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Nanotechnology Applications
in the Food Industry
http://taylorandfrancis.com
Nanotechnology Applications
in the Food Industry
Edited by
V Ravishankar Rai
Jamuna A. Bai
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to
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Part I
Introduction to Nanotechnology in the Food Sector
Chapter 1
Development of Bio-Based Nanostructured Systems by Electrohydrodynamic Processes...............3
Maria Jose Costa, Philippe Emmanuel Ramos, Pablo Fuciños, José António Teixeira,
Lorenzo Miguel Pastrana, and Miguel Ângelo Cerqueira
Chapter 2
Carbon Nanomaterial-Based Fertilizers Can Improve Plant Growth..............................................21
Guixue Song, Madelyn Pandorf, Paul Westerhoff, and Yun Ma
Chapter 3
Nanomaterials in Food Applications................................................................................................45
Ahmed S. Khan
Chapter 4
Market Potential of Food Nanotechnology Innovations..................................................................59
Rajesh P. Shastry and V Ravishankar Rai
Part II
Nanotechnology in Food Packaging
Chapter 5
Nanomaterials Applicable in Food Protection.................................................................................75
Josef Jampílek and Katarína Kráľová
Chapter 6
Use of Nanopolymers, Nanocomposites, and Nanostructured Coatings in Food Packaging..........97
Semih Ötleş and Buket Yalçın Şahyar
Chapter 7
Starch Nanocomposite Films for Food Packaging.........................................................................107
Oswaldo Ochoa Yepes, Lucas Guz, Santiago Estevez Areco, Roberto Candal,
Silvia Goyanes, and Lucía Famá
Chapter 8
Electrospun Nanofibers: Development and Potential in Food Packaging Applications................141
Carlos A. Fuenmayor and Paula J. P. Espitia
v
VI CONTENTS
Part III
Nanosensors for Safe and Quality Foods
Chapter 9
Nanosensors in the Food Industry.................................................................................................183
Fabrizio Sarghini and Francesco Marra
Chapter 10
Applications of Aptamers to Nanobiosensors and Smart Packaging............................................203
Luis Eduardo Suárez-Nájera, Stefany Cárdenas-Pérez, José Jorge Chanona-Pérez,
Arturo Manzo-Robledo, Jaime Vargas-Cruz, Mayra Luna-Trujillo,
Miriam Rodríguez-Esquivel, and Mauricio Salcedo-Vargas
Part IV
Nanotechnology for Nutrient Delivery in Foods
Chapter 11
Nanoemulsions Produced by Low-Energy Methods: Fundamentals and Food Applications.......221
Samantha C. Pinho, Cynthia de Carli, and Marilia Moraes-Lovison
Chapter 12
Application of Nanotechnology in the Safe Delivery of Bioactive Compounds..........................237
Behrouz Ghorani, Sara Naji-Tabasi, Aram Bostan, and Bahareh Emadzadeh
Chapter 13
Electrospinning of Edible, Food-Based Polymers.........................................................................293
Serife Akkurt, Lin Shu Liu, and Peggy Tomasula
Chapter 14
Role of Polymeric Nanoparticles in Nutraceutical Delivery..........................................................315
Rubiana Mara Mainardes and Najeh Maissar Khalil
Chapter 15
Nanoemulsions and Nanodispersions: A Fundamental View of Their Preparation,
Characterization, Stability Evaluation, and Application................................................................333
Tai Boon Tan and Chin Ping Tan
Chapter 16
Lipid Nanocarriers for Phytochemical Delivery in Foods.............................................................357
Bojana D. Balanč, Kata T. Trifković, Radoslava N. Pravilović, Verica B. Đorđević,
Steva M. Lević, Branko M. Bugarski, and Viktor A. Nedović
CONTENTS VII
Chapter 17
Role of Bioactive Compounds to Improve Nanomechanical Properties and Functionality
of Polymeric Vehicles....................................................................................................................385
Alonso Villafán-Rangel, Juan Eduardo René Cortés-Millán, Miriam Madrid-Mendoza,
Israel Arzate-Vázquez, Monserrat Escamilla-García, Ollin Celeste Martínez-Ramírez,
and Angélica Gabriel Mendoza-Madrigal
Chapter 18
Microscopy Techniques for Structural Characterization, Evaluation of Nanomechanical
Properties, and Biosensing of Food Systems.................................................................................403
Luis Eduardo Suárez-Nájera, Stefany Cárdenas-Pérez, Juan Vicente Méndez-Méndez,
José Jorge Chanona-Pérez, Alejandra Valdivia-Flores, Georgina Calderón-Domínguez,
and Rubén López-Santiago
Chapter 19
Chitosan Micro- and Nanoparticles for Vitamin Encapsulation....................................................427
Patricia Rosales-Martínez, Maribel Cornejo-Mazón, Izlia J. Arroyo-Maya,
and Humberto Hernández-Sánchez
Chapter 20
Nanoparticle Nutrient Carriers.......................................................................................................441
Nily Dan
Chapter 21
Electrospinning and Electrospraying Technologies and Their Potential Applications
in the Food Industry.......................................................................................................................461
Alex López-Córdoba, Clara Duca, Jonathan Cimadoro, and Silvia Goyanes
Part V
Safety Assessment for Use of Nanomaterials in Food and Food Production
Chapter 22
Advanced Approaches for Efficacy Evaluation and Risk Assessment of Nanomaterials in Food...483
Marco Roman, Catia Contado, Christian Micheletti, Iolanda Olivato, Erik Tedesco,
and Federico Benetti
Chapter 23
Effect of Nanoparticles on Gastrointestinal Tract..........................................................................503
Jamuna A. Bai and V Ravishankar Rai
Chapter 24
Regulatory Framework for Food Nanotechnology........................................................................517
Kangkana Banerjee and V Ravishankar Rai
Index.............................................................................................................................................. 529
http://taylorandfrancis.com
Preface
Nanotechnology Applications in the Food Industry is a comprehensive reference book containing
exhaustive information on nanotechnology and the scope of its applications in the food industry. The
various sectors in the food industry where nanotechnology finds extensive application include the
production, processing, packaging, and preservation of foods. Nanotechnology is also increasingly
used to enhance flavor and color and in nutrient delivery and bioavailability and to improve food
safety and in quality management.
The book focuses on the overview of nanotechnology development for food industries and the
impact it is having on the state of science in the food industry. The book has five sections delving into
all aspects and the key role of nanotechnology in the food industry in the present scenario and the
future trends. Part I (Introduction to Nanotechnology in the Food Sector) covers the technological
basis for its application in the food industry and in agriculture, the use of nanosized foods and
nanomaterials in food, the safety issues pertaining to its applications in the foods, and on market
analysis and consumer perception of food nanotechnology. Part II (Nanotechnology in Food Pack-
aging) reviews the use of nanopolymers, nanocomposites, and nanostructured coatings in food
packaging. The potential of nanotechnology in active packaging applications, intelligent packaging,
and multifunctional packaging for improving the safety and quality of foods are discussed. Part III
(Nanosensors for Safe and Quality Foods) provides an overview on nanotechnology in the develop-
ment of biosensors for pathogen and food contaminant detection and in sampling and food quality
management. The challenges and trends in nanosensor design for food applications are discussed. Part
IV (Nanotechnology for Nutrient Delivery in Foods) deals with the use of nanotechnology in foods for
controlled and effective release of nutrients. The use of nanoparticles in developing, increasing the
functionality and bioactivity of dietary foods, functional foods, and nutraceuticals are covered. Part V
(Safety Assessment for Use of Nanomaterials in Food and Food Production) deliberates on the benefits
and risks associated with the extensive and long-term application of nanotechnology in the food sector.
The issues on nanoparticles and their residues in food during food production, migration of
nanoparticles into foods during processing and packaging, behavior of nanoparticles in the gastro-
intestinal tract, and safety and risk assessment of nanomaterials in the food are reviewed. Legal and
ethical barriers for the application of nanotechnology in food industry, regulatory aspects of its
application in food, and food production and labeling of nano ingredients in foods are addressed.
The book is a valuable reference material discussing the basics and trends in the application of
nanotechnology in the food industry. It is exhaustive and comprehensive, focusing on all aspects of
technological strategies in the nanofood segment. The book is beneficial for graduate students,
researchers, scientists working on application aspects of nanotechnology and food industry and food
policy makers.
We would like to thank all the authors for contributing the chapters and sharing their expertise.
ix
http://taylorandfrancis.com
Editors
V Ravishankar Rai earned his MSc and PhD from the University of Mysore, India. Currently,
Dr. Rai is working as a professor in the Department of Studies in Microbiology, University of
Mysore, India. He was awarded a fellowship from the UNESCO Biotechnology Action Council,
Paris (1996), the Indo-Israel Cultural Exchange Fellowship (1998), the Biotechnology Overseas
Fellowship, Government of India (2008), the Indo-Hungarian Exchange Fellowship (2011), Indian
National Academy Fellowship (2015), and Cardiff Incoming Visiting Fellowship (2017). Presently,
he is the coordinator for the Department of Science and Technology, Promotion of University
Research and Scientific Excellence and University Grants Commission innovative programs.
Jamuna A. Bai has completed her MSc and PhD in microbiology from the University of Mysore,
India. She is working as a researcher in the University Grants Commission-sponsored University
with Potential Excellence Project, University of Mysore, India. She has previously worked as Indian
Council of Medical Research Senior Research Fellow and carried research on food safety, role of
quorum sensing and biofilms in food-related bacteria, and developing quorum-sensing inhibitors.
Her research interests also include antimicrobial application of functionalized nanomaterials against
food-borne pathogens.
xi
http://taylorandfrancis.com
Contributors
Serife Akkurt Bojana D. Balanč
Dairy and Functional Foods Research Unit Faculty of Technology and Metallurgy
Eastern Regional Research Center Department of Chemical Engineering
Agricultural Research Service University of Belgrade
United States Department of Agriculture Belgrade, Serbia
Wyndmoor, Pennsylvania
Kangkana Banerjee
and Department of Studies in Microbiology
Rutgers University of Mysore
Department of Food Science Mysore, India
The State University of New Jersey
New Brunswick, New Jersey Federico Benetti
European Center for the Sustainable Impact
of Nanotechnology
Santiago Estevez Areco
EcamRicert Srl
Facultad de Ciencias Exactas y Naturales
Rovigo, Italy
Departamento de Física, Laboratorio
de Polímeros y Materiales Compuestos
Aram Bostan
(LP&MC)
Department of Food Nanotechnology
Instituto de Física de Buenos Aires
Research Institute of Food Science
(IFIBA-CONICET)
and Technology
Universidad de Buenos Aires
Mashhad, Iran
Buenos Aires, Argentina
Branko M. Bugarski
Izlia J. Arroyo-Maya Faculty of Technology and Metallurgy
Departamento de Procesos y Tecnología, Department of Chemical Engineering
Unidad Cuajimalpa University of Belgrade
Universidad Autónoma Metropolitana Belgrade, Serbia
Mexico City, Mexico
Georgina Calderón-Domínguez
Israel Arzate-Vázquez Departamento de Ingeniería Bioquímica
Laboratorio de Microscopía de Fuerza Atómica Escuela Nacional de Ciencias Biológicas
y Nanoindentación, Centro de Nanociencias Instituto Politécnico Nacional
y Micro y Nanotecnologías Mexico City, Mexico
Instituto Politécnico Nacional
Unidad Profesional Adolfo López Mateos Roberto Candal
Mexico City, Mexico Instituto de Investigación e Ingeniería
Ambiental, Consejo Nacional
Jamuna A. Bai de Investigaciones Científicas y Técnicas
Department of Studies in Microbiology Universidad Nacional de San Martín
University of Mysore Buenos Aires, Argentina
Mysore, India
xiii
XIV CONTRIBUTORS
Bahareh Emadzadeh
Catia Contado
Department of Food Nanotechnology
Department of Chemical
Research Institute of Food Science
and Pharmaceutical Sciences
and Technology
University of Ferrara
Mashhad, Iran
Ferrara, Italy
Monserrat Escamilla-García
Maribel Cornejo-Mazón Facultad de Química
Departamento de Biofísica, Escuela Nacional Universidad Autónoma de Querétaro
de Ciencias Biológicas del Instituto Santiago de Querétaro, Mexico
Politécnico Nacional
Unidad Profesional Lázaro Cárdenas Paula J. P. Espitia
Mexico City, Mexico Nutrition and Dietetics School
University of Atlantico
Juan Eduardo René Cortés-Millán Atlantico, Colombia
Laboratorio de Investigación A
Facultad de Nutrición Lucía Famá
Universidad Autónoma del Estado de Morelos Facultad de Ciencias Exactas y Naturales
Cuernavaca, Mexico Departamento de Física, Laboratorio de
Polímeros y Materiales Compuestos (LP&MC)
Maria Jose Costa Instituto de Física de Buenos Aires
Centre of Biological Engineering (IFIBA-CONICET)
University of Minho Universidad de Buenos Aires
Braga, Portugal Buenos Aires, Argentina
CONTRIBUTORS XV
Francesco Marra
University of Salerno
Fisciano, Italy
CONTRIBUTORS XVII
Peggy Tomasula
Dairy and Functional Foods Research Unit
Eastern Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Wyndmoor, Pennsylvania
PART I
Introduction to Nanotechnology
in the Food Sector
http://taylorandfrancis.com
CHAPTER 1
Maria Jose Costa, Philippe Emmanuel Ramos, Pablo Fuciños, José António Teixeira,
Lorenzo Miguel Pastrana, and Miguel Ângelo Cerqueira
CONTENTS
1.1 INTRODUCTION
Nanotechnology offers many benefits for the development of structures with enhanced proper-
ties. Due to their dimension, nanostructured systems present different physicochemical properties
(i.e., optical, thermal, absorption, and stability) when compared with micro- and macroscale systems,
making their use in food processing and applications of great interest to the industry. The main aspect
that influences their different behavior at the nanoscale is the area-to-volume ratio. It determines the
physicochemical characteristics and brings several advantages, such as a high encapsulation effi-
ciency and stability, a tailored control release, an enhanced solubility, and the prevention of unde-
sirable chemical reactions (Cerqueira et al. 2014, 2017a).
In recent years, the development of high-performance nanostructured systems for food appli-
cations has improved food safety (e.g., sensor and nanoparticles). These systems have been applied
3
4 NANOTECHNOLOGY APPLICATIONS IN THE FOOD INDUSTRY
in several areas such as the encapsulation and controlled release of compounds, in the development
of new food processing methodologies, and in food packaging. Aiming for commercialization,
several nanotechnology-based products have been market launched in the last 10 years, claiming
enhanced functionality based on their nanosized features (Silva, Cerqueira, and Vicente 2015). The
development of bio-based nanostructured systems, for food applications, has been presented by
researchers through a high number of published works. These works present the potential of
using those systems for several applications such as for the protection and delivery of bioactive
compounds, enzyme immobilization, detection of contaminants and microorganisms through the
development of sensors, removal of chemicals from foods, water purification through nanofiltra-
tion, and the development of nanocomposites for packaging. This great number of applications is
explained by the possibility of developing bio-based nanostructures with distinct architectures that,
according to the materials and methodologies used, can be designed with different shapes and
sizes. The common shapes of bio-based nanostructured systems are spheroids (capsules or particles),
fibers (membranes), thin films (nanocoating for food packaging), and tubes (sensors) (Cerqueira et al.
2017b).
Different approaches can be used for the development of nanostructured systems, giving
importance to the control of the driving forces (e.g., electrostatic and hydrophobic interactions) and
the free energy of the system (e.g., to assess the thermodynamic stability), which leads to systems
with distinct properties and functionalities. During the fabrication process, nanostructured systems
can be developed by the bottom-up and top-down methods, which are two of the common ways to
classify the developed system (Livney 2015; Silva, Cerqueira, and Vicente 2011). Despite all the
advantages of using bio-based nanostructures, the scale-up process from the laboratory to an
industrial scale is still a hard task. The major challenge is controlling the main characteristics and
properties of the nanostructures from the laboratory to the industrial production. In addition, some of
the challenges regarding the scaling-up of nanostructure production are the batch versus continuous
production, the increasing flow rate, and the homogenization process, which leads to a considerable
number of trials for process optimization at industrial scale. While for inorganic nanostructures
(i.e., ZnO, TiO2, and SiO2), the scale-up and commercialization is in the exponential step, where
several companies have shown the capacity to produce several kilograms per day, for organic
nanostructures, the industrial production is still in the beginning (Piccinno et al. 2012; Tsuzuki
2009). Some of the methodologies showing the capacity to be scaled-up for the production of food-
grade bio-based nanostructures are high-pressure homogenization, microfluidics, vibrational atom-
ization (nanospray drier), and nanoprecipitation (Arpagaus 2012; Cerqueira et al. 2014; Lu et al.
2016; Trierweiler and Trierweiler 2011).
Other processes that show promising advantages are the electrohydrodynamic processes, such as
electrospinning and electrospraying that have been explored for the production of food-grade bio-
based nanostructured systems. These new processes are starting to change and improve the food
industry through their use in several applications with a wide range of bio-based materials generally
recognized as safe (GRAS) by the US Food and Drug Administration (FDA) and/or the European
Food Safety Authority (EFSA) (Kaur Bhullar, Kaya, and Jun 2015). Several studies confirmed
that electrospinning and electrospraying processes are very effective in producing bio-based
nanostructures with several advantages that overcome the existing technology limitations, such as
different sizes range (micro to nano) and type of structures (fibers and particles), no heating required,
ability to scale up (multinozzle systems), versatility in morphology (porosity and roughness), and
low or no organic solvent requirement (Ghorani and Tucker 2015). Besides, the use of food-grade
biopolymers for the production of structures able to guarantee high encapsulation efficiencies,
a good stability, and a controlled release of bioactive compounds is also an important advantage
(Anu Bhushani and Anandharamakrishnan 2014). However, they can present some limitations such
as the high price of the equipment and the difficult scale-up of the process (Quirós, Boltes, and Rosal
2016).
DEVELOPMENT OF BIO-BASED NANOSTRUCTURED SYSTEMS 5
In the food industry, electrohydrodynamic processing is still recent and only slightly studied, its
use being unusual in food structuring. Nevertheless, electrospinning and electrospraying are proving
to be excellent options for use in the encapsulation of several functional compounds with interest for
the food industry and in packaging applications (Ghorani and Tucker 2015; Pérez-Masiá, Lagaron,
and López-Rubio 2014). The interest of researchers and industry has been driven by several technical
advantages such as the facility of use, the available equipment, and the possibility of tuning the final
properties of the materials by changing the processing conditions.
The electrohydrodynamic processes use an electrically driven force to produce single or multi-
layer fibers or particles that can be at the micro- and nanometric scale. During the process, an
electrically charged fluid cone jet is formed by the biopolymer solution or molten biopolymer that is
formed between the spinneret and the collector. The applied electric field leads to the formation of a
cone-like shape, called the Taylor cone, that is obtained when the equilibrium of the electric forces
and surface tension is destroyed. In the case of the formation of fibers (electrospinning), continuous
production is achieved when the fluid is ejected from the tip of the Taylor cone and an extended fiber
is formed by an electrostatic field that quickly solidifies on the collector (Figure 1.1a) (Quirós,
Boltes, and Rosal 2016). Due to the high instability of the process, the fiber deposition and orien-
tation is difficult to control, as the fibers are randomly oriented. To achieve a “more” controlled
deposition of the fibers, the movement of the nozzle and/or collector can be controlled as well as the
distance to the collector. For the production of particles (electrospray), the phenomenon is similar
(Figure 1.1b), although, in this case, the electric field causes the deformation and distribution of the
jet into droplets that, after being spray dried, are deposited in the collector (Jaworek and Sobczyk
2008). In the case of electrospraying, it is also possible to electrospray the biopolymers on a cross-
linking solution (mostly used for the alginate cross-linking using CaCl2) to achieve more stable
particles (Ghayempour and Mortazavi 2013).
Choosing a molten biopolymer or the use of a biopolymer solution will highly influence the
equipment requirements for the electrospinning/electrospraying process. While for processing, using
a biopolymer solution, no heating is needed; for the process using a molten biopolymer, equipment
with a heating module is needed. In fact, the use of the melting process is not common in food
applications, mostly because some of the biopolymers and functional compounds used are
thermosensitive and the use of heating can in most cases be a disadvantage (Zhang et al. 2016). One
of the possibilities with electrohydrodynamic processing is to use nozzles with different diameters
– –
Collector Collector
(a) (b)
Figure 1.1 Main composition of (a) electrospinning and (b) electrospraying equipment during the processing of a
biopolymer solution.
6 NANOTECHNOLOGY APPLICATIONS IN THE FOOD INDUSTRY
and multiaxial geometries (monoaxial, coaxial, or triaxial) that will influence the morphology and the
properties of the produced structures (Chakraborty et al. 2009; Xu et al. 2013). The multiaxial
(coaxial/triaxial) geometries consist in different spinneret components which allow the simultaneous
spinning/spraying of different liquids (Quirós, Boltes, and Rosal 2016). The use of coaxial and
triaxial nozzles allows coating solid, liquid, or gas phases with a solid shell and produce multilayer
structures, bringing several advantages, such as a controlled and tunable release of functional
compounds, and encapsulation of different compounds in the same structure, allowing their release at
different stages.
The collectors can also have different geometries and morphologies, such as flat surface (stainless-
steel plate) or a cylinder (rotating mandrel), that can be in motion during the processing (Cerqueira et
al. 2016; Gómez-Mascaraque, Lagarón, and López-Rubio 2015). The collector movements can be
used to define the pattern of the developed structures (Bu et al. 2012), the use of a flat collector
(working in the x and y directions) and the distance from the spinneret to the collectors (z direction)
allow the development of three-dimensional (3D) structures (Zhang et al. 2016).
Besides the equipment, the different possibilities to electrospin the biopolymer (melted or in
solution) and the processing parameters are also very important factors when the objective is to
obtain fibers or particles. Other important variables are the applied voltage between the nozzle and
collector that, together with the solution and/or biopolymers characteristics, determines the electric
field strength and thus the electrohydrodynamic jetting mode. These parameters will be discussed in
the next section.
1.2.2 Parameters
The electrohydrodynamic processes can be influenced by several parameters that will define
the aspect, size, and morphology of the produced structures. The most influential parameters are
(a) the polymer solution type, (b) processing, and (c) ambient conditions used during the electro-
hydrodynamic process. For the biopolymer solution, specific characteristics such as solvent type,
conductivity, molecular weight, viscosity, and surface tension are the most influential. The process
parameters that influence the obtained structure include the tip to collector distance, diameter of
spinneret, applied voltage, and flow rate. The ambient conditions such as relative humidity, air flow,
and temperature of the surroundings are also important during the process (Chong et al. 2007). The
control of these variables will allow controlling the size, density, and morphology of the produced
structures (Rogina 2014), although it is important to mention that to achieve reproducible results, a
stable cone-jet mode should be obtained (Bock, Dargaville, and Woodruff 2012).
The biopolymer concentration has a direct impact in viscosity, being one of the most important
variables to obtain a stable cone-jet mode. An optimal concentration mainly depends on which
structure type is desired, it being possible to obtain particles or fibers. Normally, with an optimal
concentration range, the low polymer concentrations do not produce a continuous jet, leading to the
production of particles, while for high polymer concentrations, a continuous flow is achieved and
fibers will be formed. In the case of middle term conditions, a mixture of both mentioned structures
will be obtained (i.e., particles and fibers) (López-Rubio and Lagaron 2012; Rogina 2014;
Wongsasulak et al. 2007). During processing, if the flow rate is low or the electric field strength is
high, the Taylor cone cannot be maintained and the process results in a phenomenon such as tilted
jetting, multijetting, and dripping (Zhang et al. 2016).
The electrohydrodynamic process produces dried structures, although to accomplish this, high
concentrations of polymer must be used in order to reduce the solvent content and thus facilitating the
solvent evaporation. However, a low viscosity is needed to allow jet formation; otherwise, a con-
tinuous electrospinning will be not possible (Huang et al. 2003; Shenoy et al. 2005). The solvent used
DEVELOPMENT OF BIO-BASED NANOSTRUCTURED SYSTEMS 7
is an important factor to allow, at first, a proper dissolution of the polymer and, at second, an efficient
drying of the electrospun fibers or electrosprayed particles (Ghorani and Tucker 2015). Therefore,
solvents with lower vapor pressure would permit an easier fiber drying (Wannatong, Sirivat, and
Supaphol 2004). Other works also refer to the fact that the mixture of different solvents might bring
important characteristics such as an easier drying process while maintaining the dissolution of the
polymer (Ghorani, Russell, and Goswami 2013).
One of the factors that influence the polymer solution viscosity the most is the molecular weight
of the polymer. In general, high molecular weight increases viscosity leading to fiber formation (Tao
and Shivkumar 2007). Therefore, low-molecular weight polymers are more likely to produce par-
ticles and high-molecular weight polymers produce fibers with large diameters (Bhardwaj and
Kundu 2010). When the polymer solution is constituted by a mixture of polymers, the molecular
weight of the polymers might also not be so influential in the production of fibers, since the polymers
have enough affinity to create several entanglement points through intermolecular interactions
(Munir et al. 2009).
One of the ways used to understand the capacity of a polymer solution to be electrospun or
electrosprayed is to evaluate the surface tension and conductivity. The surface tension is mainly
dependent on the solvent used rather than on the polymer. High surface tension might prevent the
formation of fibers and capsules or even complicate Taylor’s cone formation (Rogina 2014). A lower
surface tension will allow the utilization of a lower electric field. To avoid a negative influence of
surface tension, a reduction of polymer concentration might be done, although it is important to be
aware that this change will also affect the viscosity of the polymer solution (Moomand and Lim 2015).
The conductivity of the solution is influenced by the polymer, solvent type, and the presence of salts.
More conductive solutions produce smaller-diameter fibers through electrospinning (Zong et al. 2002;
Jiang et al. 2004). Therefore, with the same conditions, a more conductive solution will produce a
higher elongated jet, thus producing a fiber with a smaller diameter (Tan et al. 2005). Aiming at
controlling this parameters, it is common to use inorganic salts, which are added to increase electrical
conductivity due to their smaller ionic diameter and higher ion mobility (Su et al. 2011).
Regarding the parameters that are controllable in the equipment used, the applied voltage, flow
rate, and collector distance are the most studied. The flow rate controls the amount of polymer that
flows to the collector during a certain period of time. The flow rate should respect the drying time, to
create dried fibers or particles. An increase in the flow rate will generate structures with bigger
diameters, as a consequence of a larger amount of electrospun polymer (Zong et al. 2002).
The applied voltage controls the electric field strength created between the spinneret and the
collection point. Ghorani and Tucker (2015) worked to overcome the normal behavior of a dropwise
solution to accomplish a Taylor’s cone. It is extremely dependent on parameters such as flow rate,
surface tension, and viscosity. Higher voltages will increase the velocity of the jet and, as a con-
sequence, the transported solution volume (Zong et al. 2002). Usually, there is a voltage range able to
produce the minimal average fiber diameter, where a higher or lower voltage will increase the
average fiber diameter (Ghorani and Tucker 2015). The distance between the tip and the collector is
essential to allow fibers and particles to dry and should be adjusted according to the polymer con-
centration and applied voltage (Guo et al. 2013; Zou et al. 2011). In general, a greater distance
between the tip and the collector will create longer flight times and higher solvent evaporation.
Consequently, the diameter of the produced fibers will be smaller and the tendency for particles
creation will be reduced (Lin et al. 2008; Yuan et al. 2004).
Other parameters that should be controlled are the ambient conditions during processing.
Temperature is an ambient parameter that mainly affects the polymer viscosity and the fiber drying
process. Higher temperatures would create a lower polymer viscosity, and as a consequence, the fiber
diameters will be smaller (Bhardwaj and Kundu 2010). Humidity can influence the fiber drying
process, where a low humidity allows an easier fiber drying process (Demir et al. 2002).
8 NANOTECHNOLOGY APPLICATIONS IN THE FOOD INDUSTRY
The use of bio-based materials in the development and production of nanostructures through
electrohydrodynamic processing is revealing several structural and functional advantages. Regarding
commercial applications in the food industry, the use of biopolymers to produce nanofibers and
nanoparticles, using electrohydrodynamic processes, has a wide area of applications such as new
food ingredients, food additives encapsulation, high-performance (active) food packaging and
coatings, and biosensors. However, and at this moment, only few companies are able to produce it
using biopolymers at industrial scale (one of the cases is Bioinicia 2017 in Spain). Another kind of
application with high potential is the use of electrohydrodynamic processing in the confectionery
industry since the electrospun structures allow the creation of new textures and coatings in foods,
leading to new and enhanced organoleptic properties (e.g., chocolate) (Altay and Okutan 2015; Luo
et al. 2012a; Nieuwland et al. 2014).
In this section, the bio-based materials used in electrohydrodynamic processing will be explored,
as well the food applications where they can be used.
Several bio-based materials from diverse origins can be used in electrohydrodynamic processes.
Bio-based materials can be divided into the following:
• Bio-based materials extracted from biomass, such as polysaccharides and proteins
• Bio-based materials obtained from biomass-derived monomers where the final biodegradable polymer is
obtained through classical chemical synthetic routes, such as poly(lactic)acid (PLA)
• Polymers obtained from natural or genetically modified microorganisms, like xanthan gum and
polyhydroxyalkanoates
Bio-based materials are all suitable for electrospinning and electrospraying with different purposes
such as encapsulation of bioactive compounds, food packaging and coating, enzyme immobilization,
and production of filtration membranes (Anu Bhushani and Anandharamakrishnan 2014; Fabra,
López-Rubio, and Lagaron 2016; Ghorani and Tucker 2015). Bio-based materials are also promising
choices due to their biodegradability and biocompatibility characteristics and to the fact that they can
be tailored to the desired properties turning them into versatile carriers (Aceituno-Medina et al. 2014;
Nieuwland et al. 2014; Stijnman, Bodnar, and Hans Tromp 2011). Another advantage of these
materials is the fact that they can be used simultaneously with different methods (e.g., layer-by-layer,
cross-linking) to enhance the final properties of structures. Concerning regulatory aspects, the choice
will fall in materials generally recognized as safe (GRAS) and approved by the regulatory agencies
(i.e., EFSA and FDA). From an economic point of view, elements such as a continuous supply, cost,
and simplicity of use are all taken into account for the selection of the matrix source material. Some of
the biopolymers used for electrospinning and/or electrospraying are presented in Table 1.1.
The main objectives of the food industry is to ensure the stability and quality of the food products
as well the process efficiency. It seeks to achieve these demands and, at the same time, maintain food
processing as simple as possible. So new and innovative food processing technologies play an
important role in the continuous improvement of food processing and their products.
This is the case for new processing technologies such as the electrohydrodynamic process that can
help the food industry in achieving greater performance, higher versatility, and innovative approaches
to the different types of applications. Some of these applications are the encapsulation of bioactive
compounds, food packaging and coating, enzyme immobilization, and bacteriophage incorporation
(Table 1.2) (Fabra, López-Rubio, and Lagaron 2016; Lee et al. 2016; Wen et al. 2016).
DEVELOPMENT OF BIO-BASED NANOSTRUCTURED SYSTEMS 9
Table 1.1 Bio-Based Material Source and Type Used in Electrohydrodynamic Processing, Developed
Structure, and Encapsulated Compounds
Biomaterial Biomaterial Encapsulated
Source Type Structure Compounds Reference
Directly extracted Chitosan Electrospun fibers CNMA Rieger and Schiffman
from biomass (2014)
Chitosan Particles and fibers (−)-Epigallocatechin Gómez-Mascaraque,
gallate Sanchez, and López-
Rubio (2016)
Sodium alginateElectrospray Folic acid Bakhshi et al. (2013)
particles
Starch Electrospun fibers BCNW Fabra et al. (2016)
Alyssum Electrospray D-limonene Khoshakhlagh et al.
homolocarpum particles (2017)
seed gum
WPI Electrospun fibers α-tocopherol Fabra, López-Rubio,
and Lagaron (2016)
Whey protein Electrospray Folic acid Pérez-Masiá et al.
concentrate particles (2015)
Caseinate Electrospun fibers N/A Tomasula et al. (2016)
SPI Electrospun fibers Allyl isothiocyanate Vega-Lugo and Lim
(2009)
API Electrospun fibers Nisin Soto et al. (2016)
Zein Coaxial Rose hip seed oil Yao et al. (2016)
electrospinning
fibers
Electrospray Green tea catechins Anu Bhushani, Kurrey,
particles and
Anandharamakrishnan
(2017)
Electrospun CNMA Cerqueira et al. (2016)
interlayers fibers
Zein Electrospun fibres β-carotene Fernandez, Torres-
Giner, and Lagaron
(2009)
Gelatin Electrospray Polyphenols Gómez-Mascaraque,
particles Lagarón, and López-
Rubio (2015)
Gelatin Electrospun fibrils N/A Nieuwland et al. (2014)
Oil-based/biomass- Polycaprolactone Electrospun fibers N/A Martins et al. (2015)
derived monomers PVA Electrospun fibers Eugenol Kayaci, Ertas, and Uyar
(2013)
PEO Electrospun fibers N/A Sullivan et al. (2014)
PLA Coaxial N/A Nguyen, Chung, and
electrospinning Park (2011)
fibers
Polymers produced PHBV Electrospun fibers Zinc oxide Castro-Mayorga et al.
by natural or (2017)
genetically Kefiran Electrospun fibers N/A Esnaashari et al. (2014)
modified
Pullulan Electro-wet-spinning N/A Kong and Ziegler (2014)
microorganisms
fibers
10 NANOTECHNOLOGY APPLICATIONS IN THE FOOD INDUSTRY
The use of nanostructures for the encapsulation of functional ingredients has been presented as
one of the most interesting systems for the protection, delivery, and controlled release of bioactive
compounds and probiotics. It is known that functional ingredients can be very sensitive to different
conditions (light, temperature, and pH) (Altay and Okutan 2015). Moreover, the lipophilic or
hydrophilic nature of bioactive compounds can influence their behavior during the encapsulation
process. So the use of bio-based materials for functional ingredient incorporation is a subject of
special attention due to many applications with different objectives, namely, the following:
Encapsulation arises as a controlled delivery system where stability and functional performance
will depend on their internal and external morphologies. The encapsulation of the functional ingre-
dients in foods must ensure no undesirable impact on the organoleptic properties. At the same time, it
must maintain their physicochemical properties providing a controlled release, ensuring the activity of
the bioactive component when eaten. The major benefits of encapsulation come from small dimension
matrices with high surface/volume ratios. These factors will lead to higher solubility, better aggre-
gation stability, faster diffusion rates, and an increase in bioavailability (Davidov-Pardo, Joye, and
McClements 2015).
Several methods were already used and evaluated to produce encapsulation structures. Conven-
tional methods such as coacervation (Yang et al. 2015), spray drying (Pérez-Masiá et al. 2015),
nanoemulsion (Silva, Cerqueira, and Vicente 2012), and extrusion (Ramos et al. 2017) are commonly
used for encapsulation. Spray drying is one of the most commonly used in the food industry due to its
affordable operational costs. However, traditional methods can present some disadvantages such as the
loss of volatile compounds and of probiotic bacteria viability due to the temperature needed during the
process. Electrohydrodynamic processes appear as a novel method to encapsulate bioactive compo-
nents due to their easy-to-use characteristics and advantages such as one-step formulation and the lack
of need to use organic solvents or high temperature. Many studies were already performed and proved
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