potential at the
“shear plane”, which is defined as the distance away from the droplet
surface below which the counter-ions remain strongly attached to
the droplet when it moves in an electrical field. Practically, the z-
potential is a better representation of the electrical characteristics of
an oil droplet because it inherently accounts for the adsorption of
any counter ions or ionic species to the droplet surface. In addition,
the z-potential is more convenient to measure than the surface
charge density or electrical potential (Hunter, 1986). Typically, the
electrical characteristics of the droplets in an emulsion are deter-
mined by measuring the z-potential versus pH under appropriate
measurement conditions (such as ionic composition).
Droplet aggregation is inhibited in many beverage emulsions by
using ionic emulsifiers that adsorb to the droplet surfaces and
prevent them from coming close together because of electrostatic
repulsion (Dickinson, 1992b; Friberg et al., 2004; McClements,
2005). Electrostatic repulsion plays a major role in determining
the aggregation stability of fat droplets coated by charged emulsi-
fiers that only form thin layers that generate short range steric
repulsion, such as globular proteins and ionic surfactants. On the
other hand, electrostatic repulsion is less important in systems
where the fat droplets are coated by emulsifiers that form thick
interfacial layers that generate long range steric repulsion, such as
polysaccharides (gum arabic and modified starch). For
electrostatically-stabilized emulsions, the magnitude of the z-po-
tential should be greater than about 20 mV to produce systems that
are stable during long-term storage. For sterically-stabilized
emulsions, the droplet charge may not be important in terms of
their physical stability, but it may still be important in systems
where chemical reactions occur within the oil droplets that are
induced by water-soluble ionic species, such as oxidation of u-3
fatty acids by transition metals.
3.5. Interfacial properties
The boundary between the oil and water phases in an emulsion
consists of a narrow region (z1e50 nm thick) that surrounds each
oil droplet, and contains a mixture of oil, water, and emulsifier
molecules, as well as possibly other molecular species, such as
mineral ions, polyelectrolytes, and polar lipids. The interfacial re-
gion makes up a significant fraction of the volume of a droplet
when the droplet diameter is less than about 1 mm (McClements &
Rao, 2011), and is therefore particularly important in beverage
emulsions since they usually contain droplets considerably smaller
than this size. The interfacial region can influence many important
physicochemical and sensory properties of beverages emulsions,
including their stability, rheology, mouthfeel, and flavor. For this
reason, it is often important to have knowledge about the interfa-
cial properties of the droplets in a beverage emulsion, and to
establish the major factors that influence them. Some of the most
important properties of the interfacial region are: composition;
structural organization; thickness; rheology; interfacial tension;
and charge. These properties are determined by the type, concen-
tration and interactions of any surface-active species present, as
well as by the events that occur before, during, and after emulsion
formation, e.g., complexation, competitive adsorption, layer-by-
layer formation (Dickinson, 2003). As mentioned earlier, the elec-
trical charge on the droplet interface influences its interaction with
other charged molecules, as well as its stability to aggregation. The
thickness and rheology of the interfacial region influences the
stability of emulsions to gravitational separation, coalescence and
flocculation, and determines the rate at which molecules leave or
enter the droplets (Dickinson, 2003; McClements, 2005). For
example, the ability of interfacial coatings to prevent droplet floc-
culation is strongly influenced by their thickness.
Beverage manufacturers should therefore be aware of the nature
of the interfacial region surrounding the oil droplets in their
products, and the fact that they may be able to manipulate its
properties to improve product performance.
3.6. Colloidal interactions
The attractive and repulsive colloidal interactions that operate
between the oil droplets in beverage emulsions determine their
stability to flocculation and coalescence, which in turn influences
their creaming stability and rheology (Friberg et al., 2004;
McClements, 2005). The colloidal interactions between two oil
droplets can be described in terms of an interaction potential (w(h)),
which is the energy required to bring two droplets from an infinite
distance apart to a surface-to-surface separation of h (Fig. 4). The
overall interaction potential is made up from contributions from
various types of interactions, with the most important being van
der Waals, steric, electrostatic, depletion, and hydrophobic in-
teractions (Israelachvili, 2011; McClements, 2005). These individual
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41 11

Table 2
Summary of major colloidal interactions operating between oil droplets in beverage
emulsions. It is assumed that the droplets are coated by the same type of emulsifier.

Interactions Sign Magnitude Range Factors affecting

Van der Attractive Intermediate Intermediate Always

Waals present
Steric Repulsive Strong Short Thickness and
chemistry of
interface
Electrostatic Repulsive Strong-to- Long-to- pH and ionic
weak short strength
Depletion Attractive Weak-to- Short Amount & type
medium of non-adsorbed
polymer
Bridging Attractive Strong Short Amount & type
of adsorbing
polymer
Hydrophobic Attractive Strong Long Surface
hydrophobicity

The most important physicochemical attributes of these systems

Fig. 4. Schematic representation of the interaction potential between two emulsion
droplets. The droplets may be stable, weakly flocculated, strongly flocculated, or
coalesced depending on the attractive and repulsive forces between them.
interactions vary in their sign (attractive or repulsive), magnitude
(weak to strong) and range (short to long). Each of the individual
interactions usually has a simple dependence on surface-to-surface
separation, but the sum of the interactions can exhibit a more
complex dependence. For example, the interaction potential be-
tween two oil droplets coated by a layer of charged polymer mol-
ecules would have a number of maximum and minimum values at
certain separations, such as short- and long-range energy barriers,
and primary and secondary minima (Fig. 4). Generally, droplets
tend to aggregate when attractive interactions dominate, but
remain as individual entities when repulsive interactions dominate
(McClements, 2005).
It is particularly important for scientists working in the beverage
industry to identify and understand the major colloidal interactions
operating between the droplets in their particular product. This
knowledge can then be used to establish the optimum approach for
maintaining product stability during production, transport and
storage. For example, if a beverage emulsion is stabilized by a
protein-based emulsifier, then electrostatic repulsive interactions
will play an important role in preventing droplet aggregation. In
this situation, the system will be sensitive to environmental
changes that reduce the magnitude and range of the electrostatic
repulsion acting between droplets, such as altering the pH or
adding salts (particularly multivalent counter-ions). On the other
hand, if the beverage emulsion is stabilized by a polysaccharide-
based emulsifier, then steric repulsive interactions will be most
important for preventing droplet aggregation. In this case, the
product will be much less sensitive to droplet aggregation when the
pH or ionic strength is changed. In this latter case, emulsion sta-
bility depends on the thickness and hydrophilicity of the interfacial
layer, which will depend on the molecular characteristics of the
polysaccharide molecules. A summary of the major colloidal in-
teractions in beverage emulsions is given in Table 2.
4. Physicochemical properties
The physicochemical properties of beverage emulsions play an
important role during the manufacturing process, as well as in
determining the perceived quality attributes of the final product.
are briefly discussed in this section. Some of these properties are
more important in the concentrated form of the beverage, whereas
others are more important in the diluted form.
4.1. Optical properties
The first cue that a consumer uses to judge the quality or desir-
ability of a finished beverage product is its visual appearance (pro-
vided it is packaged or poured into a transparent container, such as a
bottle or cup). Each type of beverage product is expected to have a
particular appearance depending on its nature, e.g., a dark brown
cola, a cloudy orange juice, or a clear green lime juice. From a sci-
entific viewpoint, emulsion appearance is categorized in terms of
their opacity and color, which can be quantitatively described using
tristimulus color coordinates, such as the L*a*b* system
(McClements, 2005). In this color system, L* represents the lightness,
and a* and b* are color coordinates: where þa* is the red
direction, a* is the green direction; þb* is the yellow direction, b*
is the blue direction; low L* is dark and high L* is light. The opacity of
an emulsion can therefore by characterized by the lightness (L*),
while the color intensity can be characterized by the chroma:
C ¼ (a*2 þ b*2)1/2. The color intensity is usually inversely related to
the lightness, so that the chroma decreases (fades) when the light-
ness increases. The optical properties of emulsions are mainly
determined by the relative refractive index, concentration, and size
distribution of the droplets they contain (Chanamai & McClements,
2002; Danviriyakul, McClements, Decker, Nawar, & Chinachoti,
2002; McClements, 2005). The lightness of an emulsion tends to
increase with increasing refractive index contrast and increasing
droplet concentration, and has a maximum value at a particular
droplet size. This has important implications for the development of
beverage products that should be either clear or opaque. In general,
the lightness of emulsions increases steeply as the oil droplet con-
centration increases from about 0 to 5 wt%, but then increases more
gradually at higher droplet concentrations (Fig. 5).
As mentioned earlier, some beverages are expected to have
optical clarity, whereas others are expected to be cloudy. Opti-
mizing the initial particle size distribution of a beverage emulsion,
as well as inhibiting any changes in the particle size during storage,
is therefore a particularly important part of designing a commercial
product with the desired optical properties. For clear products, the
majority of droplets should be less than about 50 nm in diameter so
that the light scattering is very weak (Wooster, Golding, &
Sanguansri, 2008). The scattering efficiency of the individual oil
droplets determines the maximum amount of oil phase that can be
12 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
Fig. 5. Lipid droplets have a major impact on the texture, appearance and stability of emulsions.
incorporated into a clear beverage before it becomes noticeably
cloudy. As a rule of thumb, a turbidity of 0.05 cm1 (at 600 nm) can
be considered to be a rough cut-off point between transparent and
cloudy products. For cloudy products, the majority of droplets
should be between about 200 and 400 nm in diameter so that the
light scattering is very strong (McClements, 2002). In this case, the
scattering efficiency of the individual oil droplets will determine
the minimum amount of a clouding emulsion required to reach a
particular turbidity in the final product.
4.2. Rheology
The rheological properties of beverage emulsions are also an
important factor determining their manufacture and utilization.
Most beverage emulsions are initially manufactured in a concen-
trated form, which is diluted appreciably during the production of
the final beverage product. The droplet concentration in the
beverage concentrate typically ranges from 3 to 30%, while that in
the final product is typically <0.1%. Industrially, the rheology of the
beverage concentrate is important since it influences the ease of
mixing, flow through a pipe, and packaging. A manufacturer typi-
cally wants to have as high an oil loading as possible, without the
product becoming too viscous or gel-like to handle easily. This re-
quires careful control of the total droplet concentration in the
system. The droplet concentration in the final beverage concen-
tration is usually so low that the rheology is dominated by the
properties of the aqueous continuous phase (see discussion below).
The rheology of dilute colloidal dispersions is normally charac-
terized by the shear viscosity (Genovese, Lozano, & Rao, 2007;
McClements, 2005). When the droplet concentration is less than
about 5% (4 < 0.05), the shear viscosity can be described by Ein-
stein’s equation:
h ¼ h0 ð1 þ 2:5fÞ
Here, h is the viscosity of the overall system, h0 is the viscosity of
the continuous phase, and 4 is the disperse phase volume fraction.
This equation under-predicts the viscosity of colloidal dispersions
with higher droplet concentrations due to the effects of droplete
droplet interactions. Einstein’s equation was derived assuming that
the colloidal particles were rigid isolated spheres surrounded by a
Newtonian fluid. Nevertheless, it still provides a good approxima-
tion of the rheological properties of dilute beverage emulsions
because the flow of the liquid within the oil phase is inhibited by
the emulsifier coating. The above equation shows that the viscosity
of a dilute emulsion increases linearly with droplet concentration,
but that the most important factor affecting the overall rheology is
the viscosity of the continuous phase. Thus the most effective
means of controlling the viscosity of a dilute beverage emulsion is
to change the viscosity of the continuous phase, e.g., by adding
sugars or polymer thickening agents.
The viscosity of concentrated emulsions can be described by a
semi-empirical equation that takes into account dropletedroplet
interactions (Berli, Deiber, & Quemada, 2005; McClements, 2005;
Quemada & Berli, 2002):
 2
f
h ¼ h0 1  (2)
fc
Here, 4 is the disperse phase volume fraction, and 4c (z0.63) is a
critical disperse phase volume fraction above which the droplets
are so closely packed together that they cannot easily flow past
each other. This equation shows that the viscosity of an emulsion
increases with increasing droplet concentration, gradually initially
and then steeply as the droplets become more closely packed
(Fig. 5). Around and above the droplet concentration where close
packing occurs, the emulsion becomes highly viscosity and may
exhibit solid-like characteristics, such as visco-elasticity and plas-
ticity (Berli et al., 2005; McClements, 2005; Quemada & Berli,
2002). In flocculated systems the critical concentration where the
system becomes highly viscous or solid-like may be much lower
than in a non-flocculated system. It is therefore important for
beverage manufactures to consider the influence of droplet con-
centration and interactions on the rheological properties of emul-
sion concentrates (Genovese et al., 2007; McClements, 2005;
Walstra, 2003).
4.3. Molecular distribution and release characteristics
A beverage emulsion may contain a number of constituents that
partition into different phases within the product, e.g., oil, aqueous,
interfacial, or gas phases (McClements, 2005). The physical location
of some of these constituents may have a major impact on the
quality attributes of the final product. For example, many flavor oils
(1) contain constituents that are chemically unstable and therefore
prone to degradation during storage (e.g., citral). The chemical
stability of these constituents is often dependent on their molec-
ular environment. For example, the rate of acid-catalyzed degra-
dation of citral has been shown to occur considerably faster when it
is located within an aqueous phase than when it is present within
an oil phase (Choi et al., 2009; Choi et al., 2010b). This would
suggest that it is better to keep citral under neutral conditions or
within the emulsion concentrate as long as possible before the final
dilution into the acid phase is carried out. The perceived flavor
profile of beverage emulsions depends on the distribution of vol-
atile molecules between the liquid and gas phases. Increasing the
oil content of an emulsion decreases the concentration of hydro-
phobic (KOW > 1) volatiles in the headspace and therefore reduces
the perceived flavor profile (Fig. 6). This phenomenon is important
to take into account when reformulating a beverage product so that
it contains a different fat concentration, e.g., fortification with a
bioactive lipid such as u-3 oils.
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41 13

3 these environmental stresses may promote emulsion instability

through a variety of physicochemical mechanisms: loss of ingre-
2.5 dient functionality (e.g., changes in solubility, surface activity, or
Relative Flavor Intensity
2
stabilization capacity); acceleration of chemical degradation re-
actions (e.g., oxidation, polymerization, or hydrolysis); acceleration
1.5 Flavor Polarity of physical instability mechanisms, (e.g., flocculation, coalescence
Non-polar
or Ostwald ripening). In this section, a brief overview of some of the
1 major instability mechanisms in beverage emulsions is given, and
Polar
0.5
some suggestions for preventing them from occurring are provided.

0 5.1. Physical stability

0 20 40 60 80
Oil Droplet Concentration (%)
Fig. 6. Initial flavor intensity of emulsions with fixed flavor content is strongly
dependent on oil droplet content.
The location of a constituent within a beverage emulsion is
governed by its equilibrium partition coefficients (e.g., oil-water,
oil-air, oil-interface) and its mass transport kinetics through the
system (McClements, 2005). When a beverage emulsion is placed
in the mouth there is a redistribution of flavor molecules, with
some of the aroma compounds leaving the product and entering
the nasal cavity. The rate at which flavor molecules leave the
droplets in beverage emulsions is usually extremely quick (<0.1 s
for KOW < 1000), and therefore droplet dimensions tend to have
little impact on the flavor release profile (McClements, 2005).
Nevertheless, it may be possible to encapsulate oil droplets within
hydrogel matrices to slow down the release of flavor molecules
within the mouth.
5. Beverage emulsion shelf-life
One of the most important factors determining the commercial
viability of beverage emulsions is their ability to resist changes in
their physical and chemical properties after their production.
Beverage emulsions experience a range of environmental stresses
during their manufacture, transport, storage, and utilization that
may reduce their shelf lives: mechanical forces (e.g., stirring, flow
through a pipe, centrifugation, vibrations, and pouring); tempera-
ture variations (e.g., freezing, chilling, warming, pasteurization, and
sterilization); exposure to light (e.g., natural or artificial visible or
ultraviolet waves); exposure to oxygen; variations in solution
properties (e.g., pH and mineral composition of water). Exposure to
100
Emulsions are thermodynamically unfavorable systems that
tend to break down over time due to a variety of physicochemical
mechanisms (Fig. 2), including gravitational separation, floccula-
tion, coalescence and Ostwald ripening (Dickinson, 1992a; Friberg
et al., 2004; McClements, 2005). All of these instability mecha-
nisms lead to a change in the structural organization of the various
components within the system, rather than in the type of mole-
cules present. Nevertheless, changes in the chemical structure of
active components can lead to changes in physical stability, and vice
versa.
5.1.1. Gravitational separation
Gravitational separation is one of the most common forms of
physical instability in commercial beverage emulsions, and it may
take the form of either creaming or sedimentation depending on the
relative densities of the oil droplets and the surrounding aqueous
phase. Creaming is the upward movement of droplets when they
have a lower density than the aqueous phase, whereas sedimen-
tation is the downwards movement of droplets when they have a
higher density than the aqueous phase. The oil phases used in
beverage emulsions consist primarily of triacylglycerol and/or fla-
vor oils, which have lower densities than water and so creaming is
more prevalent (Table 3). However, if a beverage emulsion con-
tained an excess of weighting agent within the oil phase then it
may be prone to sedimentation. A beverage emulsion is also prone
to sedimentation if it contains very small oil droplets covered by
relatively thick and dense interfacial layers (see below)
(McClements, 2011).
One of the most common problems reported in beverage
emulsions is “ringing”, which is the accumulation of a visible ring of
oil droplets on the top of a product. This effect is due to droplet
creaming, which may have occurred because a population of

Table 3
Physicochemical properties of oil phase, water phase, and weighting agents commonly used in the formulations of beverage emulsions (Chanamai & McClements, 2000;
McClements, 2005). The restriction levels based on USA regulations are also reported.

Components Structure Natural Density (kg m3) Restriction level (ppm)

Aqueous phases

Sugared e e z1050 e
Low calorie e e z1000 e
Oil phases
Flavor oils Mainly terpenes Yes 840e850 e
Vegetable oils Mainly triglycerides Yes 900e920 e
Weighting agents
Brominated Brominated hydrocarbon No 1240e1330 15
vegetable oil chain of triacylglycerols
Dammar gum Exudate from Caesalpinaceae Yes 1060 Not approved for
and Dipterocarpaceae shrubs use in the
United States
Ester gum Hydrophobic polymer Defined by 1080 100
manufacturer
Sucrose acetate Esterification of sucrose with No 1146 300
isobutyrate acetic and isobutyric anhydrides
14 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
droplets in the initial emulsion was too large, or because some
droplet growth occurred during storage, e.g., due to flocculation,
coalescence, or Ostwald ripening (see later sections). To a first
approximation, the velocity that an oil droplet moves upwards in a
dilute emulsion due to gravity is given by Stokes’ law:
 
2
2grparticle rparticle  r0
v ¼  (3)
9h0
where, v is the creaming velocity, rparticle is the particle radius,
rparticle is the particle density, r0 is the aqueous phase density, h0 is
the aqueous phase viscosity, and g is the acceleration due to gravity.
This equation shows that the rate of droplet creaming should
decrease as the droplet size decreases, the density contrast de-
creases, or the aqueous phase viscosity increases. Gravitational
forces cause droplets to move either upwards or downwards
depending on their density relative to the surrounding aqueous
phase. Hence, if only gravitational forces operated, then the drop-
lets would accumulate at either the top or the bottom of an
emulsion. In practice, droplets may also move because of Brownian
motion associated with the thermal energy of the system. Brow-
nian motion favors the random distribution of the droplets
throughout the entire volume of the emulsion, rather than their
accumulation at either the top or bottom. Gravitational forces tend
to dominate droplet movement in emulsions containing relatively
large droplets (r > 100 nm), whereas Brownian motion forces tend
to dominate droplet movement in emulsions containing smaller
droplets (McClements, 2011). Consequently, emulsions become
more stable to creaming or sedimentation as the particle size de-
creases because the creaming velocity decreases (v f r2) and
because Brownian motion effects increase.
The above calculations assume that the particles in beverage
emulsions are homogeneous spheres consisting entirely of oil
phase. In practice, the particles in beverage emulsions actually have
a coreeshell structure, consisting of an oil core and an interfacial
shell. In this case, the overall particle radius is given by
rparticle ¼ rcore þ d, and the overall particle density (rparticle) depends
on the densities of the core (rC) and shell (rS) materials and the
volume fraction of the shell (FS):
rparticle ¼ FS rS þ ð1  FS ÞrC (4)
The shell layer usually has a higher density than the oil or
aqueous phases, so that an increase in the volume fraction of the
shell layer will tend to increase the overall particle density. This has
important implications for preventing gravitational separation in
beverage emulsions with small droplets sizes since it reduces the
density contrast between the particles and aqueous phase. In
addition, very small particles may actually sediment rather than
cream if they contain sufficiently thick and dense emulsifier layers.
Thus, it should be possible to produce density matched particles in
beverage emulsions by controlling the oil core size and the thick-
ness of the adsorbed emulsifier layer.
The above discussion has highlighted a number of approaches
that can be used to inhibit or prevent gravitational separation in
beverage emulsions. First, gravitational separation can be pre-
vented by matching the density of the dispersed (oil) and contin-
uous (aqueous) phases. The density of the aqueous phase typically
varies from about 1000e1050 kg m3, depending on the amount of
sugars and other solutes present (Table 3). The density of most oil
phases is less than this value, and therefore oil droplets will tend to
move upwards. As already mentioned, the density of the coreeshell
particles within a beverage emulsion can be matched to the sur-
rounding aqueous phase by adding a weighting agent to the oil
phase, or by controlling the thickness and density of the emulsifier
layer. Second, gravitational separation can be inhibited by reducing
the size of the droplets in the emulsion, since the creaming velocity
is proportional to the droplet size squared (Stoke’s Law). If the
droplets are sufficiently small, then Brownian motion effects will
dominate and the system will remain stable to creaming or sedi-
mentation. Third, gravitational separation can be inhibited by
increasing the viscosity of the aqueous phase, e.g., by adding
thickening or gelling agents. This approach may not always be
viable since it will also influence the texture and mouthfeel of the
final product.
Another approach some beverage manufacturers have used to
mask the undesirable effects of creaming (“ringing”) on the
appearance of a product is to design the packaging so as to obscure
the effect, e.g., with appropriate placement of the labels or cap.
5.1.2. Droplet aggregation
The aggregation state of the droplets in a beverage emulsion is
important because it influences the stability of the product to
gravitational separation. Changes in particle size during storage
may also influence other important quality attributes of beverage
products, such as their appearance (cloudiness or homogeneity).
The tendency for droplet aggregation to occur in a beverage
emulsion depends on the balance of attractive and repulsive forces
operating between the droplets (see earlier). The nature of the
colloidal interactions operating in a particular beverage emulsion
depends on the physicochemical properties of the oil, water and
interfacial phases (e.g., dielectric constant and refractive index), oil
core characteristics (such as radius), interfacial shell characteristics
(such as thickness, charge, packing, rheology and hydrophobicity),
and the properties of the intervening fluid (such as pH, ionic
strength, osmotic pressure, and temperature). To a first approxi-
mation the overall colloidal interactions between a pair of droplets
in a beverage emulsion can be described by the sum of the van der
Waals (wVDV), electrostatic (wE), and steric (wS) interactions
(McClements, 2005):
wðhÞ ¼ wVDV ðhÞ þ wE ðhÞ þ wS ðhÞ (5)
The van der Waals interactions are attractive, whereas the steric
and electrostatic interactions are usually repulsive (Table 2). The
van der Waals attraction operates between all kinds of droplets and
would always cause aggregation if there were no opposing repul-
sive forces. The magnitude and range of the steric repulsion depend
on the thickness and chemistry of the interfacial layer, whereas the
magnitude and range of the electrostatic repulsion depend on the
droplet charge (z-potential) and the ionic composition of the
aqueous phase. To design a product that is stable to droplet ag-
gregation one must assure that the repulsive interactions dominate
the attractive interactions. This is usually achieved by using an
emulsifier that generates repulsive interactions between the
droplets. The emulsifiers used in the beverage industry typically
stabilize the droplets against aggregation by generating steric and/
or electrostatic repulsive interactions. Emulsifiers that form rela-
tively thick open interfaces (such as polysaccharides and non-ionic
surfactants with large hydrophilic head-groups) can generate a
steric repulsion that is sufficient strong and long range to overcome
the attractive van der Waals interactions, and thereby stabilize the
system against aggregation. Emulsifiers that form highly charged
interfaces (such as proteins and ionic surfactants) can generate a
strong electrostatic repulsion between droplets that prevent ag-
gregation. However, emulsifiers that can only stabilize emulsions
due to electrostatic interactions may be prone to instability when
the pH or ionic strength is changed. Some emulsifiers use a com-
bination of electrostatic and steric repulsion to stabilize the system,
e.g., such as casein and whey proteins.
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
The droplets in emulsions are in continual motion because of
the effects of thermal energy, gravity, or applied mechanical forces,
and as they move about they frequently collide with their neigh-
bors. After a collision, emulsion droplets may either move apart or
remain aggregated, depending on the relative magnitude of the
attractive and repulsive interactions between them. Droplets
aggregate when there is a primary or secondary minimum in the
interaction potential that is sufficiently deep and accessible to the
droplets (Fig. 4). The two major types of aggregation in beverage
emulsions are flocculation and coalescence.
5.1.2.1. Flocculation. Droplet flocculation is the process whereby
two or more droplets come together to form an aggregate in which
the droplets retain their individual integrity (Fig. 2). Droplet floc-
culation is usually detrimental to beverage emulsion quality
because it accelerates the rate of gravitational separation thereby
reducing their shelf-life. Flocculation can also cause an appreciable
increase in the viscosity of beverage emulsion concentrates, and
may even lead to the formation of a gel. This may be undesirable
since it would influence the transport, handling and dispersibility
of the product. Flocculation may occur in beverage emulsions
through a variety of different processes that either increase the
attractive forces or decrease the repulsive forces operating between
the droplets. The mechanism that is important in a particular
emulsion depends largely on the nature of the emulsifier used and
the solution conditions (e.g., pH, ion type and concentration, and
functional ingredients).
Reduced electrostatic repulsion: Electrostatically stabilized
emulsions may flocculate when the electrostatic repulsion between
the droplets is reduced. A number of physicochemical changes may
cause this reduction in electrostatic repulsion (Israelachvili, 2011):
(i) the pH is altered so that the net charge on the droplets is
reduced; (ii) counter-ions bind to the surface of the droplets and
reduce their charge (“charge neutralization”); (iii) the ionic
strength of the aqueous phase is increased to screen the electro-
static interactions (“electrostatic screening”). Protein-coated oil
droplets are particularly sensitive to flocculation due to reduction
in the electrostatic repulsion between them when the pH or ionic
composition is altered (Demetriades, Coupland, & McClements,
1997a; McClements, 2004).
Increased depletion attraction: The presence of non-adsorbing
colloidal entities in the continuous phase of an emulsion, such as
biopolymers or surfactant micelles, generates an increase in the
attractive force between the droplets due to an osmotic effect
associated with the exclusion of the colloidal entities from a narrow
region surrounding each droplet (Israelachvili, 2011). This attrac-
tive force increases as the concentration of colloidal entities in-
creases, until eventually it becomes large enough to overcome the
repulsive interactions between the droplets and causes them to
flocculate. This type of droplet aggregation is usually referred to as
depletion flocculation. The presence of relatively high concentra-
tions of non-adsorbed biopolymer emulsifiers (gum arabic and
modified starch) have been shown to induce depletion flocculation
in model beverage emulsions (Chanamai & McClements, 2001).
Depletion flocculation may also be promoted by other kinds of
biopolymers that might be used in beverages, such as maltodextrin,
pectin, xanthan gum, and carrageenan (Cao, Dickinson, & Wedlock,
1990; Cho & McClements, 2009; Gu, Decker, & McClements, 2004;
Gunning, Hibberd, Howe, & Robins, 1988).
Increased hydrophobic interactions: This type of interaction is
important in emulsions that contain droplets that have some non-
polar regions exposed to the aqueous phase. A good example of this
type of interaction is the effect of thermal processing on the floc-
culation stability of oil-in-water emulsions stabilized by globular
proteins (Demetriades, Coupland, & McClements, 1997b). At room
15
temperature, whey protein stabilized emulsions (pH 7) are stable to
flocculation because of the large electrostatic repulsion between
the droplets, but when they are heated above 70  C they become
unstable. The globular proteins adsorbed to the surface of the
droplets unfold above this temperature and expose non-polar
amino acids that were originally located in their interior. Expo-
sure of these non-polar amino acids increases the hydrophobic
character of the droplet surface and therefore leads to flocculation
because of the increased hydrophobic attraction between the
droplets.
Formation of biopolymer bridges: Many types of biopolymer
promote flocculation by forming bridges between two or more
droplets. Biopolymers may adsorb either directly to the bare oil
surfaces of the droplets or to the adsorbed emulsifier molecules
that form the interfacial layer. To be able to bind to the droplets
there must be a sufficiently strong attractive interaction between
segments of the biopolymer and the droplet surface. The most
common types of interaction that operate in food emulsions are
hydrophobic and electrostatic (Dickinson, 2003). For example, a
positively charged biopolymer (such as chitosan) might adsorb to
the surface of two negatively charged emulsion droplets causing
them to flocculate (Ogawa, Decker, & McClements, 2003) or a
negatively charged biopolymer (such as pectin, carrageenan or
xanthan) might adsorb to the surface of two positively charged
droplets causing them to flocculate (Dickinson, 2003; Guzey &
McClements, 2006).
The development of a suitable strategy to prevent droplet floc-
culation in a particular beverage emulsion therefore depends on
identification of the physicochemical origin of flocculation in that
system. In general, flocculation can be prevented by ensuring that
the repulsive forces dominate the attractive forces, and that there
are no additives that can promote bridging.
5.1.2.2. Coalescence. Coalescence is the process whereby two or
more liquid droplets merge together to form a single larger droplet
(Fig. 2). Coalescence causes emulsion droplets to cream or sediment
more rapidly because of the increase in their particle size. In
beverage emulsions, coalescence eventually leads to the formation
of a layer of oil on top of the material, which is referred to as oiling
off. This process is one of the main reasons for the shiny oily layers
often seen on top of unstable beverage emulsions.
The susceptibility of a beverage emulsion to droplet coalescence
is highly dependent on the nature of the emulsifier used to stabilize
the system, since this instability mechanism involves two or more
droplets fusing together. In general, the susceptibility of oil droplets
to coalescence is determined by the nature of the forces that act
between the droplets (i.e. gravitational, colloidal, hydrodynamic
and mechanical forces) and the resistance of the interfacial layer to
rupture. The stability of emulsions to coalescence can be improved
by preventing the droplets from coming into close proximity for
extended periods, e.g., by preventing droplet flocculation, pre-
venting the formation of a creamed layer, or having too high droplet
concentrations (McClements, 2005). Alternatively, one can control
the properties of the interfacial layer surrounding the oil droplets to
make it more resistant to rupture, e.g., by selecting an appropriate
emulsifier or other additives that alter surface properties.
5.1.3. Ostwald ripening
This susceptibility of a beverage emulsion to Ostwald ripening
(OR) is mainly determined by the solubility of the oil phase in the
aqueous phase: the higher the solubility, the more unstable the
emulsion. Oil phases with very low water-solubilities (such as the
vegetable oils used in clouding emulsions) do not exhibit OR, but oil
phases with relatively high water-solubilities (such as flavor or
essential oils) may be highly unstable. Mechanistically, OR is the
16 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
process whereby the size of the oil droplets in an oil-in-water
emulsion increases over time due to diffusion of oil molecules
from small to large droplets through the intervening aqueous phase
(Kabalnov, 2001; Kabalnov & Shchukin, 1992). The driving force for
this effect is the fact that the water-solubility of an oil contained
within a spherical droplet increases as the radius of the droplet
decreases, which means that there is a higher concentration of
solubilized oil molecules in the aqueous phase surrounding a small
droplet than surrounding a larger one (Kabalnov & Shchukin, 1992;
McClements, 2005). The presence of this concentration gradient
means that solubilized oil molecules tend to move from the im-
mediate vicinity of smaller droplets to that of larger droplets. This
leads to an increase in mean droplet size over time, which can be
described by the following equation once steady state conditions
have been achieved (Kabalnov & Shchukin, 1992):
3 3 32
dðtÞ  dð0Þ ¼ ut ¼ aSN Dt
9
Here, d(t) is the number-weighted mean droplet diameter at time t,
d0 is the initial number-weighted mean droplet diameter, u is the
Ostwald ripening rate, a ¼ 2gVm/RT, SN is the water-solubility of the
oil phase in the aqueous phase, D is the translational diffusion co-
efficient of the oil molecules through the aqueous phase, Vm is the
molar volume of the oil, g is the oil-water interfacial tension, R is
the gas constant, and T is the absolute temperature.
The most important factor determining the stability of a
beverage emulsion to OR is the water-solubility of the oil phase
(SN) (Weiss, Herrmann, & McClements, 1999). For this reason OR is
not usually a problem for emulsions prepared using oils with a very
low water-solubility, such as long chain triglycerides (e.g., corn, soy,
sunflower, or fish oils). On the other hand, OR may occur rapidly for
emulsions prepared using oils with an appreciable water-solubility,
such as flavor oils and essential oils (Li, Le Maux, Xiao, &
McClements, 2009; McClements et al., 2012; Wooster et al.,
2008). OR can be retarded in these systems by adding a sub-
stance known as a ripening inhibitor. A ripening inhibitor is a non-
polar molecule that is soluble in the oil phase but insoluble in the
water phase, e.g., a long chain triacylglycerol (such as corn oil). This
type of molecule can inhibit OR by generating an entropy of mixing
effect that counter-balances the curvature effects.
Consider an oil-in-water emulsion that contains droplets
comprised of two different lipid components: a water-insoluble
component and a water-soluble component. The water-soluble
molecules will diffuse from the small to the large droplets due to
OR. Consequently, there will be a greater concentration of water-
insoluble molecules in the smaller droplets than in the larger
droplets after OR occurs. Differences in the composition of emul-
sion droplets are thermodynamically unfavorable because of the
entropy associated with mixing: it is more favorable to have the
two lipids distributed evenly throughout all of the droplets, rather
than to be located in particular droplets. Consequently, there is a
thermodynamic driving force that operates in the opposite direc-
tion to the OR effect. The change in droplet size distribution with
time then depends on the concentration and solubility of the two
components within the oil droplets. This approach has previously
been used to improve the stability of food-grade nanoemulsions,
such as those containing short chain triglycerides, essential oils,
and flavor oils (Li et al., 2009; McClements et al., 2012; Wooster
et al., 2008). An example of this effect is shown in Fig. 7 which
shows that droplet growth in orange oil-in-water emulsions during
storage can be inhibited by adding a sufficiently high concentration
of corn oil (the ripening inhibitor) (McClements et al., 2012). Or-
ange oil (4-fold) has a relatively high solubility in water, and
therefore is highly prone to OR, which leads to an appreciable
5
0% corn oil
2.5% corn oil
5% corn oil
Mean droplet diameter (µm)
4
10% corn oil
3
2
1
(6)
0
0 5 10 15
Storage Time (day)
Fig. 7. Droplet growth due to Ostwald ripening of orange oil emulsions can be
inhibited by adding a corn oil, which acts as a ripening inhibitor (McClements et al.,
2012).
increase in mean droplet size during storage. On the other hand,
corn oil has a very low solubility in water, and therefore it can
retard OR if it is incorporated into the oil phase prior to homoge-
nization. These results show that incorporating  10% corn oil into
the oil phase was sufficient to inhibit OR in these systems (Fig. 7).
OR may also be retarded by adding certain kinds of weighting
agents (such as ester gums) since these substances also have a very
low water solubility and therefore act as ripening inhibitors (Lim
et al., 2011).
5.2. Chemical stability
A number of lipophilic compounds that may be present in
beverage emulsions can undergo chemical degradation during
storage, which leads to a loss of color, flavor and/or nutrients. A few
representative examples of chemical degradation of lipophilic
components in oil-in-water emulsions are given below.
Citrus degradation. Several mechanisms lead to the chemical
decomposition of citrus flavor components (such as citral, d-limo-
nene, and citronellal), including oxidation, hydrolytic reactions, the
formation of terpene alcohols, and the cyclization of terpene al-
dehydes (Clark, Powell, & Radford, 1977; Kimura, Iwata, &
Nishimura, 1982; Kimura, Nishimura, Iwata, & Mizutani, 1983a,
1983b). Acid-catalyzed decomposition and oxidation reactions
change the desirable flavor profile of citrus oils by reducing the
concentration of desirable flavor components and increasing the
concentration of undesirable flavor components (Tan, 2004; Ueno,
Masuda, & Ho, 2004). The beverage industry would therefore like to
identify effective strategies for preventing these undesirable
chemical degradation reactions.
There has been a great deal of research on establishing the
major factors that influence the chemical degradation of citral
because this is one of the most important flavor compounds found
in commercial beverages. The degradation rate of citral in aqueous
solutions has been shown to increase with decreasing pH (Choi
et al., 2009) (Fig. 8). Most commercial beverages have acidic
aqueous phases and are therefore highly susceptible to flavor loss
during storage due to this acid-catalyzed mechanism. The
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
0.05
Citral Concentration (%)
0.04
0.03
pH 7
pH 6
0.02 pH 5
pH 4
pH 3
0.01
0 1 2 3 4 5 6 7
Storage Time (days)
Fig. 8. Influence of pH on the chemical degradation rate of citral in aqueous solutions:
the degradation rate increases with decreasing pH (Choi et al., 2009).
chemical stability of citral has been shown to be much higher
when it is located within an oil phase than in an aqueous phase
(Choi et al., 2009). Consequently, the chemical degradation of
citral in beverage emulsions can be improved by ensuring that the
citral molecules are located primarily in an oil phase rather than in
the aqueous phase. Indeed, studies have shown that citral stability
can be improved by increasing the oil droplet concentration (Choi
et al., 2009) or by adding surfactant micelles to the aqueous phase
(Choi et al., 2010b), although these strategies may not be practical
for most commercial products. It was proposed that citral stability
may be improved by encapsulating it within solid lipid particles
rather than within liquid oil droplets, however the opposite was
found to be true experimentally, which was attributed to the
expulsion of the citral molecules into the aqueous phase after
droplet crystallization (Mei et al., 2010). Addition of various kinds
of natural antioxidants to flavor oil emulsions has also been shown
to improve the stability of citral to chemical degradation (Yang,
Tian, Ho, & Huang, 2011). The oil droplets in beverage emulsions
are surrounded by a coating of emulsifier molecules, and so it may
be possible to improve the stability of the citral molecules within
them by engineering the properties of the interfacial layer (Decker
& McClements, 2001; Given, 2009). Indeed, studies have shown
that citral degradation was faster in flavor oil droplets coated by an
anionic surfactant than those coated by a non-ionic or cationic
surfactant, which was attributed to differences in the accumula-
tion of catalytic protons near the droplet surfaces (Choi, Decker,
Henson, Popplewell, & McClements, 2010a). A high local concen-
tration of protons is believed to accelerate the citral degradation
mechanism at the droplet surfaces. Coating flavor oil droplets with
a cationic biopolymer layers has also been shown to improve the
stability of citral to chemical degradation (Djordjevic, Cercaci,
Alamed, McClements, & Decker, 2007, 2008; Yang, Tian, Ho, &
Huang, 2012).
Polyunsaturated lipid degradation. There has been great interest
in the beverage industry in fortifying products with u-3 lipids (such
as flax, fish and algal oils) since these lipids have been claimed to
have health benefits and are currently under-consumed by the
general population. Nevertheless, there are many technical diffi-
culties associated will incorporating these lipids into beverage
products due to their high susceptibility to oxidation. Lipid oxida-
tion affects the quality of emulsion-based products, influencing
17
their flavor, odor, and nutritive value (Frankel, Satué-Gracia, Meyer,
& German, 2002). The oxidation of polyunsaturated lipids is a
highly complex series of chemical reactions that is initiated when a
lipid interacts with an oxygen reactive species, and proceeds
through molecular cleavage and oxygen addition reactions to the
formation of a wide variety of volatile compounds (McClements &
Decker, 2000; Waraho, McClements, & Decker, 2011). The rate at
which oxidation takes place is dependent on several factors: the
molecular structure of the lipids; storage conditions; the presence
of pro-oxidants and antioxidants; and the structural organization of
the system. Based on this knowledge a variety of strategies have
been developed to inhibit or prevent lipid oxidation in emulsified
products: addition of oil-soluble and water-soluble antioxidants;
chelation of pro-oxidant transition metals; engineering the inter-
face to prevent pro-oxidants from coming into close proximity to
lipid substrates; controlling environmental conditions, such as
exposure to heat, oxygen, or light.
Carotenoid degradation. Carotenoids are natural compounds
found in many fruits and vegetables that are may be used in foods
as colorants or nutraceuticals because of their potential health
benefits (Mayne, 1996; Ryan, O’Connell, O’Sullivan, Aherne, &
O’Brien, 2008). One of the major factors currently limiting the
incorporation of carotenoids into many food and beverage products
is their high susceptibility to chemical degradation. In particular,
carotenoids have a conjugated polyunsaturated hydrocarbon chain
that makes them highly prone to autoxidation (Boon, McClements,
Weiss, & Decker, 2009). A number of factors have previously been
shown to promote the oxidation of carotenoids, including highly
acidic environments (Konovalov & Kispert, 1999), light (Mortensen
& Skibsted, 1996), heat (Mader, 1964), singlet oxygen (Krinsky,
1998), transition metals (Gao & Kispert, 2003; Williams et al.,
2001), and free radicals (Liebler & McClure, 1996; Woodall, Lee,
Weesie, Jackson, & Britton, 1997). Once carotenoid degradation
has been initiated a number of secondary reaction products may
form, including epoxides, endoperoxides, apocarotenals and apoc-
arotenones (Gao & Kispert, 2003; Woodall et al., 1997; Yamauchi,
Miyake, Inoue, & Kato, 1993). The chemical degradation of carot-
enoids leads to color fading, and may reduce their beneficial health
properties.
Recent studies have examined the influence of interfacial
properties (i.e., emulsifier type), storage conditions (i.e., pH, ionic
strength, and temperature) and antioxidant addition (i.e., vitamin
E, Coenzyme Q10, EDTA and ascorbic acid) on the chemical
degradation of b-carotene encapsulated within oil-in-water
nanoemulsions (Qian, Decker, Xiao, & McClements, 2012). The
rate of b-carotene degradation was found to increase with
decreasing pH and increasing temperature, was faster for a non-
ionic surfactant (Tween 20) than for a protein (b-lactoglobulin),
and decreased with increasing antioxidant addition to either the
oil or aqueous phase.
5.3. Defining the end of shelf life
The end of the shelf life of a product can be defined as the time
when it becomes unacceptable to consumers, which depends on
the rate of the various physical and chemical instability mecha-
nisms occurring. A product may become unacceptable when a ring
of oil droplets is visible at the top of the bottle, when the flavor
components decompose/oxidize and create an unacceptable flavor
profile, when the color changes beyond an acceptable level, or
when the product is microbiologically unsafe to consume. A
beverage manufacture should establish quantitative criteria that
can be used to establish the end of the shelf life of their particular
product. They should then develop a systematic testing scheme
that can be used to predict the shelf life of products.
18 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
6. Beverage emulsion manufacture
Beverage emulsions are usually prepared using a two-step
process: a beverage emulsion concentrate (3e30 wt% oil) is pre-
pared, which is then diluted extensively to create the finished
product (<0.1 wt% oil) (Tan, 2004). In this section, we briefly
describe the major characteristics of the concentrate and finished
products, and then review some of the major manufacturing ap-
proaches for forming stable beverage emulsions.
Beverage emulsion concentrates: When beverages are prepared
using high energy homogenization methods (see below), all the
aqueous phase components are usually mixed together and all of
the oil phase components are mixed together prior to homogeni-
zation. The aqueous phase often has to be heated and mechanically
agitated to facilitate dissolution and dispersion of water-soluble
components (such as emulsifiers, thickening agents, buffers, min-
erals and other functional ingredients). Similarly, the oil phase may
also have to be heated and mechanically agitated to facilitate the
melting and dispersion of any antioxidants, weighting agents,
ripening inhibitors, or colors. Once the oil and aqueous phases have
been prepared they are blended together using a high-shear mixer
to form a coarse emulsion (d z 1e10 mm), which is then homog-
enized using a mechanical device to form a fine emulsion (d z 0.1e
1 mm). When beverages are prepared using low energy homoge-
nization methods a different approach may be taken (see below). In
this case, water-soluble surfactants and some other water-soluble
components may initially be incorporated into the oil phase,
which is then mixed with the aqueous phase. This process can lead
to the spontaneous formation of a microemulsion, nanoemulsion,
or emulsion depending on system composition and preparation
procedure. After preparation the beverage emulsion concentrate is
often pasteurized to reduce the microbial load, and then stored or
transported to the place where it will be used.
Finished product: The finished product is created by diluting the
beverage emulsion concentrate with another aqueous phase, which
may contain various other ingredients, such as colors, flavors,
preservatives, pH regulators etc. Typically, the concentrate is
diluted 500e1000 times to produce a final product that often has
an oil concentration < 20 mg per liter for a ready-to-drink product
Fig. 9. Schematic representation of mechanical devices that can be used to produce beverages emulsions using the high-energy approach: high pressure valve homogenizer,
microfluidizer and continuous ultrasonic homogenizer’.
(Given, 2009). The final product may be homogenized again to
ensure that any non-polar colors, flavors, and preservatives are
incorporated into the oil droplets. Appropriate selection of in-
gredients and processing conditions may lead to beverage products
with shelf lives longer than 12 months. However, the perceived
quality of a product may deteriorate after extended storage due to
detrimental changes in its physical or chemical properties.
Beverage emulsions are susceptible to various physical instability
mechanisms that can lead to undesirable changes in appearance,
such as ringing and oiling off (see earlier section). Beverage emul-
sions are also liable to undesirable quality changes due to chemical
degradation, e.g., changes in flavor profile due to degradation of
flavor molecules (such as citral) or color fading due to degradation
of colorants (such as carotenoids). These challenges can often be
overcome using appropriate packaging materials and/or proper
product formation. The design and formulation of successful soft
drink products requires careful selection of functional ingredients
(oil type, emulsifiers, weighting agents, ripening inhibitors, anti-
oxidants, etc.), preparation conditions (e.g., homogenization
method and operating conditions), and storage conditions (e.g.,
exposure to elevated temperatures, light, and oxygen).
A number of different methods can be used to form beverage
emulsion concentrates. In general, these approaches can be cate-
gorized as either high-energy or low-energy approaches depending
on the underlying physical principle of droplet formation (Acosta,
2009; Anton & Vandamme, 2009; Leong, Wooster, Kentish, &
Ashokkumar, 2009; Pouton & Porter, 2006; Tadros, Izquierdo,
Esquena, & Solans, 2004). High-energy approaches utilize me-
chanical devices (“homogenizers”) that generate intense forces
capable of disrupting and intermingling the oil and aqueous phases
leading to the formation of very fine oil droplets (Fig. 9). The most
commonly used homogenizers utilized in the beverage industry for
forming emulsions are high pressure valve homogenizers, but
microfluidizers and ultrasonic methods may also be used
(Gutierrez et al., 2008; Leong et al., 2009; Velikov & Pelan, 2008;
Wooster et al., 2008). High-energy approaches are probably the
most common method used for preparing beverage emulsions at
present because they are capable of large-scale production, and
they can be used to prepare emulsions from a variety of different
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
starting materials. Low energy approaches rely on the spontaneous
formation of fine oil droplets within mixed surfactant-oil-water
systems when the solution or environmental conditions are
altered (Anton, Benoit, & Saulnier, 2008; Bouchemal, Briancon,
Perrier, & Fessi, 2004; Chu, Ichikawa, Kanafusa, & Nakajima, 2007;
Freitas, Merkle, & Gander, 2005; Tadros et al., 2004; Yin, Chu,
Kobayashi, & Nakajima, 2009). A number of different low energy
approaches have been developed, and some of these are suitable for
utilization within the beverage industry, e.g., phase inversion and
spontaneous emulsification methods (Fig. 10). The minimum par-
ticle size that can be produced using either approach depends on
many different factors, which are highlighted in the sections below.
6.1. High-energy approaches
The size of the droplets generated by high energy approaches is
determined by a balance between two opposing processes occur-
ring within the homogenizer: droplet disruption and droplet coa-
lescence (Jafari, Assadpoor, He, & Bhandari, 2008). Only those
mechanical devices that are capable of generating extremely
intense disruptive forces are capable of producing the tiny droplets
required for most beverage emulsion applications (Fig. 9), i.e., high-
pressure valve homogenizers, microfluidizers, and ultrasonic de-
vices (Leong et al., 2009; Tadros et al., 2004). The smallest droplet
size that can be produced by a particular high-energy device de-
pends on homogenizer design (e.g., flow and force profiles), ho-
mogenizer operating conditions (e.g., energy intensity, duration),
environmental conditions (e.g. temperature), sample composition
(e.g., oil type, emulsifier type, concentrations), and the physico-
chemical properties of the component phases (e.g., interfacial ten-
sion, viscosity) (Kentish et al., 2006; Wooster et al., 2008).
High energy homogenizers are widely used to produce beverage
emulsions because they can be utilized with a wide variety of
different types of oils and emulsifiers. Once the homogenization
conditions have been optimized, beverage emulsions can be pro-
duced using triacylglycerol oils or flavor oils as the oil phase, and
Fig. 10. Schematic representation of various methods that can be used to produce beverages emulsions using a low-energy approach: emulsion inversion point method, spon-
taneous emulsification and phase inversion temperature.
19
proteins, polysaccharides, phospholipids, or surfactants as emulsi-
fiers. Thus, high-energy methods are suitable for producing both
cloud emulsions and flavor emulsions. Even so, the size of the
droplets produced depends strongly on the characteristics of the oil
and emulsifier used (see below). For example, it is usually easier to
produce very small droplets when the oil phase has a low viscosity
and/or interfacial tension (e.g., flavor oils) than when it has a high
viscosity and/or interfacial tension (e.g., triacylglycerol oils).
6.1.1. High pressure valve homogenizers
High pressure valve homogenizers are currently the most
common high-energy method of producing beverage emulsions.
Initially, a coarse emulsion is produced using a high shear mixer
and then this is fed directly into the inlet of the high pressure valve
homogenizer. The homogenizer has a pump that pulls the coarse
emulsion into a chamber on its backstroke and then forces it
through a narrow valve at the end of the chamber on its forward
stroke (Fig. 9). As the coarse emulsion passes through the valve it
experiences a combination of intense disruptive forces that cause
the larger droplets to be broken down into smaller ones. Different
nozzle designs are available to increase the efficiency of droplet
disruption. The droplet size produced using a high pressure valve
homogenizer usually decreases as the number of passes and/or the
homogenization pressure increases. It also depends on the viscosity
ratio of the two phases (usually oil and water) being homogenized.
Small droplets can only usually be produced when the disperse-to-
continuous phase viscosity ratio falls within a certain range
(0.05 < hD/hC < 5) (Tadros et al., 2004; Walstra, 1993, 2003). Finally,
it is important to have sufficient emulsifier present to cover all the
new droplet surfaces formed during homogenization, and to use an
emulsifier that can rapidly adsorb to the droplet surfaces to prevent
re-coalescence (Jafari et al., 2008). Usually, there is a linear rela-
tionship between the logarithm of the homogenization pressure (P)
and the logarithm of the droplet diameter (d): log d f log P, with
the constant of proportionality depending on homogenizer type
(McClements, 2005). To reduce the droplet size to the level required
20 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
in beverage emulsions it is sometimes necessary to operate at
extremely high pressures and to use multiple passes through the
homogenizer. Even then, it is only possible under certain circum-
stances to obtain droplets less than 100 nm in radius (e.g., high
emulsifier levels, low interfacial tensions, and appropriate viscosity
ratios).
6.1.2. Microfluidizers
The formation of beverage emulsions using a microfluidizer also
involves forcing a coarse emulsion through a narrow orifice under
high pressure to facilitate droplet disruption. However, the design
of the channels through which the emulsion is made to flow within
a microfluidizer is different from that of a high pressure valve ho-
mogenizer (Fig. 9). The microfluidizer divides an emulsion into two
streams that are then made to impinge on each other in an inter-
action chamber. Intense disruptive forces are generated within the
interaction chamber when the two fast moving streams of emul-
sion collide, leading to highly efficient droplet disruption.
A number of studies have examined the potential application of
microfluidizers for the production of model beverage emulsions
(Dalgleish, West, & Hallett, 1997; Henry, Fryer, Frith, & Norton,
2010; Klein, Aserin, Svitov, & Garti, 2010). These studies have
shown that small droplets can be produced provided that condi-
tions are optimized to facilitate droplet disruption and inhibit
droplet coalescence. The droplet size tends to decrease with
increasing homogenization pressure, number of passes, emulsifier
concentration, and decreasing disperse-to-continuous phase vis-
cosity ratio (Wooster et al., 2008). Again, there is usually a linear
relationship between the logarithm of homogenization pressure
and the logarithm of the droplet diameter: log d f log P. Recent
studies have identified some of the major factors influencing the
formation of fine emulsions using microfluidizers (Qian &
McClements, 2011). This study showed that the logarithm of the
mean droplet diameter decreased linearly with the logarithm of the
homogenization pressure for both an ionic surfactant (SDS) and a
globular protein (b-lactoglobulin) (Fig. 11). However, the slope of
the log(d) versus log(P) relationship was appreciably steeper for the
surfactant (0.57) than for the protein (0.29), which was
2.4
2.35
2.3
Log (d/ nm)
2.25
2.2 BLG
2.15
2.1 SDS
2.05
0.6 0.7 0.8 0.9 1 1.1
Log (P/ kpsi)
Fig. 11. Influence of homogenization pressure in a microfluidizer on the mean droplet
diameter of oil-in-water emulsions stabilized by either b-lactoglobulin (BLG) or so-
dium dodecyl sulfate (SDS). The oil phase density was increased by adding increasing
amounts of weighting agent (Qian, McClements, 2011).
attributed to the fact that the protein may adsorb more slowly to
the droplet surfaces, and that it may form a viscoelastic coating that
inhibits further droplet breakup. The dependence of the mean
droplet diameter on viscosity ratio (hD/hC) was also examined by
preparing emulsions using different oil phase and aqueous phase
compositions. For the ionic surfactant there was a distinct decrease
in mean droplet diameter with decreasing viscosity ratio, which
suggested that droplet disruption within the homogenizer became
easier as the viscosity of the two phases became more similar. On
the other hand, little change was found in mean droplet size with
viscosity ratio when a globular protein was used as an emulsifier,
which again may be due to the relatively slow adsorption of the
protein and its ability to form a coating that inhibits further droplet
disruption.
6.1.3. Ultrasonic homogenizers
Beverage emulsions can also be formed continuously using ul-
trasonic homogenizers. This type of homogenizer utilizes high in-
tensity ultrasonic waves to generate intense disruptive forces
(mainly generated by cavitation) that break the oil and water
phases into very small droplets (Kentish et al., 2006; Leong et al.,
2009; Lin & Chen, 2008). Batch and continuous ultrasonic ho-
mogenizers are available for producing emulsions (Leong et al.,
2009). However, continuous ultrasonic homogenizers are prob-
ably the most commonly used methods for the large scale pro-
duction of fine emulsions (Fig. 9). The size of the droplets produced
using these devices tends to decrease as the intensity of the ul-
trasonic waves is increased or the residence time in the disruption
zone is increased (Abismail, Canselier, Wilhelm, Delmas, &
Gourdon, 1999; Maa & Hsu, 1999). The homogenization efficiency
also depends on the type and amount of emulsifier present, and the
viscosity of the oil and aqueous phases (Jafari, He, & Bhandari,
2006; Kentish et al., 2006; Leong et al., 2009; Maa & Hsu, 1999).
Ultrasonic homogenizers are particularly suitable for low-viscosity
fluids, but are less suitable for more viscous systems.
6.2. Low-energy approaches
The formation of emulsions using low-energy approaches relies
on the spontaneous formation of oil droplets in surfactant-oil-water
mixtures when either their composition or their environment is
altered in a specific way (Anton & Vandamme, 2009; Anton et al.,
2008; Bouchemal et al., 2004; Yin et al., 2009). A number of
methods for preparing fine emulsions are based on the low-energy
approach, including spontaneous emulsification and phase inver-
sion methods (Fig. 10) (Anton & Vandamme, 2009; Anton et al., 2008;
Fernandez, Andre, Rieger, & Kuhnle, 2004; Maestro, Sole, Gonzalez,
Solans, & Gutierrez, 2008). Some of these low energy methods are
already used in the beverage industry for forming oil-in-water
emulsions, whereas others may also be for certain applications.
Low energy approaches are often more effective at producing
small droplet sizes than high energy approaches, but they are often
more limited in the types of oils and emulsifiers that can be used.
For example, it is currently not possible to use proteins or poly-
saccharides as emulsifiers in most of the low energy approaches
used to form very fine emulsions. Instead, relatively high concen-
trations of synthetic surfactants are usually required to form stable
emulsions by these approaches, which limit their use for some
beverage applications.
6.2.1. Spontaneous emulsification methods
In this method an emulsion is spontaneously formed when an
organic phase and an aqueous phase are mixed together (Anton &
Vandamme, 2009; Miller, 1988; Pouton & Porter, 2006). The
organic phase usually contains oil, hydrophilic surfactant, and
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
possibly water-miscible solvent, whereas the aqueous usually
contains water and possibly cosolvent and cosurfactant. The two
phases can be brought together in various ways: the organic phase
may be titrated into the aqueous phase (Anton & Vandamme,
2009), or the aqueous phase may be titrated into the organic
phase (Sonneville-Aubrun et al., 2009). When the two phases come
into contact the hydrophilic surfactant and/or solvent move from
the oil phase to the aqueous phase, which generates tiny oil
droplets at the phase boundary (Horn & Rieger, 2001). The size of
the droplets produced can be controlled by varying the composi-
tions of the two initial phases, as well as the mixing conditions.
The spontaneous emulsification method was recently compared
with a high energy method (microfluidization) of producing fine
emulsions (Yang, Marshall-Breton, Leser, Sher, & McClements,
2012). The surfactant-oil-water system used consisted of 15.4 wt%
non-ionic surfactant, 23.1 wt% MCT, and 61.5% water, with the
surfactant containing a 50:50 mixture of a hydrophilic (Tween 80)
and lipophilic (Tween 85) surfactant. In the high energy method,
the surfactant, oil and water were blended together, and then
passed through a microfluidizer. In the low energy method, the oil
and surfactant were mixed together, and then simply titrated into
the water using slow stirring. The microfluidization method pro-
duced droplets with a diameter of about 110 nm, whereas the
spontaneous emulsification method could produce droplets with
diameters around 140 nm. This simple experiment demonstrated
that nanoemulsions could be produced using the spontaneous
emulsification method, provided that the system composition was
optimized, i.e., surfactant, oil, and water contents. However, a much
higher surfactant-to-oil ratio (SOR) is required to produce small
droplets using the low energy method than with the high energy
method. The influence of SOR on the mean droplet diameter of
vitamin E nanoemulsions produced using the spontaneous emul-
sification approach is shown in Fig. 12. These measurements show
that there is a minimum in the mean droplet size at a particular
SOR, and therefore the composition of the system has to be care-
fully controlled to obtain a particular droplet size.
180
170
160
150
Mean Droplet Diameter (nm)
140
130
120
110
100
90
80
70
60
50
25 50 75 100 125 150
Surfactant-to-Oil Ratio (%)
Fig. 12. Influence of surfactant-to-oil ratio on the formation of 20 wt% oil-in-water
emulsions stabilized by a non-ionic surfactant (Tween 80) prepared using the spon-
taneous emulsification method (Saberi, Fang, & McClements, 2013). The oil phase
consisted of 80% vitamin E acetate and 20% MCT.
21
The ability of fine emulsions to be formed using the sponta-
neous emulsification method depends on the system composition
(surfactant, oil, and water levels), surfactant type, oil type, and
preparation method (order of addition, mixing speeds). This
approach is suitable for producing flavor or cloud emulsions, pro-
vided that an appropriate surfactant is used (such as a non-ionic
surfactant with a particular HLB number) and the surfactant-to-
oil ratio is optimized. The main advantage of this method is that
it is inexpensive, simple, and requires no major equipment,
whereas the disadvantage is that relatively high surfactant levels
are required (SOR z 1).
6.2.2. Phase inversion methods
A number of methods have been developed to formulate fine
emulsions that depend on inducing a phase inversion from a W/O
to O/W form, e.g., phase inversion temperature (PIT) and emulsion
inversion point (EIP) methods (Fernandez et al., 2004; Thakur,
Villette, Aubry, & Delaplace, 2008). In the PIT method the change
from one type of an emulsion to another involves a transitional
phase inversion, whereas in the EIP method it involves a cata-
strophic phase inversion (Fig. 13). A transitional phase inversion
occurs when the surfactant properties are altered by adjusting a
formulation variable, such as temperature, pH, or ionic strength. A
catastrophic phase inversion occurs when the ratio of the oil-to-
water phases is altered while the surfactant properties remain
constant.
6.2.2.1. Phase inversion temperature method. The PIT method is
based on changes in the optimum curvature and relative solubility
of non-ionic surfactants with changing temperature (Anton, Gayet,
Benoit, & Saulnier, 2007; Anton & Vandamme, 2009; Gutierrez
et al., 2008). Emulsions containing very fine droplets can be
spontaneously formed using the PIT method by varying the
temperature-time profile of appropriate mixtures of surfactant, oil,
and water. This type of phase inversion usually involves the
controlled transformation of an emulsion from one type to another
(e.g., W/O to O/W or vice versa) through an intermediate state. This
intermediate state is typically a liquid crystalline or bicontinuous
microemulsion phase. The driving force for this type of phase
inversion is the change in the physicochemical properties of the
surfactant molecules caused by temperature changes, e.g., molec-
ular geometry and solubility (Fig. 10). The molecular geometry of a
surfactant can be characterized by a packing parameter, p
(Israelachvili, 2011):
aT
p ¼ (7)
aH
where, aT and aH are the cross-sectional areas of the lipophilic tail-
group and hydrophilic head-group respectively. Surfactants spon-
taneously associate in water to form monolayers that have a cur-
vature that allows the most efficient packing of the surfactant
molecules. The optimum curvature of a monolayer depends on the
packing parameter of the surfactant: for p < 1, the optimum cur-
vature is convex (favoring O/W systems); for p ¼ 1, monolayers
with zero curvature are preferred (favoring lamellar structures);
and, for p > 1 the optimum curvature is concave (favoring W/O
systems). For non-ionic surfactants, the head group is relatively
large compared to the tail group (p < 1) at temperatures below the
175 PIT and so O/W emulsions are favored. Upon heating, the head
group becomes progressively dehydrated and so the packing
parameter increases. At the phase inversion temperature (PIT), the
head group and tail group have similar sizes (p ¼ 1) and so liquid
crystals or microemulsions are formed. Above the PIT, the head
group is relatively small compared to the tail group (p > 1) and so
22 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41

Fig. 13. Schematic diagram of formulation-composition map for a typical surfactant-oil-water system. This map can be used to understand the formation of emulsions and
nanoemulsions suing various phase inversion methods.

W/O emulsions are favored. The relative solubility of non- droplet coalescence when they are stored at temperatures
surfactants in the oil and water phases also changes with temper- approaching the PIT. This could be a problem in food and beverage
ature because of head group dehydration, which has also been used applications that require some form of thermal treatment (such as
to interpret the PIT phenomenon (Anton & Vandamme, 2009; pasteurization, sterilization or cooking) or that are stored at
Anton et al., 2007). At low temperatures, the head group is highly elevated temperatures (e.g., in warm or hot climates). Recently, we
hydrated and so the surfactant tends to be more soluble in water. As developed an approach to overcome this problem by forming
the temperature is raised and the head group becomes progres- emulsions using a non-ionic surfactant with a relatively low PIT,
sively dehydrated and the solubility of the surfactant in water de- and then diluting the resulting emulsions in a solution containing
creases, while its solubility in oil increases. At a particular another surfactant with a high PIT (Rao & McClements, 2010). This
temperature (zPIT), the solubility of the surfactant in the oil and second surfactant partially displaces some of the original surfactant
water phases is approximately equal. At higher temperatures, the
surfactant becomes more soluble in the oil phase than in the water
phase. Thus at high temperatures the surfactant is mainly located in
the oil phase, and when the system is cooled it has a tendency to
move into the aqueous phase. Thus, oil droplets are formed by a
mechanism similar to spontaneous emulsification.
The PIT method is relatively straightforward to implement
(Fig. 10). A mixture of surfactant, oil, and water (SOW) is initially
heated up to a temperature around or slightly above the PIT, which
leads to the formation of a microemulsion or liquid crystalline
phase. The SOW system is then quench cooled to a temperature
well below the PIT with continuous stirring, which leads to the
spontaneous formation of an oil-in-water emulsion or nano-
emulsion (Anton & Vandamme, 2009). An example of the phase
behavior of a SOW mixture consisting of a non-ionic surfactant (13%
Tween 80), a flavor oil (10 wt% lemon oil), and water (77%) upon
heating and cooling is shown in Fig. 14 (Rao & McClements, 2010).
Initially, the surfactant, oil and water were blended together to
form a coarse O/W emulsion that was optically opaque. Upon
heating the system becomes transparent when the PIT is reached,
and then becomes opaque when heated above the PIT due to for-
mation of a W/O emulsion. Upon cooling, the system goes from
turbid to transparent indicating that a nanoemulsion was formed
Fig. 14. Change in turbidity when a coarse lemon oil emulsion (10% lemon oil, 13%
(d ¼ 45 nm). Tween 80, 77% water) is heated and cooled. A very fine transparent nanoemulsion is
One of the limitations of the phase inversion temperature formed when the system is heated, and then cooled below its phase inversion tem-
method is that the emulsions produced are often highly prone to perature. (Rao & McClements, 2010).
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41 23

from the droplet surfaces, thereby altering the optimum curvature

and PIT of the surfactant monolayer, as well as increasing the
repulsive interactions between the droplets. This approach could
be used in the food and beverage industry to form very fine droplets
using the PIT method, and then stabilizing them by diluting them in
a different surfactant solution.
The PIT method can only be used for certain combinations of oils
and surfactants. The PIT must be within a practical range that can
be implemented within the food industry (e.g. somewhere between
40 and 90  C) e if it is too high then it will not be possible to create
emulsions, and if it is too low the emulsions formed will be highly
unstable to droplet growth. The PIT tends to increase with
increasing molecular weight and hydrophobicity of oil molecules,
which means that for many triacylglycerol oils the PIT is too high to
practically reach. On the other hand, flavor oils seem to be
amenable to emulsification using the PIT method. Nevertheless, it is
still important to select an appropriate type and amount of sur-
factant to ensure the PIT is in the correct range.

6.2.2.2. Emulsion inversion point (EIP) method. The emulsion

inversion point (EIP) method can also be implemented very easily
(Fig. 10). It simply involves titrating increasing amounts of an
aqueous phase into an organic phase to induce a catastrophic phase
inversion from a W/O to an O/W system. Initially, an organic phase
is prepared that contains oil and a hydrophilic surfactant. The
aqueous phase is then slowly titrated into this organic phase with
constant stirring. As the amount of water added increases the
system converts from a W/O emulsion, to an O/W/O multiple
emulsion, to an O/W emulsion (Jahanzad, Crombie, Innes, & Sajjadi,
2009; Sajjadi, 2006). The formation of these multiple emulsions
requires that the hydrophilic surfactant is initially located in the oil
phase. At relatively low surfactant concentrations the formation of
multiple emulsions is suppressed and only relatively large oil
droplets are produced in the final emulsion, which are similar in
size to those that would be produced if the surfactant had been
dissolved in the water phase prior to homogenization (Jahanzad
et al., 2009). At relatively high surfactant concentrations, multiple
emulsions are formed during the titration process, and the final oil
droplet size within the O/W emulsions is determined by the size of
the inner oil droplets in the intermediate O/W/O emulsions. The
value of the critical concentration where phase inversion occurs, as
well as the size of the oil droplets produced, depends on process
variables, such as the stirring speed, the rate of water addition, and
the emulsifier concentration (Thakur et al., 2008). The emulsifiers
used in catastrophic phase inversion are usually limited to small
molecule surfactants that can stabilize both W/O emulsions (at
least over the short term) and O/W emulsions (over the long term).
We have recently used the EIP method to produce emulsions
with relatively small droplet diameters (<100 nm) (Ostertag, Weiss,
& McClements, 2012). We titrated water into an organic phase
containing a mixture of oil and water-miscible surfactant. The
droplet size produced by this method depended on: (i) oil type:
medium chain triglycerides (MCT) < flavor oils (orange and
limonene) < long chain triglycerides (olive, grape, sesame, peanut
and canola oils); (ii) surfactant type: Tween 80 < Tween
20 < Tween 85; (iii) surfactant concentration: smaller droplets
were produced at higher surfactant-to-oil ratios (SOR); (iv) sur-
factant location: surfactant initially in oil < surfactant initially in
water. As an example, the data for the influence of oil type on
droplet size produced using the EIP method is shown in Fig. 15. The
EIP method was also compared to a high energy method (micro-
fluidization). Small droplets (d < 160 nm) could be produced by
both methods, but that much less surfactant was needed for the
high energy method (SOR  0.1) than the low energy method
(SOR  0.7). The EIP method may therefore be suitable for
Fig. 15. Influence of oil type on mean droplet diameter in emulsions produced using
the emulsion inversion point (EIP) method by titrating water into an oil-surfactant
mixture (Ostertag, Weiss and McClements, 2012).
producing fine emulsions suitable for use in the beverage industry
without the need for expensive homogenization equipment, pro-
vided that having relatively high amounts of surfactant present is
not a problem. In the finished product, the levels of surfactant may
be quite small (even when SOR z 1), since the beverage emulsion
concentrates are diluted so much.
7. Beverage emulsion ingredients
7.1. Oil phase components
7.1.1. Flavor oils
Flavor oils, such as orange, lemon and peppermint oils, are widely
used in the food and beverage industries as flavoring agents, since
they contain volatile constituents with characteristic aroma profiles.
The composition of natural flavor oils depends on their biological
origin, the extraction procedure used to isolate them, and any sub-
sequent processing steps. For example, lemon oil is usually obtained
from lemon peel by cold pressing, and it may then be further refined
using steam distillation and various other methods (Misharina,
Terenina, Krikunova, & Medvedeva, 2010). Commercially, flavor oils
are available in various forms (“folds”) that differ in chemical
composition due to differences in isolation and processing procedures
used. Flavor oils extracted by cold pressing are usually referred to as
single-fold (1  ) oils, while those that have undergone further pro-
cessing (such as distillation) are referred to as higher fold oils e.g.,
three-fold (3  ), five-fold (5  ), or ten-fold (10  ) oils (Gamarra,
Sakanaka, Tambourgi, & Cabral, 2006). Normally, higher-fold oils
have different and more intense flavor profiles than lower-fold oils.
Differences in the chemical composition of flavor oils also leads to
differences in their physicochemical properties (e.g., water solubility,
density, viscosity, refractive index, and optical properties), which in-
fluences their ability to form and stabilize beverage emulsions (Rao &
McClements, 2012a, 2012c). In recent studies, our laboratory has
examined the influence of lemon oil fold (1 , 3 , 5 and 10) on the
formation and properties of oil-in-water microemulsions, nano-
emulsions and emulsions (Rao & McClements, 2012b, 2012c). The
composition, molecular characteristics, and physicochemical
24 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
properties of the four lemon oils were tabulated. The main constitu-
ents in 1 lemon oil were monoterpenes (>90%), whereas the major
constituents in 10 lemon oil were monoterpenes (z35%), sesqui-
terpenes (z14%) and oxygenates (z33%). The concentration of both
polar and non-polar components increased with increasing oil fold,
while intermediate polar components decreased. The density, inter-
facial tension, viscosity, and refractive index of the lemon oils
increased as the oil fold increased (i.e., 1 <3 <5 <10 ). The
stability of oil-in-water emulsions produced by high pressure ho-
mogenization was strongly influenced by lemon oil type. Emulsions
produced using lower fold oils (1, 3, 5) were highly unstable to
droplet growth during storage, with the growth rate increasing with
increasing storage temperature and decreasing oil fold. Droplet
growth was mainly attributed to Ostwald ripening i.e., the diffusion of
water-soluble lemon oil components from small to large droplets.
Emulsions prepared using the highest fold oil (10) were stable to
droplet growth, which was attributed to the presence of an appre-
ciable fraction of low water-solubility constituents that acted as
“ripening inhibitors” (see later). On the other hand, the lower fold oils
were more suitable for forming microemulsions than the higher fold
oils, presumably because they contained constituents that more easily
fit into micelle structures.
A number of recent studies have examined the major factors
influencing the formation and stability of beverage emulsions
containing flavor oils, including the preparation method used
(Qian & McClements, 2011; Rao & McClements, 2011, 2012c),
emulsifier type (Mirhosseini, Tan, Aghlara, et al., 2008; Mirhosseini,
Tan, Hamid, & Yusof, 2008; Qian & McClements, 2011), droplet
charge (Choi et al., 2010a), addition of antioxidants (Yang et al.,
2011), presence of surfactant micelles (Choi et al., 2010b), and the
physical state of the oil phase (Mei et al., 2010). Many flavor oils
used in beverage emulsions are unstable to chemical degradation
during storage. For example, citral decomposes rapidly during
storage at acidic pH by a series of cyclization and oxidation re-
actions (Choi et al., 2009). This effect is highlighted in Fig. 16, which
shows the amount of citral remaining in aqueous solution during
storage at different pH values: the degradation rate increases
rapidly as the pH is decreased. Citral degradation reduces the level
of desirable aroma compounds present as well as increasing the
levels of undesirable aroma compounds, thus limiting the shelf life
of many beverages. The rate of citral degradation in emulsions is
affected by environmental and compositional factors, such as
Fig. 16. Influence of pH and storage time on the chemical degradation of 0.05% citral
dispersed in citrate buffer solutions (Choi et al., 2009). The citral chemically degrades
rapidly at acidic pH values.
temperature, oxygen availability, and antioxidant addition (Choi
et al., 2009; Liang, Wang, Simon, & Ho, 2004a, 2004b; Ueno,
Kiyohapa, Ho, & Masuda, 2006; Ueno et al., 2003). It also depends
on the location of the citral molecules within an emulsion, e.g., oil,
water, or interfacial regions (Choi et al., 2009; Choi et al., 2010b). If a
labile component is located within an environment where it is
isolated from other components that promote its chemical degra-
dation, then it is possible to reduce the degradation rate. Since citral
degradation occurs predominantly in acidic aqueous solutions, it is
possible to reduce its degradation rate by altering its partitioning
between the oil and aqueous phases. For example, when citral is
located predominantly within a non-polar environment, such as
the interior of a lipid droplet or surfactant micelle, it is partially
protected from degradation. This effect is highlighted in Fig. 17,
which shows that the rate of citral degradation in oil-in-water
emulsions decreases as the total fat droplet concentration in-
creases. This effect can be attributed to the fact that a lower fraction
of the citral is present within the acidic aqueous phase as the fat
content increases due to equilibrium partitioning effects (Fig. 18).
This phenomenon may be important for beverage emulsion con-
centrates that have relatively high fat contents, since in this case an
appreciable fraction of the citral will be present within the oil
phase. Choosing an oil type and concentration that ensures that
most of the citral is present within the oil droplets, rather than the
aqueous phase, will then help to inhibit citral degradation during
storage. On the other hand, once an emulsion concentrate is diluted
to form the finished product nearly all of the flavor molecules
partition into the aqueous phase and therefore any protective effect
is lost.
7.1.2. Cloud oils
The oil droplets in cloud emulsions are composed mainly of
non-flavor oils, such as triacylglycerol or terpene oils. Tri-
acylglycerol oils are typically derived from natural sources such as
vegetable, corn, canola and sunflower oils, whereas terpene oils are
usually isolated by distillation of natural flavor oils. These oils have
very low water-solubilities and are therefore stable to Ostwald
ripening (unlike flavor oils). The main purpose of cloud oils is to
produce droplets that scatter light strongly so as to give a product a
0.04
Citral Degradation Rate (/day)
0.03
0.02
0.01
0
1 2 5 10 20
Fat Content (%)
Fig. 17. Influence of oil droplet concentration on the chemical degradation of citral
dispersed within MCT oil-in-water emulsions (Choi et al., 2009). The citral chemically
degrades more rapidly in an aqueous than an oil environment, and therefore the less
oil present the faster the degradation rate.
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
Fig. 18. Influence of oil droplet concentration on the partitioning of citral within MCT
oil-in-water emulsions (Choi et al., 2009). The mass fraction of citral in the aqueous
phase decreases as the oil concentration increases.
desirable turbid or cloudy appearance, and so it is important that
the droplets are within the size range where efficient light scat-
tering occurs (typically around 200e500 nm). For commercial ap-
plications, it is also important that the droplets remain physically
and chemically stable during storage, transport, and handling.
Cloud oils do not usually contribute directly to the flavor profile of
beverage emulsions, but they may indirectly influence flavor due to
their effects on the partitioning of flavor molecules between the oil,
water, and headspace regions (McClements, 2005). They may also
adversely affect the flavor profile of a beverage if they are suscep-
tible to chemical degradation, e.g., the oxidation of unsaturated
lipids products rancid off-flavors.
The physicochemical properties of cloud oils may also play an
important role in the formation and stability of cloud emulsions.
The viscosity of cloud oils will influence their ability to form small
droplets during the homogenization process, with higher viscos-
ities normally leading to larger droplets. The density of cloud oils
determines the creaming velocity of the droplets within an emul-
sion, and may therefore influence their long-term stability. The
melting characteristics of cloud oils may also be important for
certain applications since partially crystalline oil droplets are sus-
ceptible to partial coalescence leading to droplet aggregation and
phase separation (McClements, 2005). This may be particularly
important for beverages that are stored in a refrigerator for pro-
longed periods. In this case, it may be necessary to use an oil phase
that remains liquid at refrigerator temperatures (e.g., winterized or
fractionated oil).
7.1.3. Nutraceutical lipids
There has been growing interest in the incorporation of various
kinds of nutraceutical lipids into commercial food and beverage
products, such as polyunsaturated fats, conjugated linoleic acid,
carotenoids, phytosterols, and fat-soluble vitamins. These nutra-
ceutical lipids are either mixed with the other oil phase compo-
nents prior to homogenization or they are encapsulated separately
and then introduced intro the product. The incorporation of nu-
traceutical lipids into commercial beverage emulsions is often
challenging because they are prone to various physical or chemical
degradation mechanisms. Each type of nutraceutical lipid has its
own particular challenges depends on its physicochemical prop-
erties, such as solubility, oil-water partition coefficient, melting
25
point, and chemical stability (McClements, Decker, Park, & Weiss,
2009). Beverage products must therefore be carefully formulated
taking into account the potential problems associated with the
specific types of nutraceutical lipids present.
7.1.3.1. Polyunsaturated lipids. There has been growing interest in
the incorporation of polyunsaturated fatty acids (PUFAs), and
especially omega-3 (u-3) fatty acids, into food and beverage
products because of their potential health benefits (Ruxton, Reed,
Simpson, & Millington, 2004, 2007; Siddiqui et al., 2004). Omega-
3 fatty acids are unsaturated fatty acids that have a double bond
that is three carbon atoms from the methyl end of the molecule.
The most common u-3 fatty acids in food oils are a-linolenic acid
(ALA, 18:3), eicosapentaenoic acid (EPA, 20:5) and docosahexaenoic
acid (DHA, 22:6), with EPA and DHA being the most bioactive.
PUFAs are normally incorporated into foods as part of tri-
acylglycerol molecules, but they may also be incorporated as
monoacylglycerols, diacylglycerols, or phospholipids. Consumption
of adequate amounts of u-3 fatty acids has been linked to decreased
risks of various diseases, including cardiovascular disease, immune
response disorders, mental disorders, and poor infant development
(Orchard, Pan, Cheek, Ing, & Jackson, 2012; Tur, Bibiloni, Sureda, &
Pons, 2012). This has prompted food manufacturers to attempt to
fortify their products with u-3 fatty acids at levels sufficiently high
to have a beneficial biological effect (McClements & Decker, 2000;
Waraho et al., 2011). However, PUFAs are extremely susceptible to
oxidative deterioration, which causes problems for the long-term
storage of these products (Arab-Tehrany et al., 2012).
The oxidation of u-3 fatty acids in emulsions involves a complex
series of chemical reactions that results in the production of rancid
off-flavors. The control of lipid oxidation often requires a combi-
nation of different approaches to achieve adequate long-term sta-
bility, including control of initial ingredient quality, removal/
deactivation of pro-oxidants (such as oxygen or transition metals),
addition of anti-oxidants, and interfacial engineering (McClements
& Decker, 2000; Waraho et al., 2011). A more detailed discussion of
the chemical stability of PUFA was given in an earlier section.
7.1.3.2. Fat soluble antioxidants. Lipophilic antioxidants can be
incorporated into the oil phase of oil-in-water emulsions to inhibit
the oxidation of encapsulated chemically labile substances (such as
u-3 oils or carotenoids), thereby extending product shelf life (Boon,
McClements, Weiss, & Decker, 2010; McClements & Decker, 2000;
Waraho et al., 2011). Alternatively, they can be encapsulated as
functional food components themselves so as to make an “antiox-
idant” claim on a product label. Some commonly used lipophilic
antioxidants utilized within the food industry include alpha-
tocopherols, ascorbyl palmitate, BHT, BHA, and rosemary extracts
(McClements & Decker, 2008). These five molecules act as free
radical scavengers and they each have the ability to absorb two free
radicals before becoming inactive. The addition of these antioxi-
dants typically increases the lag phase of the oxidation reaction.
7.1.3.3. Fat soluble vitamins. There is considerable interest in
incorporating various types of fat-soluble vitamins (A, D, E, and K)
and nutraceuticals (e.g., carotenoids, phytosterols, flavonoids, and
curcumin) into food and beverage products to improve their
nutritional value (Sagalowicz & Leser, 2010; Velikov & Pelan, 2008).
In this section, we use recent studies on the incorporation of
vitamin E into emulsions to demonstrate some of the potential
benefits and challenges associated with its use in beverages. The
term “vitamin E” actually refers to a group of fat-soluble vitamins
that are widely used as functional ingredients in food, pharma-
ceutical, and cosmetic preparations, with a-tocopherol being the
most biologically active form (Chiu & Yang, 1992). The major
26 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
biological function of Vitamin E appears to be as an oil-soluble
antioxidant, although other health benefits have been claimed,
including reducing cardiovascular disease, diabetes, and cancer
(Sylvester et al., 2011; Traber, Frei, & Beckman, 2008; Weng-Yew &
Brown, 2011). For these reasons, there has been interest in forti-
fying many foods and beverages with Vitamin E (Sagalowicz &
Leser, 2010). Vitamin E is unstable to oxidation and may therefore
be lost during processing, storage, and utilization of commercial
products (Gawrysiak-Witulska, Siger, & Nogala-Kalucka, 2009;
Yoon & Choe, 2009). For this reason, vitamin E acetate (rather than
vitamin E) is used in many food and beverage applications since it
has a higher oxidative stability. After consumption vitamin E ace-
tate is broken down to vitamin E in the gastrointestinal tract by the
action of pancreatic esterases (Brisson et al., 2008). The recom-
mended daily intake (RDI) of Vitamin E is 15 mg/day (Gonnet,
Lethuaut, & Boury, 2010; Institute of Medicine, 2000).
Vitamin E is a highly lipophilic molecule that cannot be directly
dispersed into aqueous solutions (Sagalowicz & Leser, 2010).
Instead, it must be incorporated into an appropriate colloidal de-
livery system prior to dispersion (Gonnet et al., 2010). A number of
previous studies have shown that vitamin E can be successfully
incorporated into emulsion-based delivery systems, such as
microemulsions (Chiu & Yang, 1992; Feng, Wang, Zhang, Wang, &
Liu, 2009), nanoemulsions (Hatanaka et al., 2010; Li et al., 2011;
Shukat, Bourgaux, & Relkin, 2012) and emulsions (Chen &
Wagner, 2004; Gonnet et al., 2010). Encapsulation of vitamin E
has been reported to improve its physicochemical stability during
storage and its biological activity after consumption (Cortesi,
Esposito, Luca, & Nastruzzi, 2002; Zuccari, Carosio, Fini, Montaldo,
& Orienti, 2005). Indeed, studies have suggested that the oral
bioavailability of Vitamin E is increased when it is delivered in
colloidal form rather than in bulk form (Feng et al., 2009), which
would make beverages particularly suitable delivery systems for
this type of nutraceutical lipid.
7.1.3.4. Carotenoids. Carotenoids are a diverse group of lipophilic
compounds that contribute to the yellow, orange and red colors of
many foods, and that have also been claimed to have some health
benefits. They are polyenes consisting of 3e13 conjugated double
bonds and in some cases 6 carbon ring structures at one or both
ends of the molecule. Carotenoids containing oxygen are known as
xanthophylls (e.g. lutein and zeaxanthin) while those without ox-
ygen are known as carotenes (e.g., lycopene and b-carotene). The
carotenoids have been proposed to exhibit several potential health
benefits: lutein and zeaxanthin may decrease age related macular
degeneration and cataracts (Stringham & Hammond, 2005); lyco-
pene may decrease the risk of prostate cancer (Basu & Imrhan,
2007). Carotenoids are relatively stable to chemical degradation
when they are present in their natural environment. However, they
become highly unstable to degradation once they are isolated,
becoming susceptible to light, oxygen, pH, and temperature
(Xianquan, Shi, Kakuda, & Yueming, 2005). Consequently, disper-
sion of carotenoids into ingredient systems can result in their rapid
degradation (Heinonen, Haila, Lampi, & Piironen, 1997; Ribeiro, Ax,
& Schubert, 2003). Carotenoids can be degraded by reactions that
cause the loss of double bonds or scission of the molecule. In
addition, the double bonds in carotenoids can undergo isomeriza-
tion to the cis configuration (Xianquan et al., 2005). Isomerization
reactions might actually be beneficial since cis isomers of carot-
enoids such as lycopene are thought to be more bioavailable and
bioactive (Schieber & Carle, 2005). An additional challenge to using
carotenoids as ingredients in functional foods is their high melting
point, making them crystalline at food storage and body tempera-
tures. A more detailed discussion of the factors governing the
chemical degradation of carotenoids was given earlier.
7.1.3.5. Phytosterols. Phytosterols and phytostanols are a group of
bioactive lipids derived from plants that have been shown to be
have biological activity (Chaiyasit, Elias, McClements, & Decker,
2007). The fortification of foods and beverages with these com-
ponents has become popular due to their ability to decrease total
and low density lipoprotein cholesterol in humans, which is mainly
attributed to their ability to inhibit the absorption of dietary
cholesterol (Ostlund, 2004; Wong, 2001). Intake of 1.6 g phytos-
terols/day results in an approximately 10% reduction in LDL
cholesterol (Hallikainen, Sarkkinen, & Uusitupa, 2000). The intes-
tinal absorption of phytosterols is very low and so dietary phytos-
terols do not have adverse effects on health.
Incorporation of phytosterols and phytostanols into aqueous-
based beverages is particularly difficult due to their low-water
solubility, low-oil solubility, high melting point, and tendency to
form crystals. Some of these problems have been overcome by
esterification of phytosterols with polyunsaturated fatty acids. After
consumption, the phytosterol esters are hydrolyzed by enzymes in
the gastrointestinal tract to produce free fatty acids and phytos-
terols. The initial applications of phytosterols were in high fat foods
(e.g. margarine and spreads) where solublization and dispersion
within the oil phase were relatively simple. For phytosterols to be
introduced into aqueous-based foods, they need to be either sus-
pended or emulsified. Phytosterols are also susceptible to chemical
degradation (oxidation) during storage (Bortolomeazzi, Cordaro,
Pizzale, & Conte, 2003; Cercaci, Rodriguez-Estrada, Lercker, &
Decker, 2007; Dutta, 1997; Lambelet et al., 2003; Soupas, Juntunen,
Lampi, & Piironen, 2004). At present, it is unclear whether oxidized
forms of phytosterols lose their bioactivity or have some toxicity as
has been observed for oxidized cholesterol. Phytosterols and phy-
tostanols must therefore be encapsulated in delivery systems that
will maintain their physical and chemical stability in beverage
emulsions.
7.1.4. Fat soluble colorants
A number of natural fat-soluble compounds have intense colors
and can therefore be used as pigments in foods, including paprika,
lycopene, and b-carotene (Gibbs, Kermasha, Alli, & Mulligan, 1999;
Kandansamy & Somasundaram, 2012; Wrolstad & Culver, 2012).
Some of these components also have biological activity, and may
therefore be used as nutraceutical lipids also. Many colorants from
natural sources are highly unstable and may chemically degrade
and fade rapidly during storage, e.g., the carotenoids discussed
earlier (Qian et al., 2012). It is therefore important to establish the
mechanism of chemical degradation for each type of fat soluble
colorant used in a beverage product and to determine the major
factors affecting its degradation (such as pH, light, oxygen, pro-
oxidants) so that an effective delivery system can be designed to
ensure appropriate product shelf-life.
7.2. Emulsifiers
7.2.1. Mechanism of action
Emulsifiers are surface-active molecules that are used in emul-
sions to facilitate droplet breakup within the homogenizer (thereby
forming smaller droplets) and to prevent droplet growth after for-
mation (thereby increasing long-term stability) (McClements, 2005;
Stauffer, 1999). During homogenization, emulsifiers absorb to the oil-
water interface, which leads to a reduction in the interfacial tension
thereby facilitating further droplet disruption. Once they have
adsorbed to the droplet surface the emulsifiers should prevent the
droplets from coalescing with each other, which means they must
for a protective coating around the oil droplets. An effective emul-
sifier system should meet a number of criteria to prevent droplet
coalescence within the homogenizer (Jafari et al., 2008): (1) the
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
emulsifier molecules must be present at a sufficiently high concen-
tration to cover all of the oil-water surface formed: (2) the emulsifier
molecules must form a coating around the droplet surfaces faster
than the droplets collide with each other; and, (3) the adsorbed
emulsifier molecules must form a coating that prevents the droplets
from coming into close proximity and merging together
(McClements, 2005). There are a number of food-grade emulsifiers
that fulfill these requirements, but they differ considerably in their
effectiveness at forming and stabilizing beverage emulsions.
7.2.2. Factors influencing selection
Emulsion formation: Two of the most important factors to
consider when selecting an appropriate emulsifier for forming a
beverage emulsion is its ability to produce small droplets during
homogenization, and the minimum amount of emulsifier required
to form a stable system (McClements, 2005). The performance of an
emulsifier can be characterized by plotting the mean droplet
diameter versus emulsifier concentration under standardized ho-
mogenization conditions, such as homogenizer type, energy input,
and duration (McClements, 2007). A typical dependence of mean
droplet diameter on emulsifier concentration for oil-in-water
emulsions produced using a high pressure homogenizer is shown
in Fig. 19. These curves can be divided into two regions: an
emulsifier-limited region and a homogenizer-limited region.
In the emulsifier-limited region the droplet size decreases with
increasing emulsifier concentration and the size of the droplets is
primarily limited by the total amount of emulsifier present (rather
than by homogenization conditions). The minimum size of the
stable droplets that can be produced in this region is given by
(McClements, 2007):
6$G$f 6$G$f
dmin ¼ ¼ 0
cS cS ð1  fÞ
Here, G is the surface load of the emulsifier at saturation (kg m2), 4
is the disperse phase volume fraction (dimensionless), cS is the
concentration of emulsifier in the emulsion (kg m3), and c0S is the
concentration of emulsifier in the aqueous phase (kg m3). This
equation shows that the droplet size should by linearly related to
the inverse of the surfactant concentration in this region. In this
6 at elevated temperatures (Rao & McClements, 2010), in this case
MS
5 WPI
GA
Mean Droplet Diameter (μm)
4 temperatures (Chanamai & McClements, 2002; Charoen et al., 2011;
3 have to be used at high levels. The stability characteristics of a
2 2005). Globular proteins and ionic surfactants tend to form thin
1 and non-ionic surfactants tend to form thick hydrophilic interfacial
0
0 1 2 3
Emulsifier Concentration (wt%)
Fig. 19. Influence of emulsifier concentration on the mean particle diameter produced
using a microfluidizer using either whey protein isolated (WPI), modified starch (MS)
or gum arabic (GA) are emulsifiers under standardized conditions.
27
region, the homogenizer initially produces small droplets but there
is insufficient emulsifier present to completely cover them all, and
so they tend to coalesce with each other and form larger droplets
under they are covered and protected from coalescence.
In the homogenizer-limited region there is more than enough
emulsifier present to cover all of the droplets formed by the ho-
mogenizer, but the disruptive energy generated by the homoge-
nizer is insufficient to form any smaller droplets. In this region, the
droplet size is therefore limited by the maximum disruptive energy
that the homogenizer can generate, rather than by the emulsifier
concentration. In this region, the droplet size could be reduced
further by increasing the homogenization pressure to that smaller
droplets are produced.
Emulsifiers differ in the abilities to form small droplets and in
the amounts required to form stable emulsions due to differences
in their molecular and physicochemical characteristics. The most
important physical characteristics are: (i) the rate at which they
absorb to the oil-water interface during homogenization; (ii) the
amount that they reduce the interfacial tension after absorption;
and, (iii) the amount required to cover a unit area of interface
(surface load). Typically, the size of the droplets produced under
standardized conditions tends to decrease with increasing ab-
sorption kinetics, decreasing interfacial tension, and decreasing
surface load.
Emulsion stability: The nature of the emulsifier used to form a
beverage emulsion has a pronounced influence on its physical and
chemical stability, and so beverage manufacturers must carefully
select an emulsifier with appropriate stability characteristics.
When selecting an emulsifier it is important to establish the set of
conditions that it is expected to work under (e.g. pH range, tem-
perature range, ionic composition, solvent composition, and me-
chanical abuse), which is likely to be highly product specific.
(8)
Emulsifiers may vary considerably in their ability to form stable
emulsions under different environmental conditions. For example,
many globular proteins form stable emulsions at low ionic
strengths and pH values far from their isoelectric point, but tend to
flocculate at high ionic strengths or pH values close to their iso-
electric point (McClements, 2004). In addition, they tend to floc-
culate when heated above their thermal denaturation temperature
due to an increase in droplet surface hydrophobicity. Emulsions
stabilized by some types of non-ionic surfactants are also unstable
because the rate of droplet coalescence increases when the sur-
factant approaches its phase inversion temperature (PIT). Emul-
sions stabilized by amphiphilic polysaccharides, such as gum arabic
and modified starch, tend to be have good stability to droplet ag-
gregation across a wide range of pH values, ionic strengths, and
Qian, Decker, Xiao, & McClements, 2011). However, these emulsi-
fiers are often not very efficient at producing small droplets, or they
particular emulsifier are largely determined by its influence on the
colloidal interactions operating between oil droplets (McClements,
interfacial layers that mainly stabilize droplets against aggregation
through electrostatic repulsion. On the other hand, polysaccharides
layers that mainly stabilize droplets through steric repulsion.
Emulsions stabilized by electrostatic interactions are particularly
susceptible to environmental changes that alter the magnitude or
range of the electrical charge, e.g., pH and ionic strength. An
example of differences in the electrical characteristics and aggre-
gation stability of emulsions stabilized by a protein (whey protein
isolate) and two polysaccharides (gum Arabic and modified starch)
are shown in Fig. 20. The protein-coated droplets tend to aggregate
28
30
Mean Droplet Diameter (μm)
3
0.3
3 4
Fig. 20. Influence of pH on the particle size and charge produced using a microfluidizer using either whey protein isolated (WPI), modified starch (MS) or gum arabic (GA).
near their isoelectric point due to their low net charge, whereas
polysaccharide-coated droplets are stable across the whole pH
range due to their thick adsorbed layers.
Legal and labeling requirements: Traditionally, many of the
emulsifiers used in food and beverage applications were synthetic
small-molecule surfactants due to their low cost and high efficiency
(Kralova & Sjoblom, 2009). However, there has been increasing
interest within the food and beverage industry in replacing syn-
thetic ingredients with natural alternatives so as to create product
labels that are more consumer-friendly. Natural ingredients often
have a higher price than synthetic ingredients, and poorer func-
tional performances. The change from artificial to natural food
components can also increase manufacturing costs and reduce
product shelf-life. In the following sections, we provide a brief
overview of some of the synthetic and natural emulsifiers that are
currently available for use in beverage emulsions.
7.2.3. Ingredient examples
In principle, many different kinds of emulsifiers can be used to
stabilize the oil-in-water emulsions used in the beverage industry.
In practice, the vast majority of commercial beverage emulsions are
made with a limited number of emulsifiers, mainly gum arabic and
modified starch. In this section, we provide an overview of both
currently used and potential emulsifiers that can be utilized in
beverage products, and classify them according to the nature of the
molecules involved (i.e., polysaccharides, proteins, or surfactants).
7.2.3.1. Polysaccharide-based emulsifiers. Gum arabic: Currently,
gum arabic (also known as gum acacia) is probably the most widely
used emulsifier in the beverage industry to formulate cloud and
flavor emulsions (Given, 2009; Tan, 2004). Gum arabic is a natural
exudate harvested from acacia trees in sub-Saharan Africa, espe-
cially Sudan (Buffo, Reineccius, & Oehlert, 2002). Exudates from
Acacia seyal and senegal have both been approved for use in food,
but the beverage industry generally acknowledges Acacia senegal as
the “gold standard” (Reiner, Reineccius, & Peppard, 2010). A. senegal
consists of at least three high molecular weight biopolymer frac-
tions. It has been proposed that the surface-active fraction consists
of branched arabinogalactan blocks attached to a polypeptide
backbone (Dickinson, 2003; Jayme, Dunstan, & Gee, 1999; Phillips &
Williams, 2000). The hydrophobic polypeptide chain is believed to
anchor the molecules to the droplet surface, while the hydrophilic
carbohydrate blocks extend into the surrounding aqueous phase.
The interfacial layer formed by gum arabic is believed to provide
stability against droplet aggregation mainly through steric repul-
sion, but with some contribution from electrostatic repulsion also.
D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
MS 40 MS
WPI WPI
20 GA
ζ-Potential (mV)
GA
0
-20
-40
-60
5 6 7 8 3 4 5 6 7 8
pH pH
The influence of a variety of processing conditions on gum arabic
functionality has been examined (Buffo & Reineccius, 2001; Buffo,
Reineccius, & Oehlert, 2001; Buffo et al., 2002; Chanamai &
McClements, 2002). For example, it has been shown that gum
arabic-coated oil droplets remain stable to flocculation when
exposed to a wide range of environmental conditions, e.g., pH (3e
9), ionic strength (0e500 mM NaCl; 0e25 mM CaCl2) and thermal
treatment (30e90  C) (Chanamai & McClements, 2002; Charoen
et al., 2011). Nevertheless, gum arabic has a relatively low affinity
for oil-water interfaces compared to most other surface-active
biopolymers, which means that it has to be used at relatively
high concentrations to form stable emulsions. For example, as
much as 20% gum arabic may be required to produce a stable 12 wt
% oil-in-water emulsion (Tse & Reineccius, 1995). For this reason, its
application as an emulsifier is restricted to products that have
relatively low droplet concentrations, e.g., beverage emulsions. In
addition, frequent problems have been reported in obtaining reli-
able sources of consistently high quality gum arabic, which has led
many food scientists to investigate alternative sources of
biopolymer emulsifiers for use in beverages, such as modified
starch and various proteins (Chanamai & McClements, 2002;
Charoen et al., 2011; Garti, 1999; Kim, Morr, & Schenz, 1996; Qian
et al., 2011; Tan, 1998; Trubiano, 1995a). Gum arabic has a high
water-solubility and a relatively low solution viscosity compared to
other gums, which facilitates its application as an emulsifier.
Modified starch: Natural (unmodified) starches have poor sur-
face activity due to their hydrophilic glucose backbones. Never-
theless, starches can be chemically modified to make them effective
emulsifiers by attaching non-polar chains along their backbones
(Trubiano, 1995b). These types of modified starch are widely used
as emulsifiers in the beverage industry. One of the most commonly
used modified starches is an octenyl succinate derivative of waxy-
maize (Stauffer, 1999; Trubiano, 1995b). It consists primarily of
amylopectin that has been chemically modified to contain a side-
group that is anionic and non-polar. These side-groups anchor
the molecule to the oil droplet surface, while the hydrophilic starch
chains protrude into the aqueous phase and protect droplets
against aggregation through steric repulsion. Because the dominant
stabilizing mechanism is steric repulsion, emulsions stabilized by
modified starch are resistant to changes in pH (3e9), ionic strength
(0e100 mM NaCl; 0e25 mM CaCl2) and temperature (30e90  C)
(Chanamai & McClements, 2002; Charoen et al., 2011; Qian et al.,
2011). Like gum arabic, modified starch has a relatively low inter-
facial activity (compared to proteins or surfactants), and so a large
excess must be added to ensure that all the droplet surfaces are
adequately coated. For example, it is had been recommended that a
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
1:1 mass ratio of modified starch to oil was required to produce a
stable oil-in-water emulsion (Tse & Reineccius, 1995). Nevertheless,
there have recently been technical advances in the manufacture of
modified starches that have led to emulsifiers that can be used at
much lower levels (1:5 mass ratio) to form stable emulsions with
small droplet sizes (Charoen et al., 2011; Qian et al., 2011). Studies
have shown that if the concentration of non-adsorbed modified
starch in the aqueous phase surrounding the oil droplets is too high,
it may promote depletion flocculation (Chanamai & McClements,
2001). Modified starches usually come in powdered or granular
forms that are easily dispersible in cold water.
Other polysaccharides: A number of other surface-active poly-
saccharides have been studied for their potential use as emulsifiers
in oil-in-water emulsions. Although these polysaccharides are not
widely used in the beverage industry at present they may find some
applications in the future. There has been debate about the mo-
lecular origin of the surface activity of these polysaccharides, and
about whether their ability to stabilize emulsions is primarily due
to their surface activity or their ability to thicken the aqueous phase
(Dickinson, 2003).
Cellulose is not a good emulsifier in its natural state because it
forms strong intermolecular hydrogen bonds, which make it
insoluble in water. Nevertheless, cellulose can be physically,
chemically, or enzymatically modified to produce food-grade in-
gredients that have interfacial activity and can be used as emulsi-
fiers (Garti et al., 1993), such as methyl cellulose (MC),
hydroxypropyl cellulose (HPC), and methyl hydroxypropyl cellulose
(MHPC). These ingredients are all non-ionic polymers that are
soluble in cold water, but tend to become insoluble when the so-
lution is heated above a critical temperature (around 50e90  C).
They have good stability to pH (2e11), salt and freeze-thaw cycling,
which may be beneficial in a number of beverage emulsion
applications.
Certain types of pectin have been shown to be surface active
molecules that can able to stabilize oil-in-water emulsions, e.g.,
beet pectin (Jung & Wicker, 2012; Nakauma et al., 2008). The origin
of this effect is believed to be due to the pectin having some protein
molecules associated with it. The amphiphilic protein portion an-
chors the pectin molecules to the oil phase, while the hydrophilic
polysaccharide chains protrude into the aqueous phase thereby
providing some steric repulsion. In addition, pectin molecules
usually have a relatively high negative charge because of the
presence of carboxylic groups (pKa ¼ 3.5), and therefore they can
also generate an electrostatic repulsion (Nakauma et al., 2008).
Soy soluble polysaccharide (SSPS) is a soluble, acidic poly-
saccharide extracted from okara that has a molecular structure that
closely resembles pectin (Nakamura, Takahashi, Yoshida, Maeda, &
Corredig, 2004; Nakamura, Yoshida, Maeda, Furuta, & Corredig,
2004). Similar to gum Arabic and beet pectin, SSPS is believed to
have a protein backbone that anchors the molecule to the oil phase
and hydrophilic anionic polysaccharide chains that protrude into
the aqueous phase and provide stabilization through steric and
electrostatic repulsion (Nakauma et al., 2008).
Corn fiber gum (CFG) is a by-product of the milling of corn
(Yadav, Johnston, Hotchkiss, & Hicks, 2007). Preliminary studies
have shown that CFG can facilitate the formation and stability of
oil-in-water emulsions (Yadav et al., 2007). The surface activity of
this polysaccharide may also be due to the presence of small
amounts of protein or lipids that are associated with it.
Research is continuing in this area, and it is likely that a variety
of other polysaccharide-based emulsifiers will be identified that
may be suitable for stabilization of beverage emulsions.
7.2.3.2. Protein-based emulsifiers. Proteins are widely used in the
food industry to stabilize various commercial food and beverage
29
products, but they are not commonly used to stabilize soft drinks.
Surface-active proteins can be isolated from various sources,
including milk, meat, fish, and plants, but the most widely used in
the food industry are those derived from bovine milk: casein and
whey proteins. The interfacial coatings formed by proteins are
usually relatively thin and electrically charged, and hence the major
mechanism preventing droplet flocculation in protein-stabilized
emulsions is electrostatic repulsion (rather than steric repulsion).
Consequently, protein-stabilized emulsions are particularly sensi-
tive to pH and ionic strength effects (Figs. 20 and 21), and will tend
to flocculate at pH values close to their isoelectric points or when
the ionic strength exceeds a certain level (Demetriades et al., 1997a,
1997b; Dickinson, 2010; McClements, 2004).
Proteins can typically be used at much lower levels that
amphiphilic polysaccharides to stabilize oil-in-water emulsions.
For example, as much as 20% gum arabic may be required to pro-
duce a stable 12.5 wt% oil-in-water emulsion, whereas less than 1%
whey protein can be used (Chanamai & McClements, 2002; Tse &
Reineccius, 1995). On the other hand, globular protein stabilized
emulsions are much more susceptible to pH, ionic strength, and
thermal processing than polysaccharide stabilized emulsions as
shown in Fig. 20 (Chanamai & McClements, 2002). The stability of
protein-stabilized emulsions to pH, salts, and thermal processing
can often be improved by mixing them with ionic polysaccharides
either before or after homogenization, such as gum arabic, pectin,
alginate, and carrageenan (Guzey & McClements, 2006, 2007;
Harnsilawat, Pongsawatmanit, & McClements, 2006; Klein et al.,
2010). These ionic polysaccharides form an interfacial complex
with the adsorbed protein molecules, which increases the steric
and electrostatic repulsion between the droplets (Dickinson, 2011).
A number of other methods have also been developed to
improve the emulsifying properties of protein ingredients,
including limited hydrolysis to form peptides, modification of
protein structure by chemical, physical, enzymatic or genetic
means, and blending of the proteins with other ingredients,
although not all of these methods are legally permitted at present.
Globular proteins: Native globular proteins tend to have fairly
compact spheroid structures with the non-polar amino acids con-
tained within their hydrophobic interiors (away from water) and
the polar amino acids located at the exterior (in contact with wa-
ter). There are many sources of globular proteins in foods that are
1.2
MS
WPI
GA
Mean Droplet Diameter (μm)
1
0.8
0.6
0.4
0 100 200 300 400 500
NaCl (mM)
Fig. 21. Influence of ionic strength on the particle size and charge produced using a
microfluidizer using either whey protein isolated (WPI), modified starch (MS) or gum
arabic (GA).
30 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
surface-active and capable of forming and stabilizing emulsions,
such as those from whey, soy, egg, pea, and various other plants
(McClements, 2005). Globular proteins tend to form relatively thin
interfacial coatings around fat droplets, and therefore primarily
stabilize emulsions against flocculation through electrostatic
repulsion (McClements, 2004). They are therefore particularly
sensitive to droplet flocculation at pH values near the isoelectric
point (where the droplet charge is low) or at high salt concentra-
tions (where the droplet charge is screened). Emulsions stabilized
by globular proteins are also particularly sensitive to heat treat-
ments, because these proteins unfold when the temperature ex-
ceeds the thermal denaturation temperature thereby exposing
reactive non-polar and sulfhydryl groups (Kim, Decker, &
McClements, 2002). These reactive groups increase the attractive
interactions between droplets, which may lead to droplet floccu-
lation through increased hydrophobic attraction and disulfide bond
formation.
The most common source of globular proteins in the food in-
dustry is the whey protein derived from bovine milk. A number of
different whey protein ingredients are available for use in the food
industry as emulsifiers, including whey protein concentrate (WPC),
whey protein isolate (WPI), and highly purified protein fractions
such as b-lactoglobulin and a-lactalbumin. These ingredients nor-
mally come as white powders that are dissolved in water prior to
utilization. WPC and WPI are commonly used as emulsifiers in
commercial food and beverage products, whereas b-lactoglobulin
and a-lactalbumin are more frequently used in fundamental
studies of protein functionality in research laboratories. Whey
protein actually contains a mixture of globular proteins: z55% b-
lactoglobulin; z24% a-lactalbumin; z15% immunoglobulins; and
z5% serum albumin (McClements, 2005). The isoelectric point of
the major whey proteins is around pH 5, and therefore droplets
stabilized by whey proteins tend to flocculate around this pH, and
especially between about pH 4 to 6 (Fig. 20). The thermal dena-
turation temperature of whey proteins is around 70e80  C, and so
they are prone to droplet aggregation when heated above this
temperature, especially in the presence of salts that screen elec-
trostatic interactions (Kim et al., 2002).
Flexible proteins: Another group of protein-based emulsifiers
commonly used in foods can be classified as flexible proteins
(Dickinson, 1992a). These molecules tend to have a more flexible
random coil type structure (although they often retain some sec-
ondary structure). The main sources of flexible proteins are gelatin
from fish and animals, and caseins from bovine milk. Gelatin is a
relatively high molecular weight protein derived from fish, porcine,
or bovine collagen (McClements, 2005). It is typically prepared by
disrupting the native structure of collagen by boiling it in the
presence of either acid (Type A gelatin) or base (Type B gelatin). The
isoelectric point of Type A gelatin (w7e9) tends be higher than that
of Type B gelatin (w5). Gelatin exists as a random coil molecule at
relatively high temperatures, but undergoes a coil-to-helix transi-
tion upon cooling below a critical temperature, which is about 10e
25  C for animal gelatin and about 0e5  C for fish gelatin. Gelatin
has been shown to be surface-active and capable of acting as an
emulsifier in oil-in-water emulsions. Nevertheless, it often pro-
duces relatively large droplet sizes when used in isolation, and
therefore it may be utilized with other ingredients to improve its
effectiveness at forming and stabilizing emulsions.
There are various casein-based emulsifiers that can be pur-
chased commercially with different compositions and functional
properties, such as sodium caseinate, calcium caseinate, and puri-
fied protein fractions, such as a b-casein. There are four main pro-
tein fractions in casein: aS1 (w44%), aS2 (w11%), b (w32%) and k
(w11%). Casein-coated droplets have been shown to be unstable to
droplet flocculation at pH values (3.5e5.3) close to the protein’s
isoelectric point. Caseinate-stabilized emulsions tend to be more
stable to heating than whey protein-stabilized emulsions, pre-
sumably because the relatively flexible casein molecules do not
undergo appreciable heat-induced conformational changes like
globular proteins do.
7.2.3.3. Small-molecule surfactants. In general, small-molecule
surfactants consist of a polar head-group and a non-polar tail
group (Kralova & Sjoblom, 2009; McClements, 2005; Stauffer,
1999). The head group may be non-ionic, anionic or cationic,
while the tail group may vary in the number, length, and degree of
unsaturation of the chains. Many surfactants can be used to fabri-
cate beverage emulsions using either low or high energy ap-
proaches, which is different from amphiphilic biopolymers that can
only be used to fabricate them using high energy methods. In
addition, many surfactants are able to form smaller oil droplets
than amphiphilic biopolymers using high energy methods because
they can adsorb more quickly to the oil-water interfaces during
homogenization and lower the interfacial tension more. Surfactants
are also able to stabilize emulsions at lower concentrations than
amphiphilic biopolymers. Despite these advantages, the food in-
dustry has been trying to replace synthetic small molecule sur-
factants with emulsifiers that are natural and more label friendly
due to consumer demands. Recently, some natural small molecule
surfactants have become commercially available, such as quillaja
saponin. A summary of some small-molecule surfactants that could
be utilized in beverage emulsions is given in Table 4.
Tweens: Tweens (also sold under the name polysorbates) are
synthetic non-ionic surfactants that consist of a non-polar fatty acid
group esterified to a polar polyoxyethylene sorbitan group. The
nature of the fatty acid and polyoxyethylene chains determines the
nomenclature and functional properties of the surfactant. Tween
20 (monolaurate), Tween 40 (monopalmitate), Tween 60 (mono-
stearate), and Tween 80 (monooleate) are hydrophilic molecules
with relatively high HLB values (14.9 and 16). They are therefore
predominantly water-soluble, form micelles in aqueous solutions,
and stabilize oil-in-water emulsions. Since Tweens are nonionic
they tend to produce droplets that are stable to aggregation over a
wide range of pH and ionic strength values. However, Tween-
coated droplets may become unstable to coalescence at elevated
temperatures close to the phase inversion temperature.
Sugar esters: Sugar esters are synthetic nonionic surfactants that
consist of a polar sugar esterified to a fatty acid chain. There has
been growing interest in the utilization of sugar esters as emulsi-
fiers within the food and beverage industry (Szuts, Budai-Szucs,
Eros, Otomo, & Szabó-Révész, 2010), which can be attributed
to their desirable sensory attributes, low toxicity, and high
Table 4
HLB numbers of selected small molecule surfactants and co-surfactants that could
be used to produce beverage emulsions. Information from various sources:
McClements (2005), National Starch, and Rahn-Group.com.
Surfactant HLB value
Sucrose monopalmitate 16
Sucrose monostearate 15
Sucrose distearate 6
Sucrose polystearate 2
Tween 20 (Polyoxyethylene Sorbitan Monolaurate) 16
Tween 40 (Polyoxyethylene Sorbitan Monopalmitate) 15.6
Tween 60 (Polyoxyethylene Sorbitan Monostearate) 14.9
Tween 80 (Polyoxyethylene Sorbitan Monoooleate) 15
Q-Naturale (Quillaja saponin) >9
Span 20 (Sorbitan monolaurate) 8.6
Span 40 (Sorbitane monopalmitate) 6.7
Span 60 (Sorbitan monostearate) 4.7
Span 80 (Sorbitan monooleate) 4.3
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
biodegradability (Sadtler, Guely, Marchal, & Choplin, 2004). In
addition, sugar esters are produced from natural products, such as
sucrose and vegetable oil, and are therefore often perceived as
being more label-friendly than petrochemical-based surfactants
(Huck-Iriart, Candal, & Herrera, 2009). Sucrose fatty acid esters are
non-ionic surfactants that have a sucrose moiety as a hydrophilic
head group and one or more fatty acids as lipophilic tail groups.
Sucrose monoesters have a single fatty acid attached to the sucrose
molecule, which means they are relatively hydrophilic, water-
soluble, have high HLB numbers, and can stabilize O/W emulsions
(Garti, Clement, Leser, Aserin, & Fanun, 1999; Glatter et al., 2001). A
number of researchers have previously examined the structure,
properties, and functionality of sucrose monoesters (Fanun, 2010;
Garti, Aserin, & Fanun, 2000; Garti, Clement, Fanun, & Leser,
2000; Garti et al., 1999). These studies have shown that sucrose
monoesters can form a range of different colloidal structures
depending on system composition and temperature, e.g., micro-
emulsions, nanoemulsions or emulsions. Emulsions formed using
sucrose monopalmitate (SMP) as the only emulsifier are highly
unstable to aggregation when stored at acidic pH values (pH 3.5),
which has been attributed to a reduction of droplet charge (Rao &
McClements, 2011). However, emulsions that are stable across a
wide range of pH can be produced by mixing SMP with a co-
surfactant (such as lecithin) that increases the electrostatic repul-
sion between droplets at low pH (Choi et al., 2011).
Quillaja saponin: Quillaja saponin is a natural surfactant
extracted from the bark of the Quillaja saponaria Molina tree. It has
been found to contain surface active components that are capable
of forming surfactant micelles and stabilizing oil-in-water emul-
sions (Mitra & Dungan, 1997; Waller & Yamasaki, 1996a, 1996b;
Yang, Leser, Sher, & McClements, 2013; Yang & McClements,
2013). The major components within this extract have been re-
ported to be saponins (van Setten, ten Hove, Wiertz, Kamerling, &
van de Werken, 1998; van Setten, van de Werken, Zomer, &
Kersten, 1995), which are high molecular weight glycosides con-
sisting of a sugar moiety attached to a triterpene or a steroid
aglycone (Hostettmann & Marston, 1995). The saponins are surface
active substances because they contain both hydrophilic regions
(such as rhamnose, xylose, arabinose, galactose, fucose, and glu-
curonic acid) and hydrophobic regions (such as quillaic acid and
gypsogenic acid) on the same molecule (Mitra & Dungan, 1997;
Sidhu & Oakenfull, 1986). Recent experiments have shown that it
can be used to form emulsions containing small droplets that are
stable to changes in pH, ionic strength, and temperature (Yang &
McClements, 2013; Yang et al., 2013).
A food ingredient based on the quillaja saponin extract has
recently been produced by the National Starch Company (Bridge-
water, NJ) under the trade name Q-NaturaleÒ. This ingredient was
released in 2008 and has been marketed as a replacement for gum
acacia in beverage emulsions. According to the suppliers, Q-Natu-
raleÒ can be used at a low level, has high oil loading, and is stable in
some forms of alcoholic beverages, unlike most forms of gum acacia
or modified food starch. It is also organic certified and is stable in
products stored at ambient or cold temperatures for up to a year.
The ingredient also comes in a liquid form, so that dissolution and
hydration steps are unnecessary.
Aside from its use as a beverage emulsion emulsifier, quillaja
extract has also been used as a foam-stabilizing agent in beverages.
The extract is added to the aqueous phase of a beverage to stabilize
foam that forms at the neck of the beverage. This foam is consid-
ered a positive attribute in root beer and some citrus juices in
various parts of the world.
7.2.3.4. Mixed emulsifier systems. There has been increasing inter-
est in using mixed emulsifier systems with the aim of producing
31
more label-friendly food ingredients. Proteins tend to be better at
producing small emulsion droplets when used at low concentra-
tions than polysaccharides, whereas polysaccharides tend to be
better at producing emulsions that are more stable to environ-
mental conditions than proteins, e.g., pH, ionic strength, tempera-
ture, freeze-thaw cycling (McClements 2004). The beneficial
attributes of these two kinds of biopolymer can be combined to
produce small emulsion droplets with good environmental stabil-
ity. A number of researchers have shown that protein-
polysaccharide complexes may have better emulsifying properties
than either of the biopolymers used in isolation (Dickinson, 2003,
2011; Guzey & McClements, 2006). These complexes may be held
together either by physical or covalent interactions, and may be
formed either before or after homogenization (McClements 2004).
Ingredients based on protein-polysaccharide interactions will have
to be legally acceptable, economically viable and show benefits
over existing ingredients before they find widespread utilization in
the food industry. It should be noted that gum arabic is actually a
naturally occurring protein-polysaccharide complex that is already
widely used in the food industry as an emulsifier.
As mentioned earlier, sucrose monoesters produce emulsions
that are not very stable under acidic conditions when they are used
in isolation, but their stability can be greatly improved by
combining them with co-surfactants, such as lysolecithin.
7.3. Weighting agents
7.3.1. Mechanism of action
Weighting agents are additives incorporated into the oil phase
of certain types of beverage emulsions to inhibit gravitational
separation of the oil droplets (McClements, 2005). As discussed
earlier, the creaming rate of a droplet within an emulsion is given
by Stokes’ law (McClements, 2005). This equation predicts that the
rate of creaming is proportional to the droplet radius squared (r2),
the density contrast between the two phases (Dr), and the recip-
rocal of the aqueous phase viscosity (h0) (Equation (3)). If Dr is
positive the particles move downwards (sediment), but if Dr is
negative they move upwards (creaming). The stability of a beverage
emulsion to gravitational separation can therefore be improved by
ensuring that the density of the oil droplets is similar to that of the
surrounding aqueous phase. The densities of some of the major
components found in beverage emulsions are listed in Table 3. The
densities of flavor oils and vegetable oils are considerably lower
than those of water and aqueous sugar solutions. Consequently,
droplets containing these oils tend to move upward during storage
leading to “ringing”, i.e., the formation of a visible ring of fat
droplets at the surface of the product. The creaming rate can be
reduced by decreasing the density contrast between the oil drop-
lets and the surrounding aqueous phase (Equation (3)). The most
common means of increasing the density of the oil phase so that it
matches that of the aqueous phase is to add weighting agents,
which are hydrophobic components that have a density that is
considerably greater than water (Table 3).
7.3.2. Factors influencing selection
A number of different weighting agents are available for utili-
zation within commercial beverage products, such as brominated
vegetable oil (BVO), SAIB (Sucrose acetate isobutyrate), ester gum,
or dammar gum (Table 3). There are a number of different factors
that will determine which of these different components is suitable
for application within a specific beverage product.
Physicochemical factors: The bulk physicochemical properties of
commercial weighting agents vary considerably, which alters their
ease of use and functional properties. The amount of a weighting
agent that is required to match the density of the oil and aqueous
32 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
phases depends on its density: the higher the density, the smaller
the amount needed. Weighting agents also vary in their rheological
and solubility properties, which will influence the preparation of
the oil phase and the formation of stable emulsions by homoge-
nization. Many beverage emulsions are sweetened by adding
sugars to the aqueous phase. Sugars increase the aqueous phase
density and would therefore be expected to increase the density
contrast between the oil and aqueous phases, which should
accelerate creaming. However, sugars also increase the viscosity of
the continuous phase. These two effects largely cancel each other
out, so that the creaming rate in sugar solutions is not much greater
than in pure water (Chanamai & McClements, 2000).
As mentioned previously, the overall density of an emulsion
droplet actually depends on the density and volume of the oil phase
and the interfacial layer. The interfacial layer is usually made up of
emulsifiers (such as surfactants, phospholipids, proteins, or poly-
saccharides) that have a higher density than both the oil and the
water phases. When the thickness of the interfacial layer is appre-
ciable compared to the dimensions of the oil core, then the overall
density of the emulsion droplet (oil core þ interfacial layer) may
become similar to that of the aqueous phase, and so the adsorbed
emulsifier acts as a weighting agent itself (McClements, 2011).
Legal and labeling factors: There are legal limits on the amount of
each type of weighting agent that can be used in beverages, which
must be adhered to when formulating a project. These legal limits
vary from country to country and therefore a manufacturer must be
aware of the appropriate legislation in each country the product
will be marketed in. There are also differences in the “label-
friendliness” of different weighting agents. Dammar and ester gum
can be considered to be natural ingredients, whereas BVO and SAIB
are synthetic ingredients.
BVO and ester gum are the two most commonly used weighting
agents in beverage emulsions. However, many countries have
restricted the amount of weighting agents that can be found in the
final product. For example, the United States restricts BVO and ester
gum’s use to 15 and 100 ppm per serving, respectively. This low
concentration of allowable weighting agents restricts the type of
products that BVO and ester gum can be used in. Beverage emul-
sions are one of the few products where these weighting agents can
be used to reduce the creaming rate, because the oil phase content
is so low (<0.1%). It is also possible to blend two or more types of
weighting agents together to achieve density matching but remain
below their individual restriction levels.
7.3.3. Ingredient examples
7.3.3.1. Brominated vegetable oil. Brominated vegetable oil (BVO) is
made when bromine is added to the double bonds of the tri-
acylglycerol molecules in corn, soybean, cotton seed, or olive oil. It
typically has a density between 1240 and 1330 kg m3, and a
permitted usage level of 15 ppm per serving in the United States.
Nevertheless, there has recently been consumer concern about the
presence of BVO in soft drinks, which has led some major beverage
manufacturers to replace it with more natural alternatives. In 2013,
a leading beverage manufacturer removed BVO from a major
product line after receiving consumer complaints and petitions
against its use. Even though BVO is permitted for use in the United
States, it has been banned from use in beverages in the European
Union and Asia.
7.3.3.2. Ester gum. Ester gum is a hydrophobic polymer made
when glycerol is esterified to gum rosin harvested from trees (such
as pine trees). It is normally supplied as a crystalline solid that can
be incorporated into the oil phase. Ester gum may not be consid-
ered to be a natural food ingredient due to the esterification step
used in its preparation. Nevertheless, it is derived from natural
components (gum rosin) and non-animal glycerol, and the name
“ester gum” may appear to be more label friendly to consumers
than BVO or SAIB. Ester gum has a density of around 1080 kg m3
and a permitted usage level of 100 ppm per serving in the United
States (FDA, USA). It performs similarly to BVO but a greater con-
centration of ester gum has to be added to the oil phase in order to
raise the density (Chanamai & McClements, 2000). Aside from its
traditional use as a weighting agent, recent studies have shown that
ester gum also retards droplet growth in model flavor emulsions
through Ostwald ripening, i.e., it acts like a ripening inhibitor (Lim
et al., 2011). This behavior would probably be demonstrated by all
weighting agents because they are highly hydrophobic materials
with low water-solubilities.
7.3.3.3. Sucrose acetate isobutyrate. Sucrose acetate isobutyrate
(SAIB) is a synthetic weighting agent produced by the esterification
of sucrose with acetic and isobutyric anhydrides. SAIB is usually
supplied in the form of a high viscosity transparent liquid that can
be mixed with the oil phase prior to homogenization. It has a
molecular weight of z845 g mol1, a refractive index of z1.454,
and a density of z1146 kg m3. SAIB also has good stability to
chemical degradation due to lipid oxidation. The level of SAIB in
beverages is currently restricted to 300 ppm per serving in the
United States (FDA, USA).
7.3.3.4. Dammar gum. Dammar gum is a natural weighting agent
that is isolated from an exudate of Caesalpinaceae and Dipter-
ocarpaceae shrubs. Of the four weighting agents mentioned in this
review, dammar gum has the lowest density at 1060 kg m3
(Table 3). Dammar gum is approved for use in several countries, but
it is not currently approved for use in the USA and it so does not
have GRAS status.
7.4. Ripening inhibitors
As discussed previously, a major form of physical instability in
many beverage emulsions is Ostwald ripening, which is the process
whereby the mean droplet size grows during storage due to
diffusion of oil molecules from small droplets to large droplets
(Kabalnov, 2001; Kabalnov & Shchukin, 1992). Once steady state
conditions have been achieved, the increase in mean droplet
diameter over time can be described by Equation (6) given earlier
(Kabalnov & Shchukin, 1992). This equation predicts that the Ost-
wald ripening rate increases as the solubility of the oil phase in the
aqueous phase increases. Many flavor oils have a relatively high
water-solubility and are therefore particularly prone to droplet
growth through this mechanism (Rao & McClements, 2012b). On
the other hand, triacylglycerol oils (such as corn, sunflower, or
canola oils) contain large non-polar triacylglycerol molecules with
relatively low water-solubilities, and therefore cloud emulsions
prepared from these types of oil are not prone to Ostwald ripening
(Coupland, Weiss, Lovy, & McClements, 1996).
An effective means of inhibiting or preventing Ostwald ripening
in an emulsion is to add a hydrophobic component with a very low
water-solubility to the oil phase prior to homogenization
(Kabalnov, Pertzov, & Shchukin, 1987). This hydrophobic compound
is referred to as a “ripening inhibitor” due to its ability to slow
droplet growth through this mechanism (Lim et al., 2011;
McClements et al., 2012). The ability of low water-solubility com-
pounds to retard Ostwald ripening in emulsions can be attributed
to an entropy of mixing effect (Kabalnov et al., 1987), which is
discussed in more detail in Section 5.1.3.
Recent studies have shown that Ostwald ripening may be
inhibited in flavor oil emulsions by adding long chain triglycerides
(such as corn oil) (McClements et al., 2012) or by adding weighting
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
agents (such as ester gum) (Lim et al., 2011). It has also been pro-
posed that some of the water-insoluble components within flavor
oils themselves may act as ripening inhibitors, which may account
for the better stability of high-fold lemon oils (e.g., 10  ) to Ostwald
ripening than low-fold lemon oils (e.g., 1  and 3  ) (Rao &
McClements, 2012c).
7.5. Thickening agents
7.5.1. Mechanism of action
Thickening agents are ingredients that are added to beverage
emulsions to increase the viscosity of the aqueous phase, and
therefore retard droplet creaming and alter product mouthfeel.
Thickening agents are usually hydrophilic biopolymers that
dissolve in the aqueous phase and occupy a volume that is much
larger than the volume of the polymer chain itself (McClements,
2005). The effectiveness of a thickening agent at increasing the
viscosity of an aqueous solution is largely determined by its mo-
lecular characteristics (e.g., molecular weight, conformation, and
interactions). To a first approximation the viscosity of a dilute
aqueous solution containing a hydrophilic biopolymer can be
described by Einstein’s equation:
h ¼ h0 ð1 þ 2:5Rv fÞ (9)
where f is the volume fraction of the biopolymer chain, and Rv is
the volume ratio (Rv ¼ Vsphere/Vpolymer), where Vsphere is the effec-
tive volume that the biopolymer occupies in solution (which in-
cludes the polymer chain and any trapped solvent), and Vpolymer is
the volume occupied by the polymer chain itself. The higher the
value of the volume ratio, the more effective is the polymer at
increasing the viscosity of a solution. Typically, Rv increases as the
molar mass, extension, and self-association of biopolymer mole-
cules increases. Thus, xanthan gum is a particularly effective
thickening agent because it has a high molecular weight and is
highly extended in aqueous solutions and therefore has a large Rv
value. Most thickening agents used in beverages are long-chain
hydrophilic polysaccharides, such as xanthan, locust bean gum,
pectin, or carrageenan. It should be noted that thickening agents
can actually promote emulsion instability under certain conditions,
due to their ability to induce bridging or depletion flocculation.
Bridging flocculation can occur when polymer molecules are
attracted to the surfaces of oil droplets, whereas depletion floccu-
lation occurs when they polymer molecules are dispersed in the
continuous phase and their concentration exceeds a particular
value.
7.5.2. Factors influencing selection
There are a number of factors that must be considered when
selecting a suitable thickening agent for use in beverage emulsions.
It is important to establish the solution and environmental condi-
tions under which the thickening agent must function. This usually
requires knowledge of the physicochemical properties of the
biopolymer molecules involved, such as helixecoil transition
temperatures (for carrageenan, alginate, pectin), electrical proper-
ties (charge groups and pKa values), hydrophobicity, ion sensitivity,
and chemical/enzymatic stability (BeMiller & Whistler, 1997). For
some applications, it is important to establish the electrical char-
acteristics of the biopolymer molecules used (z-potential versus pH
profile), since electrostatic interactions influence ingredient in-
teractions, emulsion stability, and mouthfeel. The electrical charge
on biopolymers depends on the nature of any ionic groups along
the chain background, as well as solution conditions (pH and ionic
composition). Some biopolymers are neutral (e.g., starch, cellulose,
LBG), some are anionic (e.g., alginate, carrageenan, xanthan), some
33
are cationic (e.g., chitosan and polylysine), and some are ampho-
teric (e.g., gelatin). The magnitude of the electrical charge on ionic
biopolymers depends on the pH relative to the pKa value of the
ionic groups. Anionic polysaccharides tend to be neutral at pH
values sufficiently below their pKa value but negative above,
whereas cationic polysaccharides tend to be neutral at pH values
sufficiently above their pKa value but positive below. Proteins are
positive below their isoelectric point, and negative above it
(Fig. 20). The most common charged groups on polysaccharide
thickening agents are sulfate groups (e.g., carrageenan), carboxyl
groups (e.g., pectin, alginate, xanthan, carboxymethylcellulose) and
amino groups (e.g., chitosan): eSO4H 4 eSO4  (pKa z 2); eCO2H
4 eCO2  (pKa z 3.5); eNH3 þ 4 eNH2 (pKa z 6.5). The most
common charged groups on proteins are carboxyl and amino
groups.
The electrical characteristics of thickening agents in aqueous
solutions may also be altered by interactions with other ionic
species in their environment, such as mineral ions, surfactants, and
other biopolymers. Monovalent or multivalent ions such as sodium,
potassium, or calcium may bind to oppositely charged groups on
biopolymer chains, altering their overall charge characteristics. In
addition, knowledge of the type of environmental and solution
conditions present within a particular food is often important for
selecting the most appropriate thickening agent. For example,
pectin can start to depolymerize when exposed to neutral or
alkaline conditions as a result of a base-catalyzed b-elimination
reaction that breaks down its sugar chain. Over time, this break-
down can result in a decline in viscosity and loss of texture (Sila
et al., 2009).
7.5.3. Ingredient examples
There are many different types of thickening agents that can be
used in commercial beverage products. These thickening agents
differ in their chemical compositions, molecular weight distribu-
tions, degrees of branching, conformations, and transition tem-
peratures, which causes variations in their functional
performances. A summary of thickening agents that could be uti-
lized in beverage emulsions is given in Table 5. There are a number
of excellent books that provide detailed information about the
molecular, physicochemical, and functional properties of thick-
ening agents in foods and beverages (Cui, 2005; Imeson, 2010;
Phillips & Williams, 2009).
7.6. Sweeteners
7.6.1. Mechanism of action
Beverage emulsions are sweetened by adding artificial or nat-
ural substances that interact with specific taste receptors on the
tongue to provide the perception of sweetness (Fernstrom et al.,
2012; McCaughey, 2008; Meyers & Brewer, 2008). It has been
proposed that mammals evolved to perceive a pleasant sensation
after ingestion of sugar-rich foods because these foods are a ready
source of energy in nature (e.g., fruits and berries). A wide variety of
substances have molecular structures that can induce a sweet
sensation, although they vary greatly in the concentrations
required to produce sweetness. Sugar molecules have different
sweetness intensities due to differences in their molecular struc-
tures, which alters how they react with the sweetness receptors in
the mouth. Conventionally, the sweetness of substances is
compared to that of sucrose (table sugar) which is taken to have a
Sweetness of 100. The relative sweetness of different types of
sweetener is established using carefully controlled sensory tests.
Fructose is the sweetest of all common sugars because it has just
the right dimensions and bond orientations to strongly interact
with the sweetness receptors in the mouth. However, many natural
34 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41

Table 5
Summary of molecular characteristics of some common food-grade polysaccharides. Adapted from Matalanis, Jones, and McClements (2011).

Name Source Main structure type Major monomer(s) Charge

Alginate Algal Linear Mannuronic & guluronic Acids Negative

Carrageenan Algal Linear/helical Sulfated galactose & Negative
anhydrogalactose
Chitosan Crustaceans, Linear Glucosamine Positive
invertebrates
Gum Arabic Acacia sap Branched coil domains Galactose Negative
on protein scaffold
Locust bean gum Carob seeds Linear Galactose and mannose Neutral
Modified celluloses Wood pulp Linear Glucose and modified Neutral or
Glucoses Negative
Modified starch waxy maize Linear Glucose with some non-polar Negative
branches
Pectin Plant cell walls Highly branched coil Glucuronate (backbone) Negative
Xanthan gum Xanthomonas Linear/Helical (High MW) Glucose (backbone) Negative
campestris exudate

and artificial compounds have much strong sweetness intensities medium-calorie beverages, which may be artificial (such as Cycla-
than sucrose, and therefore can be used at much lower levels, mate, Aspartame, Acesulfame K, Saccharin, Sucrolose, and Neo-
which is the basis of many high-intensity sweeteners used in low- tame) or natural (such as Stevia).
calorie products.
8. Commercial aspects of beverage emulsion formulation
7.6.2. Factors influencing selection
A number of factors must be considered when selecting a
Beverage emulsions are developed internally and externally by
suitable sweetening system for a commercial beverage product.
commercial manufacturers of soft drinks products. External
The sweeteners used must provide a flavor profile that consumers
development is usually contracted to flavor houses that often
find acceptable and desirable. One of the main limitations of
compete with each another for a flavor contract with a beverage
many high-intensity sweeteners is that they do not produce a
manufacturer. This contract can be worth thousands to millions of
flavor profile similar to that normally provided by sugars (Nahon,
dollars depending on the product and length of the contract. Fac-
Roozen, & DeGraaf, 1996), or that they produce undesirable off-
tors considered for selecting the most appropriate flavor delivery
flavors (such as bitterness or metallic) or mouthfeel (such as
system include stability, cost, volume capacity, safety audits,
astringency) (DuBois & Prakash, 2012). In addition, the sweet-
kosher/halal certification, and the ingredient line of the beverage
eners must remain physically and chemically stable within the
emulsion. Because of these various factors, the best-tasting, most
product throughout processing, transport, and storage. Some
stable flavor may not always be chosen as the final flavor used in a
sweeteners may breakdown when exposed to elevated tempera-
commercial application.
tures and are therefore unsuitable for use in beverages that un-
Beverage manufacturers normally supply flavor houses with a
dergo thermal processing. Concern about overweight and obesity
base of the intended product into which the flavor is intended to be
has driven consumer demand for reduced calorie products, which
incorporated. A base consists of all ingredient components except
has led the beverage industry to produce low- and mid-calorie
the flavor. By doing this, the manufacturers do not have to disclose
versions of their conventional high-calorie products. However,
confidential formulations and the flavor houses can develop a fla-
many of the high-intensity sweeteners used to replace sugars
vor specific to the product. Shelf-life studies (accelerated and non-
have undesirable flavor profiles or are perceived as being “un-
accelerated) are performed to determine how well the prototype
natural”, and so the beverage industry is trying to introduce
flavors hold up in the formulation. If chemical or physical in-
natural low-intensity sweeteners with desirable flavor profiles
stabilities are observed, the flavor can be reformulated to increase
(such as Stevia).
its stability. Depending on the project’s timeline this can take as
little as a few days or up to a year. If the product is being rushed to
7.6.3. Ingredient examples
market and only a few days are allotted for formulation, the flavor
There are many different types of sweeteners that can be used in
house can rely on past knowledge of how flavors behave in similar
commercial beverage products, which vary according to their
products. This can enable the fast development of a flavor that will
chemical structure, origins (natural versus artificial), and intensity
have a high-probability of success in a given formulation. If
(low- versus high-intensity). The most commonly used low-
development is done internally, the same steps are followed: pro-
intensity sweeteners are sugars (such as sucrose, glucose, and
totype formulation; shelf-life studies; reformulation (if necessary);
fructose) and sugar alcohols (such as sorbitol, mannitol, xylitol and
and then commercialization.
erythritol). These substances may be added as individual in-
gredients, or they may be part of more complex ingredients, such as
high fructose corn syrup, honey, and sugar cane. The human body 9. Recent developments in beverage emulsions
does not have the appropriate enzymes in its digestive tract to
break down sugar alcohols in the same manner that sugars are There have been a number of recent developments and in-
broken down. Consequently, the body breaks sugar alcohols down novations in the beverage industry over the past few years. In this
more slowly and less efficiently that sugars, which means they have section, we highlight a number of the most important ones. The
less calories per gram (about 50e75%), which may be useful for the compositions and calorie content of a number of common com-
development of reduced calorie products. However, high-intensity mercial beverages is summarized in Table 6, whereas some of the
sweeteners are more commonly used to produce low-calorie or claims that can be made on beverages in given in Table 7.
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41 35

Table 6
Examples of the composition and calorie content of some commercial beverage products currently on the market.

Product Brand Manufacturer Beverage Sweetener Calories Emulsifier Weighting Natural

type system (per 8 oz. ready to drink) agent claim

Half and Half Iced Arnold Palmer AriZona RTD HFCS, Sucralose, 50 GA None No
Tea Lemonade Ace-K Listed
Half and Half Iced Arnold Palmer AriZona RTD Sucralose 0 GA None No
Tea Lemonade Zero Listed
Cherry Citrus BodyArmor Body Armor RTD Cane Sugar 70 GA EG Yes
Nutrition
Tropical Mandarin BodyArmor Body Armor RTD Cane Sugar 70 GA EG Yes
Nutrition
Lemon Lime Xion4 Coca-Cola RTD HFCS 80 GA EG No
(Powerade)
Orange Xion4 Coca-Cola RTD HFCS 80 GA EG No
(Powerade)
Strawberry Lemonade Xion4 Coca-Cola RTD HFCS 80 GA EG No
(Powerade)
Sour Melon Xion4 Coca-Cola RTD HFCS 80 M-FS SAIB No
(Powerade)
Orange Soda Fanta Coca-Cola RTD HFCS 120 M-FS EG, BVO No
Original Citrus Fresca Coca-Cola RTD APM, Ace-K 0 GA EG, BVO No
Energy - Tropical Citrus Vitamin Water Coca-Cola RTD Fructose, 120 GA EG No
Cane Sugar
Multi-V - Lemonade Vitamin Water Coca-Cola RTD Fructose, 120 GA EG No
Cane Sugar
Essential OrangeeOrange Vitamin Water Coca-Cola RTD Fructose, 120 GA, M-FS EG No
Cane Sugar,
Sorbitol
Squeezed Lemonade Vitamin Coca-Cola RTD Erythritol, 0 GA EG No
Water Zero Rebiana
Orange Soda Sunkist Dr. Pepper RTD HFCS 110 M-FS EG No
Snapple
Orange Diet Crush Dr. Pepper RTD APM, Ace-K 0 GA EG No
Snapple
Citrus Soda Sun Drop Dr. Pepper RTD HFCS 120 GA EG, BVO No
Snapple
Pineapple Orange Guava Nantucket Dr. Pepper RTD Sucrose 120 GA None Yes
Nectar’s Snapple Listed
Orange Mango Nantucket Dr. Pepper RTD Sucrose 120 GA None Yes
Nectar’s Snapple Listed
Strawberry Kiwi Snapple Dr. Pepper RTD Sucrose 100 GA EG Yes
Snapple
Lemonade Farmer’s The Farmer’s RTD Cane Sugar 120 GA EG Yes
Daughter Cow
Strawberry Lemonade Farmer’s The Farmer’s RTD Cane Sugar 110 GA EG Yes
Daughter Cow
Lemonade MiO Kraft Foods LC Sucralose, 0 GA SAIB No
Ace-K
Orange Tangerine MiO Kraft Foods LC Sucralose, 0 GA SAIB No
Ace-K
Sparkling Lemonade N/A Lorina RTD Sucrose 90 GA EG No
Pink Citrus Lemonade N/A Lorina RTD Sucrose 120 GA EG No
Lemonade G2 of Gatorade PepsiCo RTD Sucrose 80 GA EG, SAIB No
G-Series
Lemon-Lime G2 of Gatorade PepsiCo RTD Sucrose 80 GA EG No
G-Series
Orange G2 of Gatorade PepsiCo RTD Sucrose 80 GA EG, BVO No
G-Series
Mtn Dew N/A PepsiCo RTD HFCS 110 GA BVO No
Diet Mtn Dew N/A PepsiCo RTD APM, Ace-K 0 GA BVO No
Lemon Nature’s Blends Poland RTD Cane Sugar 50 GA EG Yes
Spring
Orange Cranberry Tangerine Skinny Water Skinny RTD Sucralose, 0 GA EG No
Nutritional Ace-K
Old-Fashioned Lemonade N/A Zeigler’s RTD Sucrose 100 GA EG No
Beverages

Ace-K: Acesulfame Potassium; APM: Aspartame; BVO: Brominated vegetable oil; EG: Ester gum; GA: Gum acacia; HFCS: High fructose corn syrup; LC: Liquid concentrate;
M-FS: Modified-food starch; RTD: Ready to drink; SAIB: Sucrose acetate isobutyrate.

9.1. “All-natural” products and cleaner ingredient lines
Consumers’ preference for natural products over artificial have
caused manufacturers to claim their products as “Natural” whenever
possible. As attractive as a “Natural” claim is, it comes at a product
functionality and financial cost. In most cases, natural ingredients are
more expensive than synthetic and their functional properties are
often not as robust. The use of synthetic ingredients creates a
cheaper, more stable product, but also one less attractive to many
consumers. A 2007 study by the University of Southampton (UK)
linked synthetic colors and additives to heightened hyperactivity in
children (McCann et al., 2007). This report led to a consumer outcry
36 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41

Table 7
Claims and justifications that can be made on beverage products.

Claim Justification Source

“0 Calories” Less than 5 cal per RACC. 21 CFR 101.60(b)

“All natural” Undefined, but regarded as a product N/A
lacking any synthetic components.
“Artificially flavored” Any substance that imparts flavor that 21 CFR 101.22 (a) (1)
is not derived from its natural source.
“Contains % juice” For juice made from concentrate, calculate 21 CFR 101.30(j), 21 CFR 101.30(h)
use-percentage from the Brix table in 21
CFR 101.30(h)(1) as the basis for 100% juice.
“Excellent source of vitamin” Contains 20% or more of the DV per RACC. 21 CFR 101.54(b)
“Good source of vitamin” Contains 10%e19% of the DV per RACC. 21 CFR 101.54(e)
“Low calorie soda” 40 cal or less per RACC. 21 CFR 101.60(b)
“Low sodium” 140 mg or less per RACC. 21 CFR 101.61
“Natural and artificial flavor” Contains natural and artificial flavors. 21 CFR 101.22 (a) (1), 21 CFR 101.22 (a) (3), 21
CFR (g) 101.22 (3)
“Naturally flavored” The flavor constituents function in the food 21 CFR 101.22 (a) (3)
as flavor, not solely as a source of nutrition
are derived from its natural source in nature.
“No added sugar” No sugar or sugar-containing ingredients are 21 CFR 101.60(c) (2)
added during processing.
“No artificial colors” Contains no colorant source outside the principle 21 CFR 101.22(k)(1) (2), 21 CFR 74
flavor components of beverage. Natural color is
considered artificial color when used for colorant purposes.
“No HFCS” Cannot contain HFCS. 21 CFR 101.65(b)(1), 21 CFR 101.65 (b)(2)
“No preservatives” Cannot contain preservatives. 21 CFR 101.65(b)(1), 21 CFR 101.65 (b)(2)
“No pulp” Cannot contain pulp. 21 CFR 101.65(b)(1), 21 CFR 101.65 (b)(2)
“Reduced sugar” At least 25% less sugars per RACC than an 21 CFR 101.60 (c)
appropriate reference food.

for the removal of synthetic ingredients from food and beverage
products aimed at children, promoting many large companies to
begin removing synthetic additives and colors. One problem with
replacing artificial additives with natural ones is that they are often
much less stable within commercial products. For example, natural
colors may rapidly degrade in the presence of acid, light, and heat.
Consequently, many commercial products have had to be reformu-
lated to include effective strategies to extend their shelf-life, e.g.,
using antioxidants and other preservatives to slow color fading.
The use of synthetic ingredients not only impacts consumer
acceptance, but also limits retail channels a product can compete
within. Certain local and national grocery chains prohibit artificial
sweeteners, preservatives, and flavors in the foods they sell. The
incorporation of brominated vegetable oil (BVO), sucrose-acetate
isobutyrate (SAIB), Tweens (polysorbate) or modified-food starch
into a product can restrict product sales in these marketplaces.
Thus beverage suppliers have to use alternative weighting agents
(such as dammar gum or ester gum) or emulsifiers (such as gum
Arabic) in these products.
The removal of all synthetic components of a product may be
unachievable for functional and financial reasons. However, man-
ufacturers can remove as many synthetic components as possible to
make “No, No, No” claims. For instance, an unnatural product can
still claim “No artificial colors, preservatives, flavors, and sweet-
eners”. A “No, No, No” claim is not as strong as a “Natural” claim, but
it may be seen favorably by consumers. Claims on product pack-
aging are regulated by the US Food and Drug Administration within
the Code of Federal Regulations (CFR), specifically Title 21.
9.2. Low-calorie and mid-calorie soft drinks
Consumer perceptions about the potential link between over-
consumption of sugary drinks and obesity promoted beverage
manufacturers to create a variety of low or zero-calorie products
(Slavin, 2012). These products have been on the market for
numerous years, but many consumers do not like their taste, and so
the beverage industry has responded by developing a number of
mid-calorie soft drinks. These drinks contain blends of caloric (e.g.,
Sucrose or High-Fructose Corn Syrup) and high-potency sweet-
eners (e.g., Acesulfame-Potassium, Aspartame, Rebiana, and
Sucralose) to reduce the total calories in sweetened beverage
products (typically by over a half compared to regular products),
while still maintaining a desirable flavor profile. Historically, these
kinds of products have not sold well in the marketplace (with a
number of products from different companies failing), but there
have been renewed attempts to introduce them again recently in
response to consumer desire for reduced calorie intake.
9.3. Energy drinks
Energy drinks are marketed as products that can enhance
physical or mental activity by providing a rapid source of energy,
nutrients, and stimulants. These drinks may be taken before, dur-
ing, or after some proposed activity. They usually contain a blend of
ingredients, such as water, sugars, minerals, proteins, vitamins and/
or stimulants (such as caffeine) that are proposed to replenish the
bodies’ reserves and enhance performance. Typically, energy drinks
come as a Ready-to-Drink beverage (serving w 8 fluid ounces),
Ready-to-Drink shot (serving w 2 fluid ounces), or Liquid
Concentrate (dilute beverage serving w 8 fluid ounces). All the
major commercial beverage manufacturers have products in this
rapidly growing product category. Emulsion technology may be
used in these products to deliver oil-soluble flavors, clouding
agents, preservatives, or nutrients. Further scientific research is
required to demonstrate the claimed biological activity of many of
these products. Recently, there has been concern about the po-
tential risks to certain individuals associated with consuming the
large amounts of caffeine in some of these products.
9.4. Beverage concentrates
Beverage concentrates are products that are sold in a concen-
trated form that consumers then dilute with water prior to con-
sumption. Concentrates may be in either a fluid or powdered form
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
and contain ingredients such as sugars, flavors, colors, and nutri-
ents that form a drinkable beverage upon dilution. Beverage con-
centrates have been used since the nineteenth century when soda
syrups were diluted by pharmacists prior to consumption by con-
sumers. This process still occurs within automated soda fountains
found in many fast-food restaurants, and within some home soda
beverage makers. More recently, beverages have been developed
that contain high-intensity sweeteners rather than sugars, which
enable higher concentration factors to be attained. One recent
successful product based on this principle involves squirting a small
amount of the concentrate from a plastic bottle into a glass of water
to form a zero-calorie beverage. A number of beverage manufac-
turers have launched products within this category in recent years.
Beverage concentrates have some unique developmental issues
due to the fact that the ingredients are present in a highly
concentrated form. For example, high acid, sweetener, flavor, buffer,
nutraceuticals and/or color concentrations can lead to accelerated
chemical degradation reactions and shorter shelf lives.
9.5. Fortification with vitamins, minerals, and nutraceuticals
As discussed earlier, there is a push to fortify many beverage
products with ingredients that are perceived as giving added health
benefits, such as vitamins, minerals, antioxidants, peptides, pro-
teins, dietary fibers, and u-3 fatty acids. These nutraceutical addi-
tives vary greatly in their molecular, physicochemical, and
biological properties, such as physical state, solubility, charge, po-
larity, interactions, and flavor profiles. For example, carotenoids
and polyunsaturated lipids may oxidize during storage and produce
undesirable flavors or changes in color. Multivalent mineral ions
(such as calcium) may precipitate from solution, promote precipi-
tation of other components (such as proteins), or cause undesirable
mouthfeel. Dietary fibers may increase the viscosity of a product,
promote depletion flocculation, or give a slimy mouthfeel. Conse-
quently, each beverage product must be carefully formulated to
take into account the specific types of nutraceutical components it
contains. This segment of the beverage industry is growing rapidly
with consumer demand for products that are perceived to be more
beneficial to human health and wellness.
9.6. Bottled water
There has been an appreciable increase in the global sales of
bottled waters in recent years, including enhanced, flavored, and
fruit-flavored waters. Enhanced water is fortified with electrolytes,
vitamins and other nutraceuticals, whereas flavored and fruit-
flavored waters are flavored with flavorants and fruit extracts,
respectively. Utilization of conventional emulsions in bottled waters
to deliver oil-soluble flavors and nutraceuticals is limited because of
the increase in turbidity caused by light scattering from the oil
droplets. However, microemulsions and nanoemulsions that contain
very fine droplets that do not scatter light strongly may be used for
this purpose.
9.7. New product innovation
New product innovation drives business growth and enables
manufacturers to meet current consumer needs. Predicting future
trends and having the first product to market can give manufac-
turers a huge advantage against competitors. However, being first
to market is also a risk due to the possibility of a new product being
rejected by consumers. Reasons for rejection may include product
unfamiliarity or a lack of consumer need for the product.
One objective of new product innovation is to develop a product
that is so novel that it can be patented. The federal government
37
then grants the manufacturer a 20-year monopoly on that product
type. A patented product can be the main driver of strong revenue
growth for years, and a manufacturer can gain additional revenue
through lawsuits due to patent infringement. On the other hand,
patent expiration can also drive significant revenue loss once
competitors have open access to the once-patented concept.
New product innovation does not necessarily mean creating the
first prototype of a new product. Studying trends in other parts of
the world and then modifying them to fit the intended marketplace
can also be used to drive innovation. For instance, Acai Berry has
been consumed in Brazil for decades, but it was only in the 2000’s
that it became a desired component of food products in the United
States. Suspending grains in beverage products has been carried out
in South America and Europe for many years, but has only recently
found its way into North America.
Determining a secondary use of manufacturing byproducts can
also generate revenue through the development of functional food
ingredients from material once destined for waste. For example, whey
protein was once a byproduct of cheese production, but is not a widely
used functional ingredient in foods and beverages. Fusing elements
from two different product categories is another way to innovate.
New product development is an integral part of the food in-
dustry and changing out components of a beverage to meet current
demands is a struggle that manufacturers have to consider every
day. Such demands include the removal of ingredients from current
products that consumers perceive as undesirable (such as artificial
dyes or High-Fructose Corn Syrup), the addition of desirable com-
ponents (such as antioxidants, minerals, or nutraceutical lipids), or
the replacement of expensive ingredients with inexpensive
alternatives.
10. Conclusions
In principle, beverage emulsions are one of the simplest forms of
oil-in-water emulsions used within the food industry, consisting of
small oil droplets dispersed within an aqueous medium. Neverthe-
less, there are still many challenges associated with developing suc-
cessful commercial products. Beverage emulsions are prepared from
various ingredients and processing operations that may vary from
run-to-run, which can cause changes in the properties and stability of
finished products. To minimize any undesirable changes in product
quality it is important that beverage manufacturers develop a robust
initial formulation and manufacturing operation, and that they also
ensure that ingredient quality and manufacturing conditions are
standardized and monitored. The beverage industry must also
reformulate products to meet changing market and consumer de-
mands: to increase profits by replacing expensive ingredients with
less expensive ones; to remove ingredients that consumers perceive
as being undesirable, such as sugar, salt, and artificial colors, flavors, or
preservatives; to fortify beverages with ingredients that consumers
perceive as desirable, such as vitamins, minerals, proteins, nutra-
ceuticals, and fibers. A thorough understanding of the science and
technology underlying the formation, properties, and stability of
beverage emulsions facilitates the development of innovative prod-
ucts, and allows any production problems to be solved more rapidly.
This review article has attempted to provide a comprehensive over-
view of the scientific and technological principles underlying
beverage emulsion development.
Acknowledgments
DJM would like to thank Prof. Eric Dickinson for introducing
him to the area of food biopolymers and colloids e it has led to
many years of interesting and stimulating work, for which I am
very grateful. We would also like to thank a number of colleagues
38 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
in industry and academia who have provided valuable comments
and suggestions on the manuscript, including Ratjika Chanamai,
Eric Decker, Yuan Fang, Anil Gaonkar, and Peter Given. We would
also like to acknowledge that this material is partly based upon
work supported by grants from the United States Department of
Agriculture (CREES, NRI Grant and NSF-EPA-USDA Grant) and the
Massachusetts Department of Agricultural Resources.
References
Abismail, B., Canselier, J. P., Wilhelm, A. M., Delmas, H., & Gourdon, C. (1999).
Emulsification by ultrasound: drop size distribution and stability. Ultrasonics
Sonochemistry, 6(1e2), 75e83.
Acosta, E. (2009). Bioavailability of nanoparticles in nutrient and nutraceutical
delivery. Current Opinion in Colloid & Interface Science, 14(1), 3e15.
Anton, N., Benoit, J. P., & Saulnier, P. (2008). Design and production of nanoparticles
formulated from nano-emulsion templates e a review. Journal of Controlled
Release, 128(3), 185e199.
Anton, N., Gayet, P., Benoit, J. P., & Saulnier, P. (2007). Nano-emulsions and nano-
capsules by the PIT method: an investigation on the role of the temperature
cycling on the emulsion phase inversion. International Journal of Pharmaceutics,
344(1e2), 44e52.
Anton, N., & Vandamme, T. F. (2009). The universality of low-energy nano-emul-
sification. International Journal of Pharmaceutics, 377(1e2), 142e147.
Arab-Tehrany, E., Jacquot, M., Gaiani, C., Imran, M., Desobry, S., & Linder, M. (2012).
Beneficial effects and oxidative stability of omega-3 long-chain polyunsaturated
fatty acids. Trends in Food Science & Technology, 25(1), 24e33.
Basu, A., & Imrhan, V. (2007). Tomatoes versus lycopene in oxidative stress and
carcinogenesis: conclusions from clinical trials. European Journal of Clinical
Nutrition, 61(3), 295e303.
BeMiller, J. N., & Whistler, R. L. (1997). Carbohydrates. In O. Fennema (Ed.), Food
Chemistry. New York, NY: Marcel Dekker, Inc.
Benichou, A., Aserin, A., & Garti, N. (2004). Double emulsions stabilized with hy-
brids of natural polymers for entrapment and slow release of active matters.
Advances in Colloid and Interface Science, 108-109, 29e41.
Berli, C. L. A., Deiber, J. A., & Quemada, D. (2005). On the viscosity of concentrated
suspensions of charged colloids. Latin American Applied Research, 35(1), 15e22.
Boon, C. S., McClements, D. J., Weiss, J., & Decker, E. A. (2009). Role of iron and
hydroperoxides in the degradation of lycopene in oil-in-water emulsions.
Journal of Agricultural and Food Chemistry, 57(7), 2993e2998.
Boon, C. S., McClements, D. J., Weiss, J., & Decker, E. A. (2010). Factors influencing the
chemical stability of carotenoids in foods. Critical Reviews in Food Science and
Nutrition, 50(6), 515e532.
Bortolomeazzi, R., Cordaro, F., Pizzale, L., & Conte, L. S. (2003). Presence of
phytosterol oxides in crude vegetable oils and their fate during refining. Journal
of Agricultural and Food Chemistry, 51(8), 2394e2401.
Bouchemal, K., Briancon, S., Perrier, E., & Fessi, H. (2004). Nano-emulsion formu-
lation using spontaneous emulsification: solvent, oil and surfactant optimisa-
tion. International Journal of Pharmaceutics, 280(1e2), 241e251.
Brisson, L., Castan, S., Fontbonne, H., Nicoletti, C., Puigserver, A., & Ajandouz, E. H.
(2008). Alpha-tocopheryl acetate is absorbed and hydrolyzed by Caco-2 cells e
comparative studies with alpha-tocopherol. Chemistry and Physics of Lipids,
154(1), 33e37.
Buffo, R. A., & Reineccius, G. A. (2001). Shelf-life and mechanisms of destabilization
in dilute beverage emulsions. Flavour and Fragrance Journal, 16(1), 7e12.
Buffo, R. A., Reineccius, G. A., & Oehlert, G. W. (2001). Factors affecting the emul-
sifying and rheological properties of gum acacia in beverage emulsions. Food
Hydrocolloids, 15(1), 53e66.
Buffo, R. A., Reineccius, G. A., & Oehlert, G. W. (2002). Influence of time-temperature
treatments on the emulsifying properties of gum acacia in beverage emulsions.
Journal of Food Engineering, 51(4), 341e345.
Cao, Y., Dickinson, E., & Wedlock, D. J. (1990). Creaming and flocculation in emul-
sions containing polysaccharide. Food Hydrocolloids, 4(3), 185e195.
Cercaci, L., Rodriguez-Estrada, M. T., Lercker, G., & Decker, E. A. (2007). Phytosterol
oxidation in oil-in-water emulsions and bulk oil. Food Chemistry, 102(1), 161e167.
Chaiyasit, W., Elias, R. J., McClements, D. J., & Decker, E. A. (2007). Role of physical
structures in bulk oils on lipid oxidation. Critical Reviews in Food Science and
Nutrition, 47, 299e317.
Chanamai, R., Horn, G., & McClements, D. J. (2002). Influence of oil polarity on
droplet growth in oil-in-water emulsions stabilized by a weakly adsorbing
biopolymer or a nonionic surfactant. Journal of Colloid & Interface Science,
247(1), 167e176.
Chanamai, R., & McClements, D. J. (2000). Impact of weighting agents and sucrose
on gravitational separation of beverage emulsions. Journal of Agricultural and
Food Chemistry, 48(11), 5561e5565.
Chanamai, R., & McClements, D. J. (2001). Depletion flocculation of beverage
emulsions by gum arabic and modified starch. Journal of Food Science, 66(3),
457e463.
Chanamai, R., & McClements, D. J. (2002). Comparison of gum arabic, modified
starch, and whey protein isolate as emulsifiers: influence of pH, CaCl2 and
temperature. Journal of Food Science, 67(1), 120e125.
Charoen, R., Jangchud, A., Jangchud, K., Harnsilawat, T., Naivikul, O., &
McClements, D. J. (2011). Influence of biopolymer emulsifier type on formation
and stability of rice bran oil-in-water emulsions: whey protein, gum arabic, and
modified starch. Journal of Food Science, 76(1), E165eE172.
Chen, C. C., & Wagner, G. (2004). Vitamin E nanoparticle for beverage applications.
Chemical Engineering Research & Design, 82(A11), 1432e1437.
Chiu, Y., & Yang, W. (1992). Preparation of vitamin E microemulsion possessing high
resistance to oxidation in air. Colloids and Surfaces, 63(3e4), 311e322.
Cho, Y. H., & McClements, D. J. (2009). Theoretical stability maps for guiding
preparation of emulsions stabilized by protein-polysaccharide interfacial
complexes. Langmuir, 25(12), 6649e6657.
Choi, S. J., Decker, E. A., Henson, L., Popplewell, L. M., & McClements, D. J. (2009).
Stability of citral in oil-in-water emulsions prepared with medium-chain tri-
acylglycerols and triacetin. Journal of Agricultural and Food Chemistry, 57(23),
11349e11353.
Choi, S. J., Decker, E. A., Henson, L., Popplewell, L. M., & McClements, D. J. (2010a).
Influence of droplet charge on the chemical stability of citral in oil-in-water
emulsions. Journal of Food Science, 75(6), C536eC540.
Choi, S. J., Decker, E. A., Henson, L., Popplewell, L. M., & McClements, D. J. (2010b).
Inhibition of citral degradation in model beverage emulsions using micelles and
reverse micelles. Food Chemistry, 122(1), 111e116.
Choi, S. J., Decker, E. A., Henson, L., Popplewell, L. M., Xiao, H., & McClements, D. J.
(2011). Formulation and properties of model beverage emulsions stabilized by
sucrose monopalmitate: influence of pH and lyso-lecithin addition. Food
Research International, 44(9), 3006e3012.
Chu, B. S., Ichikawa, S., Kanafusa, S., & Nakajima, M. (2007). Preparation and char-
acterization of beta-carotene nanodispersions prepared by solvent displace-
ment technique. Journal of Agricultural and Food Chemistry, 55(16), 6754e6760.
Clark, B. C., Powell, C. C., & Radford, T. (1977). Acid-catalyzed cyclization of citral.
Tetrahedron, 33(17), 2187e2191.
Cortesi, R., Esposito, E., Luca, G., & Nastruzzi, C. (2002). Production of lipospheres as
carriers for bioactive compounds. Biomaterials, 23(11), 2283e2294.
Coupland, J. N., Weiss, J., Lovy, A., & McClements, D. J. (1996). Solubilization kinetics
of triacyl glycerol and hydrocarbon emulsion droplets in a micellar solution.
Journal of Food Science, 61(6), 1114e1117.
Cui, S. W. (2005). Food carbohydrates: Chemistry, physical properties and applications.
Boca Raton, FL: Taylor and Francis.
Dalgleish, D. G., West, S. J., & Hallett, F. R. (1997). The characterization of small
emulsion droplets made from milk proteins and triglyceride oil. Colloids and
Surfaces A-Physicochemical and Engineering Aspects, 123, 145e153.
Danviriyakul, S., McClements, D. J., Decker, E., Nawar, W. W., & Chinachoti, P. (2002).
Physical stability of spray-dried milk fat emulsion as affected by emulsifiers and
processing conditions. Journal of Food Science, 67(6), 2183e2189.
Decker, E. A., & McClements, D. J. (2001). Transition metal and hydroperoxide in-
teractions: an important determinant in the oxidative stability of lipid disper-
sions. Inform, 12, 215e255.
Demetriades, K., Coupland, J. N., & McClements, D. J. (1997a). Physical properties of
whey protein stabilized emulsions as related to pH and NaCl. Journal of Food
Science, 62(2), 342e347.
Demetriades, K., Coupland, J. N., & McClements, D. J. (1997b). Physicochemical
properties of whey protein-stabilized emulsions as affected by heating and
ionic strength. Journal of Food Science, 62(3), 462e467.
Dickinson, E. (1992a). Introduction to food colloids. Cambridge, UK: Royal Society of
Chemistry.
Dickinson, E. (1992b). An introduction to food colloids. Oxford: Oxford Science
Publishers.
Dickinson, E. (2003). Hydrocolloids at interfaces and the influence on the properties
of dispersed systems. Food Hydrocolloids, 17(1), 25e39.
Dickinson, E. (2010). Flocculation of protein-stabilized oil-in-water emulsions.
Colloids and Surfaces B-Biointerfaces, 81(1), 130e140.
Dickinson, E. (2011). Mixed biopolymers at interfaces: competitive adsorption and
multilayer structures. Food Hydrocolloids, 25(8), 1966e1983.
Dickinson, E., & Stainsby, G. (1982). Colloids in foods. London: Applied Science.
Djordjevic, D., Cercaci, L., Alamed, J., McClements, D. J., & Decker, E. A. (2007).
Chemical and physical stability of citral and limonene in sodium dodecyl
sulfate-chitosan and gum arabic-stabilized oil-in-water emulsions. Journal of
Agricultural and Food Chemistry, 55(9), 3585e3591.
Djordjevic, D., Cercaci, L., Alamed, J., McClements, D. J., & Decker, E. A. (2008).
Stability of citral in protein- and gum arabic-stabilized oil-in-water emulsions.
Food Chemistry, 106(2), 698e705.
DuBois, G. E., & Prakash, I. (2012). Non-caloric sweeteners, sweetness modulators, and
sweetener enhancers. In M. P. Doyle, & T. R. Klaenhammer (Eds.), Annual Review of
Food Science and Technology (Vol. 3; pp. 353e380). Palo Alto: Annual Reviews.
Dutta, P. C. (1997). Studies on phytosterol oxides .2. Content in some vegetable oils
and in French fries prepared in these oils. Journal of the American Oil Chemists’
Society, 74(6), 659e666.
Fanun, M. (2010). Microemulsions with mixed nonionic surfactants and flavor oil.
Journal of Surfactants and Detergents, 13(3), 321e328.
Feng, J.-L., Wang, Z.-W., Zhang, J., Wang, Z.-N., & Liu, F. (2009). Study on food-grade
vitamin E microemulsions based on nonionic emulsifiers. Colloids and Surfaces
A: Physicochemical and Engineering Aspects, 339(1e3), 1e6.
Fernandez, P., Andre, V., Rieger, J., & Kuhnle, A. (2004). Nano-emulsion formation by
emulsion phase inversion. Colloids and Surfaces A-Physicochemical and Engi-
neering Aspects, 251(1e3), 53e58.
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
Fernstrom, J. D., Munger, S. D., Sclafani, A., de Araujo, I. E., Roberts, A., & Molinary, S.
(2012). Mechanisms for sweetness. Journal of Nutrition, 142(6), 1134Se1141S.
Frankel, E. N., Satué-Gracia, T., Meyer, A. S., & German, J. B. (2002). Oxidative sta-
bility of fish and Algae oils containing long-chain polyunsaturated fatty acids in
bulk and in oil-in-water emulsions. Journal of Agricultural and Food Chemistry,
50(7), 2094e2099.
Freitas, S., Merkle, H. P., & Gander, B. (2005). Microencapsulation by solvent
extraction/evaporation: reviewing the state of the art of microsphere prepa-
ration process technology. Journal of Controlled Release, 102(2), 313e332.
Friberg, S., Larsson, K., & Sjoblom, J. (2004). Food emulsions (4 ed.). New York: Marcel
Dekker.
Gamarra, F. M. C., Sakanaka, L. S., Tambourgi, E. B., & Cabral, F. A. (2006). Influence
on the quality of essential lemon (Citrus aurantifolia) oil by distillation process.
Brazilian Journal of Chemical Engineering, 23(1), 147e151.
Gao, Y. L., & Kispert, L. D. (2003). Reaction of carotenoids and ferric chloride:
equilibria, isomerization, and products. Journal of Physical Chemistry B, 107(22),
5333e5338.
Garti, N. (1999). Hydrocolloids as emulsifying agents for oil-in-water emulsions.
Journal of Dispersion Science and Technology, 20(1e2), 327e355.
Garti, N., Aserin, A., & Fanun, M. (2000). Non-ionic sucrose esters microemulsions
for food applications. Part 1. Water solubilization. Colloids and Surfaces A-
Physicochemical and Engineering Aspects, 164(1), 27e38.
Garti, N., & Bisperink, C. (1998). Double emulsions: progress and applications.
Current Opinion in Colloid & Interface Science, 3(6), 657e667.
Garti, N., Clement, V., Fanun, M., & Leser, M. E. (2000). Some characteristics of sugar
ester nonionic microemulsions in view of possible food applications. Journal of
Agricultural and Food Chemistry, 48(9), 3945e3956.
Garti, N., Clement, V., Leser, M., Aserin, A., & Fanun, M. (1999). Sucrose ester
microemulsions. Journal of Molecular Liquids, 80(2e3), 253e296.
Garti, N., Reichman, D., Hendrickx, H., Dickinson, E., Jackson, L. K., & Bergenstahl, B.
(1993). Hydrocolloids as food emulsifiers and stabilizers. Food Structure, 12(4),
411e426.
Gawrysiak-Witulska, M., Siger, A., & Nogala-Kalucka, M. (2009). Degradation of
tocopherols during near-ambient rapeseed drying. Journal of Food Lipids, 16(4),
524e539.
Genovese, D. B., Lozano, J. E., & Rao, M. A. (2007). The rheology of colloidal and
noncolloidal food dispersions. Journal of Food Science, 72(2), R11eR20.
Gibbs, B. F., Kermasha, S., Alli, I., & Mulligan, C. N. (1999). Encapsulation in the food
industry: a review. International Journal of Food Sciences and Nutrition, 50(3),
213e224.
Given, P. S., Jr. (2009). Encapsulation of flavors in emulsions for beverages. Current
Opinion in Colloid & Interface Science, 14(1), 43e47.
Glatter, O., Orthaber, D., Stradner, A., Scherf, G., Fanun, M., Garti, N., et al. (2001).
Sugar-ester nonionic microemulsion: structural characterization. Journal of
Colloid & Interface Science, 241(1), 215e225.
Gonnet, M., Lethuaut, L., & Boury, F. (2010). New trends in encapsulation of lip-
osoluble vitamins. Journal of Controlled Release, 146(3), 276e290.
van der Graaf, S., Schroen, C. G. P. H., & Boom, R. M. (2005). Preparation of double
emulsions by membrane emulsification e a review. Journal of Membrane Sci-
ence, 251(1e2), 7e15.
Gu, Y. S., Decker, E. A., & McClements, D. J. (2004). Influence of pH and iota-
carrageenan concentration on physicochemical properties and stability of
beta-lactoglobulin-stabilized oil-in-water emulsions. Journal of Agricultural and
Food Chemistry, 52(11), 3626e3632.
Gunning, P. A., Hibberd, D. J., Howe, A. M., & Robins, M. M. (1988). Gravitational
destabilization of emulsions flocculated by non-adsorbed xanthan. Food Hy-
drocolloids, 2(2), 119e129.
Gutierrez, J. M., Gonzalez, C., Maestro, A., Sole, I., Pey, C. M., & Nolla, J. (2008). Nano-
emulsions: new applications and optimization of their preparation. Current
Opinion in Colloid & Interface Science, 13(4), 245e251.
Guzey, D., & McClements, D. J. (2006). Formation, stability and properties of
multilayer emulsions for application in the food industry. Advances in Colloid
and Interface Science, 128, 227e248.
Guzey, D., & McClements, D. J. (2007). Impact of electrostatic interactions on formation
and stability of emulsions containing oil droplets coated by beta-lactoglobulin-
pectin complexes. Journal of Agricultural and Food Chemistry, 55(2), 475e485.
Hallikainen, M. A., Sarkkinen, E. S., & Uusitupa, M. I. J. (2000). Plant stanol eaters
affect serum cholesterol concentrations of hypercholesterolemic men and
women in a dose-dependent manner. Journal of Nutrition, 130(4), 767e776.
Harnsilawat, T., Pongsawatmanit, R., & McClements, D. J. (2006). Stabilization of
model beverage cloud emulsions using protein-polysaccharide electrostatic
complexes formed at the oil-water interface. Journal of Agricultural and Food
Chemistry, 54(15), 5540e5547.
Hatanaka, J., Chikamori, H., Sato, H., Uchida, S., Debari, K., Onoue, S., et al. (2010).
Physicochemical and pharmacological characterization of a-tocopherol-loaded
nano-emulsion system. International Journal of Pharmaceutics, 396(1e2), 188e193.
Heinonen, M., Haila, K., Lampi, A. M., & Piironen, V. (1997). Inhibition of oxidation in
10% oil-in-water emulsions by beta-carotene with alpha- and gamma-tocoph-
erols. Journal of the American Oil Chemists’ Society, 74(9), 1047e1052.
Henry, J. V. L., Fryer, P. J., Frith, W. J., & Norton, I. T. (2010). The influence of phos-
pholipids and food proteins on the size and stability of model sub-micron
emulsions. Food Hydrocolloids, 24(1), 66e71.
Horn, D., & Rieger, J. (2001). Organic nanoparticles in the aqueous phase e theory,
experiment, and use. Angewandte Chemie-International Edition, 40(23), 4331e
4361.
39
Hostettmann, K., & Marston, A. (1995). Saponins (1st ed.). Cambridge, UK: Cam-
bridge University Press.
Huck-Iriart, C., Candal, R., & Herrera, M. (2009). Effects of addition of a palmitic
sucrose ester on low-trans-fat blends crystallization in bulk and in oil-in-water
emulsions. Food Biophysics, 4(3), 158e166.
Hunter, R. J. (1986). Foundations of colloid science (Vol. 1). Oxford: Oxford University
Press.
Imeson, A. (2010). Food stabilizers, thickeners and gelling agents. Chichester, UK: John
Wiley & Sons.
Institute of Medicine. (2000). Dietary reference intakes for vitamin C, vitamin E, se-
lenium, and carotenoids. Washington, D.C.: The National Academies Press.
Israelachvili, J. (2011). Intermolecular and surface forces (3rd ed.). London, UK: Ac-
ademic Press.
Jafari, S. M., Assadpoor, E., He, Y. H., & Bhandari, B. (2008). Re-coalescence of
emulsion droplets during high-energy emulsification. Food Hydrocolloids, 22(7),
1191e1202.
Jafari, S. M., He, Y. H., & Bhandari, B. (2006). Nano-emulsion production by soni-
cation and microfluidization e a comparison. International Journal of Food
Properties, 9(3), 475e485.
Jahanzad, F., Crombie, G., Innes, R., & Sajjadi, S. (2009). Catastrophic phase inversion
via formation of multiple emulsions: a prerequisite for formation of fine
emulsions. Chemical Engineering Research & Design, 87(4A), 492e498.
Jayme, M. L., Dunstan, D. E., & Gee, M. L. (1999). Zeta potentials of gum arabic
stabilised oil in water emulsions. Food Hydrocolloids, 13(6), 459e465.
Jung, J. Y., & Wicker, L. (2012). Laccase mediated conjugation of sugar beet pectin
and the effect on emulsion stability. Food Hydrocolloids, 28(1), 168e173.
Kabalnov, A. (2001). Ostwald ripening and related phenomena. Journal of Dispersion
Science and Technology, 22(1), 1e12.
Kabalnov, A. S., Pertzov, A. V., & Shchukin, E. D. (1987). Ostwald ripening in 2-
Component disperse phase systems e application to emulsion stability. Col-
loids and Surfaces, 24(1), 19e32.
Kabalnov, A. S., & Shchukin, E. D. (1992). Ostwald ripening theory e applications to
fluorocarbon emulsion stability. Advances in Colloid and Interface Science, 38,
69e97.
Kabalnov, A., & Wennerstrom, H. (1996). Macroemulsion stability: the oriented
wedge theory revisited. Langmuir, 12(2), 276e292.
Kandansamy, K., & Somasundaram, P. D. (2012). Microencapsulation of colors by
spray drying e a review. International Journal of Food Engineering, 8(2).
Kentish, S., Wooster, T. J., Ashokkumar, A., Balachandran, S., Mawson, R., & Simons, L.
(2006). The use of ultrasonics for nanoemulsion preparation. In 3rd Innovative
foods centre conference on food innovation: Emerging science, technologies and
applications (pp. 170e175). Melbourne, Australia.
Kim, H. J., Decker, E. A., & McClements, D. J. (2002). Role of postadsorption confor-
mation changes of beta-lactoglobulin on its ability to stabilize oil droplets against
flocculation during heating at neutral pH. Langmuir, 18(20), 7577e7583.
Kim, Y. D., Morr, C. V., & Schenz, T. W. (1996). Microencapsulation properties of gum
Arabic and several food proteins: liquid orange oil emulsion particles. Journal of
Agricultural and Food Chemistry, 44(5), 1308e1313.
Kimura, K., Iwata, I., & Nishimura, H. (1982). Studies on the deterioration mecha-
nism of lemon flavor .1. Relationship between acid-catalyzed cyclization of citral
and deterioration of lemon flavor. Agricultural and Biological Chemistry, 46(5),
1387e1389.
Kimura, K., Nishimura, H., Iwata, I., & Mizutani, J. (1983a). Deterioration mechanism
of lemon flavor .2. Formation mechanism of off-odor substances arising from
citral. Journal of Agricultural and Food Chemistry, 31(4), 801e804.
Kimura, K., Nishimura, H., Iwata, I., & Mizutani, J. (1983b). Studies on the deterio-
ration mechanism of lemon flavor .3. Identification of acidic substances from
deteriorated citral and effects of anti-oxidant on their formation. Agricultural
and Biological Chemistry, 47(7), 1661e1663.
Klein, M., Aserin, A., Svitov, I., & Garti, N. (2010). Enhanced stabilization of cloudy
emulsions with gum Arabic and whey protein isolate. Colloids and Surfaces B-
Biointerfaces, 77(1), 75e81.
Konovalov, V. V., & Kispert, L. D. (1999). AM1, INDO/S and optical studies of car-
bocations of carotenoid molecules. Acid induced isomerization. Journal of the
Chemical Society-Perkin Transactions, 2(4), 901e909.
Kralova, I., & Sjoblom, J. (2009). Surfactants used in food industry: a review. Journal
of Dispersion Science and Technology, 30(9), 1363e1383.
Krinsky, N. I. (1998). The antioxidant and biological properties of the carotenoids.
Towards Prolongation of the Healthy Life Span, 854, 443e447.
Lambelet, P., Grandgirard, A., Gregoire, S., Juaneda, P., Sebedio, J. L., & Bertoli, C.
(2003). Formation of modified fatty acids and oxyphytosterols during refining
of low erucic acid rapeseed oil. Journal of Agricultural and Food Chemistry, 51(15),
4284e4290.
Leong, T. S. H., Wooster, T. J., Kentish, S. E., & Ashokkumar, M. (2009). Minimising oil
droplet size using ultrasonic emulsification. Ultrasonics Sonochemistry, 16(6),
721e727.
Li, X., Anton, N., Thi, M. C. T., Zhao, M. J., Messaddeq, N., & Vandamme, T. F. (2011).
Microencapsulation of nanoemulsions: novel Trojan particles for bioactive lipid
molecule delivery. International Journal of Nanomedicine, 6, 1313e1325.
Li, Y., Le Maux, S., Xiao, H., & McClements, D. J. (2009). Emulsion-based delivery
systems for tributyrin, a potential colon cancer preventative agent. Journal of
Agricultural and Food Chemistry, 57(19), 9243e9249.
Liang, C. P., Wang, M. F., Simon, J. E., & Ho, C. T. (2004a). Antioxidant activity of plant
extracts on the inhibition of citral off-odor formation. Molecular Nutrition &
Food Research, 48(4), 308e317.
40 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
Liang, C. P., Wang, M. F., Simon, J. E., & Ho, C. T. (2004b). Stabilization of citral flavor
and fish oil fatty acids by phenolic extracts. Abstracts of Papers of the American
Chemical Society, 228, 012 (AGFD).
Liebler, D. C., & McClure, T. D. (1996). Antioxidant reactions of beta-carotene:
identification of carotenoid-radical adducts. Chemical Research in Toxicology,
9(1), 8e11.
Lim, S. S., Baik, M. Y., Decker, E. A., Henson, L., Popplewell, L. M., McClements, D. J.,
et al. (2011). Stabilization of orange oil-in-water emulsions: a new role for ester
gum as an Ostwald ripening inhibitor. Food Chemistry, 128(4), 1023e1028.
Lin, C. Y., & Chen, L. W. (2008). Comparison of fuel properties and emission char-
acteristics of two- and three-phase emulsions prepared by ultrasonically
vibrating and mechanically homogenizing emulsification methods. Fuel, 87(10e
11), 2154e2161.
Maa, Y. F., & Hsu, C. C. (1999). Performance of sonication and microfluidization for
liquid-liquid emulsification. Pharmaceutical Development and Technology, 4(2),
233e240.
McCann, D., Barrett, A., Cooper, A., Crumpler, D., Dalen, L., Grimshaw, K., et al.
(2007). Food additives and hyperactive behaviour in 3-year-old and 8/9-year-
old children in the community: a randomised, double-blinded, placebo-
controlled trial. Lancet, 370(9598), 1560e1567.
McCaughey, S. A. (2008). The taste of sugars. Neuroscience and Biobehavioral Re-
views, 32(5), 1024e1043.
McClements, D. J. (2002). Theoretical prediction of emulsion color. Advances in
Colloid and Interface Science, 97(1e3), 63e89.
McClements, D. J. (2004). Protein-stabilized emulsions. Current Opinion in Colloid &
Interface Science, 9(5), 305e313.
McClements, D. J. (2005). Food Emulsions: Principles, practices, and techniques (2nd
ed.). Boca Raton, Fl: CRC Press.
McClements, D. J. (2007). Critical review of techniques and methodologies for
characterization of emulsion stability. Critical Reviews in Food Science and
Nutrition, 47(7), 611e649.
McClements, D. J. (2011). Edible nanoemulsions: fabrication, properties, and func-
tional performance. Soft Matter, 7(6), 2297e2316.
McClements, D. J. (2012). Nanoemulsions versus microemulsions: clarification of
differences, similarities and terminology. Soft Matter, 8(6), 1719e1729.
McClements, D. J., & Decker, E. A. (2000). Lipid oxidation in oil-in-water emulsions:
impact of molecular environment on chemical reactions in heterogeneous food
systems. Journal of Food Science, 65(8), 1270e1282.
McClements, D. J., & Decker, E. A. (2008). Lipids. In S. Damodaran, K. L. Parkin, &
O. R. Fennema (Eds.), Food chemistry (4th ed.). (pp. 155e216) Boca Raton: CRC
Press.
McClements, D. J., Decker, E. A., Park, Y., & Weiss, J. (2009). Structural design
principles for delivery of bioactive components in nutraceuticals and functional
foods. Critical Reviews in Food Science and Nutrition, 49(6), 577e606.
McClements, D. J., Decker, E. A., & Weiss, J. (2007). Emulsion-based delivery systems
for lipophilioc bioactive components. Journal of Food Science, 72(8), R109eR124.
McClements, D. J., Henson, L., Popplewell, L. M., Decker, E. A., & Choi, S. J. (2012).
Inhibition of Ostwald ripening in model beverage emulsions by addition of
poorly water soluble triglyceride oils. Journal of Food Science, 77(1), C33eC38.
McClements, D. J., & Li, Y. (2010). Structured emulsion-based delivery systems:
controlling the digestion and release of lipophilic food components. Advances in
Colloid and Interface Science, 159(2), 213e228.
McClements, D. J., & Rao, J. (2011). Food-grade nanoemulsions: formulation, fabri-
cation, properties, performance, biological fate, and potential toxicity. Critical
Reviews in Food Science and Nutrition, 51(4), 285e330.
Mader, I. (1964). Beta-carotene e thermal degradation. Science, 144(361), 533.
Maestro, A., Sole, I., Gonzalez, C., Solans, C., & Gutierrez, J. M. (2008). Influence of
the phase behavior on the properties of ionic nanoemulsions prepared by the
phase inversion composition method. Journal of Colloid & Interface Science,
327(2), 433e439.
Matalanis, A., Jones, O. G., & McClements, D. J. (2011). Structured biopolymer-based
delivery systems for encapsulation, protection, and release of lipophilic com-
pounds. Food Hydrocolloids, 25(8), 1865e1880.
Mayne, S. T. (1996). Beta-carotene, carotenoids, and disease prevention in humans.
The FASEB Journal, 10(7), 690e701.
Mei, L. Y., Choi, S. J., Alamed, J., Henson, L., Popplewell, M., McClements, D. J., et al.
(2010). Citral stability in oil-in-water emulsions with solid or liquid Octadecane.
Journal of Agricultural and Food Chemistry, 58(1), 533e536.
Meyers, B., & Brewer, M. S. (2008). Sweet taste in man: a review. Journal of Food
Science, 73(6), R81eR90.
Miller, C. A. (1988). Spontaneous emulsification produced by diffusion e a review.
Colloids and Surfaces, 29(1), 89e102.
Mirhosseini, H., Tan, C. P., Aghlara, A., Hamid, N. S. A., Yusof, S., & Chern, B. H. (2008).
Influence of pectin and CMC on physical stability, turbidity loss rate, cloudiness
and flavor release of orange beverage emulsion during storage. Carbohydrate
Polymers, 73(1), 83e91.
Mirhosseini, H., Tan, C. P., Hamid, N. S. A., & Yusof, S. (2008). Effect of Arabic gum,
xanthan gum and orange oil on flavor release from diluted orange beverage
emulsion. Food Chemistry, 107(3), 1161e1172.
Misharina, T. A., Terenina, M. B., Krikunova, N. I., & Medvedeva, I. B. (2010).
Autooxidation of a mixture of lemon essential oils, methyl linolenoate, and
methyl oleinate. Applied Biochemistry and Microbiology, 46(5), 551e556.
Mitra, S., & Dungan, S. R. (1997). Micellar properties of quillaja saponin .1. Effects of
temperature, salt, and pH on solution properties. Journal of Agricultural and Food
Chemistry, 45(5), 1587e1595.
Mortensen, A., & Skibsted, L. H. (1996). Kinetics of photobleaching of beta-carotene
in chloroform and formation of transient carotenoid species absorbing in the
near infrared. Free Radical Research, 25(4), 355e368.
Nahon, D. F., Roozen, J. P., & DeGraaf, C. (1996). Sweetness flavour interactions in
soft drinks. Food Chemistry, 56(3), 283e289.
Nakamura, A., Takahashi, T., Yoshida, R., Maeda, H., & Corredig, M. (2004). Emul-
sifying properties of soybean soluble polysaccharide. Food Hydrocolloids, 18(5),
795e803.
Nakamura, A., Yoshida, R., Maeda, H., Furuta, H., & Corredig, M. (2004). Study of the
role of the carbohydrate and protein moieties of soy soluble polysaccharides in
their emulsifying properties. Journal of Agricultural and Food Chemistry, 52(17),
5506e5512.
Nakauma, M., Funami, T., Noda, S., Ishihara, S., Al-Assaf, S., Nishinari, K., et al. (2008).
Comparison of sugar beet pectin, soybean soluble polysaccharide, and gum
arabic as food emulsifiers. 1. Effect of concentration, pH, and salts on the
emulsifying properties. Food Hydrocolloids, 22(7), 1254e1267.
Ogawa, S., Decker, E. A., & McClements, D. J. (2003). Production and characterization
of O/W emulsions containing cationic droplets stabilized by lecithin-chitosan
membranes. Journal of Agricultural and Food Chemistry, 51(9), 2806e2812.
Orchard, T. S., Pan, X. L., Cheek, F., Ing, S. W., & Jackson, R. D. (2012). A systematic
review of omega-3 fatty acids and osteoporosis. British Journal of Nutrition, 107,
S253eS260.
Ostertag, F., Weiss, J., & McClements, D. J. (2012). Low-energy formation of edible
nanoemulsions: factors influencing droplet size produced by emulsion phase
inversion. Journal of Colloid & Interface Science, 388, 95e102.
Ostlund, R. E. (2004). Phytosterols and cholesterol metabolism. Current Opinion in
Lipidology, 15(1), 37e41.
Phillips, G. O., & Williams, P. A. (2000). Gum Arabic. In Handbook of Hydrocolloids
(pp. 165). CRC.
Phillips, G. O., & Williams, P. A. (2009). Handbook of Hydrocolloids (2nd ed.). Boca
Raton, FL: CRC Press.
Pouton, C. W., & Porter, C. J. H. (2006). Formulation of lipid-based delivery systems
for oral administration: materials, methods and strategies. In Annual Meeting of
the American-Association-of-Pharmaceutical-Scientists (pp. 625e637). San
Antonio, TX.
Qian, C., Decker, E. A., Xiao, H., & McClements, D. J. (2011). Comparison of
biopolymer emulsifier performance in formation and stabilization of orange oil-
in-water emulsions. Journal of the American Oil Chemists’ Society, 88(1), 47e55.
Qian, C., Decker, E. A., Xiao, H., & McClements, D. J. (2012). Physical and chemical
stability of beta-carotene-enriched nanoemulsions: influence of pH, ionic
strength, temperature, and emulsifier type. Food Chemistry, 132(3), 1221e1229.
Qian, C., & McClements, D. J. (2011). Formation of nanoemulsions stabilized by
model food-grade emulsifiers using high-pressure homogenization: factors
affecting particle size. Food Hydrocolloids, 25(5), 1000e1008.
Quemada, D., & Berli, C. (2002). Energy of interaction in colloids and its implications
in rheological modeling. Advances in Colloid and Interface Science, 98(1), 51e85.
Rao, J. J., & McClements, D. J. (2010). Stabilization of phase inversion temperature
nanoemulsions by surfactant displacement. Journal of Agricultural and Food
Chemistry, 58(11), 7059e7066.
Rao, J. J., & McClements, D. J. (2011). Food-grade microemulsions, nanoemulsions
and emulsions: fabrication from sucrose monopalmitate & lemon oil. Food
Hydrocolloids, 25(6), 1413e1423.
Rao, J. J., & McClements, D. J. (2012a). Food-grade microemulsions and nano-
emulsions: role of oil phase composition on formation and stability. Food Hy-
drocolloids, 29(2), 326e334.
Rao, J. J., & McClements, D. J. (2012b). Impact of lemon oil composition on formation
and stability of model food and beverage emulsions. Food Chemistry, 134(2),
749e757.
Rao, J. J., & McClements, D. J. (2012c). Lemon oil solubilization in mixed surfactant
solutions: rationalizing microemulsion & nanoemulsion formation. Food Hy-
drocolloids, 26(1), 268e276.
Reiner, S. J., Reineccius, G. A., & Peppard, T. L. (2010). A comparison of the stability of
beverage cloud emulsions formulated with different gum acacia- and starch-
based emulsifiers. Journal of Food Science, 75(5), E236eE246.
Ribeiro, H. S., Ax, K., & Schubert, H. (2003). Stability of lycopene emulsions in food
systems. Journal of Food Science, 68(9), 2730e2734.
Ruxton, C. H. S., Reed, S. C., Simpson, M. J. A., & Millington, K. J. (2004). The health
benefits of omega-3 polyunsaturated fatty acids: a review of the evidence.
Journal of Human Nutrition and Dietetics, 17(5), 449e459.
Ruxton, C. H. S., Reed, S. C., Simpson, M. J. A., & Millington, K. J. (2007). The health
benefits of omega-3 polyunsaturated fatty acids: a review of the evidence.
Journal of Human Nutrition and Dietetics, 20(3), 275e285.
Ryan, L., O’Connell, O., O’Sullivan, L., Aherne, S. A., & O’Brien, N. M. (2008). Micel-
larisation of carotenoids from raw and cooked vegetables. Plant Foods for Hu-
man Nutrition (Formerly Qualitas Plantarum), 63(3), 127e133.
Saberi, A. H., Fang, Y., & McClements, D. J. (2013). Fabrication of vitamin E-enriched
nanoemulsions: factors affecting particle size using spontaneous emulsification.
Journal of Colloid & Interface Science, 391, 95e102.
Sadtler, V., Guely, M., Marchal, P., & Choplin, L. (2004). Shear-induced phase tran-
sitions in sucrose ester surfactant. Journal of Colloid & Interface Science, 270(2),
270e275.
Sagalowicz, L., & Leser, M. E. (2010). Delivery systems for liquid food products.
Current Opinion in Colloid & Interface Science, 15(1e2), 61e72.
Sajjadi, S. (2006). Nanoemulsion formation by phase inversion emulsification: on
the nature of inversion. Langmuir, 22(13), 5597e5603.
 D.T. Piorkowski, D.J. McClements / Food Hydrocolloids 42 (2014) 5e41
van Setten, D. C., ten Hove, G. J., Wiertz, E. J. H. J., Kamerling, J. P., & van de
Werken, G. (1998). Multiple-stage tandem mass spectrometry for structural
characterization of saponins. Analytical Chemistry, 70(20), 4401e4409.
van Setten, D. C., van de Werken, G., Zomer, G., & Kersten, G. F. A. (1995). Glycosyl
compositions and structural characteristics of the potential immuno-adjuvant
active saponins in the Quillaja saponaria Molina extract Quil A. Rapid Commu-
nications in Mass Spectrometry, 9(8), 660e666.
Schieber, A., & Carle, R. (2005). Occurrence of carotenoid cis-isomers in food:
technological, analytical, and nutritional implications. Trends in Food Science &
Technology, 16(9), 416e422.
Shukat, R., Bourgaux, C., & Relkin, P. (2012). Crystallisation behaviour of palm oil
nanoemulsions carrying vitamin E. Journal of Thermal Analysis and Calorimetry,
108(1), 153e161.
Siddiqui, R. A., Shaikh, , Sr., Sech, L. A., Yount, H. R., Stillwell, W., & Zaloga, G. P.
(2004). Omega 3-fatty acids: health benefits and cellular mechanisms of action.
Mini-Reviews in Medicinal Chemistry, 4(8), 859e871.
Sidhu, G., & Oakenfull, D. (1986). A mechanism for the hypocholesterolaemic ac-
tivity of saponins. British Journal of Nutrition, 55(3), 643e649.
Sila, D. N. S., Van Buggenhout, T., Duvetter, I., Fraeye, A. D., Roeck, A., Loey, Van, et al.
(2009). Pectins in processed fruits and vegetables: part IIdstructureefunction
relationships. Comprehensive Reviews in Food Science and Food Safety, 8(2), 86e
104.
Slavin, J. (2012). Beverages and body weight: challenges in the evidence-based
review process of the Carbohydrate Subcommittee from the 2010 Dietary
Guidelines Advisory Committee. Nutrition Reviews, 70, S111eS120.
Sonneville-Aubrun, O., Babayan, D., Bordeaux, D., Lindner, P., Rata, G., & Cabane, B.
(2009). Phase transition pathways for the production of 100 nm oil-in-water
emulsions. Physical Chemistry Chemical Physics, 11(1), 101e110.
Soupas, L., Juntunen, L., Lampi, A. M., & Piironen, V. (2004). Effects of sterol struc-
ture, temperature, and lipid medium on phytosterol oxidation. Journal of Agri-
cultural and Food Chemistry, 52(21), 6485e6491.
Stauffer, S. (1999). Emulsifiers. St Paul, MN: Eagen Press.
Stringham, J. M., & Hammond, B. R. (2005). Dietary lutein and zeaxanthin: possible
effects on visual function. Nutrition Reviews, 63(2), 59e64.
Sylvester, P. W., Wali, V. B., Bachawal, S. V., Shirode, A. B., Ayoub, N. M., & Akl, M. R.
(2011). Tocotrienol combination therapy results in synergistic anticancer
response. Frontiers in Bioscience-Landmark, 16, 3183e3195.
Szuts, A., Budai-Szucs, M., Eros, I., Otomo, N., & Szabó-Révész, P. (2010). Study of gel-
forming properties of sucrose esters for thermosensitive drug delivery systems.
International Journal of Pharmaceutics, 383(1e2), 132e137.
Tadros, T., Izquierdo, R., Esquena, J., & Solans, C. (2004). Formation and
stability of nano-emulsions. Advances in Colloid and Interface Science, 108e09,
303e318.
Tan, C. T. (1998). Beverage flavor emulsion-a form of emulsion liquid membrane
encapsulation. In E. T. Contis (Ed.), Food flavors: Formation, analysis and pack-
aging influences (pp. 29). New York: Elsevier.
Tan, C. T. (2004). Beverage emulsions. In F. S, L. K, & S. J (Eds.), Food emulsions (4th
ed.). New York: Marcel Decker.
Thakur, R. K., Villette, C., Aubry, J. M., & Delaplace, G. (2008). Dynamic emulsification
and catastrophic phase inversion of lecithin-based emulsions. Colloids and
Surfaces A-Physicochemical and Engineering Aspects, 315(1e3), 285e293.
Traber, M. G., Frei, B., & Beckman, J. S. (2008). Vitamin E revisited: do new data
validate benefits for chronic disease prevention? Current Opinion in Lipidology,
19(1), 30e38.
Trubiano, P. C. (1995a). The role of specialty food starches in flavor emulsions. In
Flavor Technology (Vol. 610; pp. 199e209).
Trubiano, P. C. (1995b). The role of specialty food starches in flavor encapsulation. In
Flavor Technology (Vol. 610; pp. 244e253).
Tse, K. Y., & Reineccius, G. A. (1995). Methods to predict the physical stability of
flavor e cloud emulsion. In Flavor Technology (Vol. 610; pp. 172e182).
Tur, J. A., Bibiloni, M. M., Sureda, A., & Pons, A. (2012). Dietary sources of omega 3
fatty acids: public health risks and benefits. British Journal of Nutrition, 107,
S23eS52.
Ueno, T., Kiyohapa, S., Ho, C. T., & Masuda, H. (2006). Potent inhibitory effects of
black tea theaflavins on off-odor formation from citral. Journal of Agricultural
and Food Chemistry, 54(8), 3055e3061.
41
Ueno, T., Masuda, H., & Ho, C. T. (2004). Formation mechanism of p-methyl-
acetophenone from citral via a tert-alkoxy radical intermediate. Journal of
Agricultural and Food Chemistry, 52(18), 5677e5684.
Ueno, T., Masuda, H., Muranishi, S., Kiyohara, S., Sekiguchi, Y., & Ho, C. T. (2003).
Inhibition of the formation of off-odour compounds from citral in an acidic
aqueous solution. In J. L. LeQuere, & P. X. Etievant (Eds.), Flavour research at the
dawn of the twenty-first century (pp. 128e131).
Velikov, K. P., & Pelan, E. (2008). Colloidal delivery systems for micronutrients and
nutraceuticals. Soft Matter, 4(10), 1964e1980.
Waller, G. R., & Yamasaki, K. (1996a). Saponins used in food and agriculture (Vol. 405).
New York, NY: Plenum Press.
Waller, G. R., & Yamasaki, K. (1996b). Saponins used in traditional and modern
medicine (Vol. 404). New York, NY: Plenum Press.
Walstra, P. (1993). Principles of emulsion formation. Chemical Engineering Science,
48, 333.
Walstra, P. (2003). Physical chemistry of foods. New York, NY.: Marcel Decker.
Waraho, T., McClements, D. J., & Decker, E. A. (2011). Mechanisms of lipid oxidation
in food dispersions. Trends in Food Science & Technology, 22(1), 3e13.
Weiss, J., Herrmann, N., & McClements, D. J. (1999). Ostwald ripening of hydro-
carbon emulsion droplets in surfactant solutions. Langmuir, 15(20), 6652e6657.
Weng-Yew, W., & Brown, L. (2011). Nutrapharmacology of tocotrienols for metabolic
syndrome. Current Pharmaceutical Design, 17(21), 2206e2214.
Williams, M. A. K., Fabri, D., Hubbard, C. D., Lundin, L., Foster, T. J., Clark, A. H., et al.
(2001). Kinetics of droplet growth in gelatin/maltodextrin mixtures following
thermal quenching. Langmuir, 17(11), 3412e3418.
Wong, N. C. W. (2001). The beneficial effects of plant sterols on serum cholesterol.
Canadian Journal of Cardiology, 17(6), 715e721.
Woodall, A. A., Lee, S. W. M., Weesie, R. J., Jackson, M. J., & Britton, G. (1997).
Oxidation of carotenoids by free radicals: relationship between structure and
reactivity. Biochimica Et Biophysica Acta-General Subjects, 1336(1), 33e42.
Wooster, T., Golding, M., & Sanguansri, P. (2008). Impact of oil type on nanoemulsion
formation and Ostwald ripening stability. Langmuir, 24(22), 12758e12765.
Wrolstad, R. E., & Culver, C. A. (2012). Alternatives to those artificial FD&C food
colorants. In M. P. Doyle, & T. R. Klaenhammer (Eds.), Annual Review of Food
Science and Technology (Vol. 3; pp. 59e77).
Xianquan, S., Shi, J., Kakuda, Y., & Yueming, J. (2005). Stability of lycopene during
food processing and storage. Journal of Medicinal Food, 8(4), 413e422.
Yadav, M. P., Johnston, D. B., Hotchkiss, A. T., & Hicks, K. B. (2007). Corn fiber gum: a
potential gum arabic replacer for beverage flavor emulsification. Food Hydro-
colloids, 21(7), 1022e1030.
Yamauchi, R., Miyake, N., Inoue, H., & Kato, K. (1993). Products formed by peroxyl
radical oxidation of beta-carotene. Journal of Agricultural and Food Chemistry,
41(5), 708e713.
Yang, Y., Leser, M. E., Sher, A. A., & McClements, D. J. (2013). Formation and stability
of emulsions using a natural small molecule surfactant: quillaja saponin (Q-
Naturale (R)). Food Hydrocolloids, 30(2), 589e596.
Yang, Y., Marshall-Breton, C., Leser, M. E., Sher, A. A., & McClements, D. J. (2012).
Fabrication of ultrafine edible emulsions: comparison of high-energy and low-
energy homogenization methods. Food Hydrocolloids, 29(2), 398e406.
Yang, Y., & McClements, D. J. (2013). Encapsulation of vitamin E in edible emulsions
fabricated using a natural surfactant. Food Hydrocolloids, 30(2), 712e720.
Yang, X. Q., Tian, H. X., Ho, C. T., & Huang, Q. R. (2011). Inhibition of citral degra-
dation by oil-in-water nanoemulsions combined with antioxidants. Journal of
Agricultural and Food Chemistry, 59(11), 6113e6119.
Yang, X. Q., Tian, H. X., Ho, C. T., & Huang, Q. R. (2012). Stability of citral in emulsions
coated with cationic biopolymer layers. Journal of Agricultural and Food Chem-
istry, 60(1), 402e409.
Yin, L. J., Chu, B. S., Kobayashi, I., & Nakajima, M. (2009). Performance of selected
emulsifiers and their combinations in the preparation of beta-carotene nano-
dispersions. Food Hydrocolloids, 23, 1617e1622.
Yoon, Y., & Choe, E. (2009). Lipid oxidation and stability of tocopherols and phos-
pholipids in soy-added fried products during storage in the dark. Food Science
and Biotechnology, 18(2), 356e361.
Zuccari, G., Carosio, R., Fini, A., Montaldo, P., & Orienti, I. (2005). Modified poly-
vinylalcohol for encapsulation of all-trans-retinoic acid in polymeric micelles.
Journal of Controlled Release, 103(2), 369e380.