Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73

Contents lists available at ScienceDirect

Food and Bioproducts Processing

journal homepage: www.elsevier.com/locate/fbp

New perspective in extraction of plant biologically

active compounds by green solvents

Marina Cvjetko Bubalo a , Senka Vidović b , Ivana Radojčić Redovniković a,∗ ,

Stela Jokić c
a University of Zagreb, Faculty of Food Technology and Biotechnology, 10000 Zagreb, Croatia
b University of Novi Sad, Faculty of Technology, Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia
c University of Josip Juraj Strossmayer in Osijek, Faculty of Food Technology Osijek, Franje Kuhaca 20, 31000 Osijek,

Croatia

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

Article history: In many industrial processes, large quantities of volatile and flammable organic solvents
Received 25 August 2017 are used in various reaction systems and separation steps define a major part of the envi-
Received in revised form 19 ronmental and economic performance of a process. Accordingly, a growing area of research
February 2018 in the development of green technologies is devoted to designing new, environmentally-
Accepted 2 March 2018 friendly, and tunable solvents the use of which would meet both technological and
Available online 10 March 2018 economical demands. A brief overview of the up to date knowledge regarding most proposed
green solvents, including supercritical and subcritical fluids (e.g. CO2 and water) and natural
Keywords: deep eutectic solvents is presented herein, with a special emphasis on green extraction of
Natural deep eutectic solvents plant biologically active compounds.
Green extraction © 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Green solvents
Subcritical water
Supercritical CO2
Plant biologically active compounds

Contents

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .52
2. Supercritical and subcritical solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.1. Supercritical fluid extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.2. Subcritical water extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3. Natural deep eutectic solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4. Future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

1. Introduction
development of new drugs (e.g. steroids and alkaloids), functional foods
(e.g. plant sterols and stanols as cholesterol-lowering ingredients in
Plants represent a valuable source of chemical compounds that are functional foods), and food additives (e.g. natural flavor, aroma and
traditionally used as the main source of components or ideas in the color) (Azmir et al., 2013). These compounds are referred to as bioac-
tive compounds due to their pharmacological or toxicological effects
in humans and animals. The typical bioactive compounds in plants
∗ are produced as secondary metabolites, generated through various
Corresponding author.
E-mail address: iradojci@pbf.hr (I. Radojčić Redovniković). biological pathways in secondary metabolism processes, and play an
https://doi.org/10.1016/j.fbp.2018.03.001
0960-3085/© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73 53

Table 1 – The six principles of green extraction (Chemat et al., 2012).

Principle Description

Innovation by selection of varieties and use of
renewable plant resources
Use of alternative solvents and principally water or
agro-solvents
Reduce energy consumption by energy recovery and
using innovative technologies
Production of co-products instead of waste to
include the bio- and agro- refining
industry
Reduce unit operations and favour safe, robust and
controlled processes
Aim for a non-denatured and biodegradable extract
without contaminants
In green extraction, fully renewable resources have to be favoured either with
intensive cultivation or in vitro growth of plant cells or organisms
The selection of a suitable solvent is based on workers’ safety, process safety,
environment protection and the sustainability of the process, meaning that green
solvent should be chemically and physically stable, low volatility, easy to use and
easy to recycle with the possibility of reuse. As green solvents water, supercritical
fluids (CO2 and water), solvents based on organic salts (ionic liquids and deep
eutectic solvents), and agrosolvents (e.g. ethanol, glycerol, methyl esters of fatty
acids of vegetable oil, terpenes) are considered.
Massive reduction of energy consumption through optimising existing processes,
recovery the energy liberated during the extraction process, assisting existing
processes with intensification, and a full process innovation (e.g. recuperating the
heat liberated during vapour condensation; the use of pulsed electric fields,
activation by microwaves or ultrasound).
The “Bio-refinery” concept can be considered as a facility that combines the
biomass conversion process with equipment to produce high value-added
compounds from agricultural and forest residues such as biofuels and biomaterials.
To be competitive industries involved in extraction of natural products (perfume,
cosmetic, pharmaceutical, food, and bio-fuel) have to combine process
intensification with cleaner and safer extraction protocols (more compact
production units and a reduced number of unit operations, energy and raw material
savings, process safety control, reduction in waste and ecological footprint).
To meet the requirements of the market and of the regulations, the extract must
meet a number of quality criteria; contrary to some popular misconceptions, the
“natural” state of the extract is no guarantee of its harmlessness to man and the
environment. The extracts must be obtained from precisely identified raw
materials; must have precise physico-chemical properties and be properly stored;
the extract should be free of all pollutants such as pesticide residues, heavy metals,
mycotoxins.

important role in protecting plants from biotic or abiotic stress (Dixon,
2001; Azmir et al., 2013).
According to biochemical pathways and chemical classes, bioac-
tive compounds in plants can be categorised in several main chemical
groups: glycosides (cardiac glycosides, cyanogenic glycosides, glucosi-
nolates, saponins and anthraquinone glycosides), phenolic compounds
(phenolic and hydroxycinnamic acids, stilbenes, flavonoids and anto-
cyanins), tannins (there are two distinct types of tannins; condensed
tannins, which are large polymers of flavonoids, and hydrolysable tan-
nins which are polymers composed of a monosaccharide core with
several catechin derivatives attached), mono- di- and sequi-terpenoids,
phenylpropanoids, lignans, resins, alkaloids, furocoumarines and
naphthodianthrones, proteins and peptides (Bernhoft, 2010). Typically,
extraction and isolation of bioactive compounds from the natural
sources proceed according to well-established procedures: (1) exhaus-
tive extraction (maceration, steam or hydro-distillation, pressing,
decoction, infusion, percolation and Soxhlet extraction); (2) additional
chemical treatment of the extracts in order to isolate target compounds
in a pure form (Chemat et al., 2012). Conventional extraction processes
are quite laborious, time-consuming, involve large amounts of solvents
such as hydrocarbons, alcohols and chloroalkanes since majority of
bioactive compounds are not soluble in water and, ultimately, may
cause some target molecule degradation and the partial loss of volatiles
(Cravotto et al., 2008). Above all, in spite of the high energy consumption
and the large amount of solvents, the yield is often very low (Chemat
et al., 2012). Therefore, in the past decade safer and more efficient
extraction techniques based on a reasonable compromise between eco-
nomic, social and environmental requirements, have been considered.
The concept of green chemistry was first used in 1991 when the
PT Anastas launched a specific programme of implementation of sus-
tainable development in chemical technology (US EPA, 2012). This
concept was based on 12 principles appearing as guidelines used to
design chemical products and processes that reduce or completely
remove the application and create harmful and dangerous substances
through the usage of chemicals and solvents barely detrimental or fully
unharmful to human health and the environment, as well as to design
energy efficient and safer processes and facilitate the usage of renew-
able feedstocks if possible (Anastas and Eghbali, 2010). Today, green
chemistry has surpassed the field of chemistry and is acknowledged
in various industrial fields, such as food technology and biotechnol-
ogy. Accordingly, the term green extraction has been introduced to
describe extraction techniques for by-products valorisation based on
green and sustainable technology through (i) improvement and opti-
mization of exciting processes; (ii) usage of non-dedicated equipment,
and (iii) innovation in processes and procedures including discovery
of alterative solvents, and is governed through six principles given in
Table 1 (Chemat et al., 2012).
The major part of the green techniques is summarized in principle
No. 2 which accounts for the design of new, environmentally-friendly
and tunable solvents which would meet both technological and eco-
nomic demands, which is also one of the priorities of EU environmental
policy and legislation for the period 2010–2050 as well as the reduc-
tion of hazardous solvents (Cvjetko Bubalo et al., 2015). According to
the principles of green chemistry, the selection of a suitable solvent
is based on workers’ safety (toxicity, carcinogenicity, mutagenicity,
absorption through the skin and respiratory system), process safety
(flammability, explosiveness, volatility, creating the potential perox-
ide), environment protection (ecotoxicity, persistence, groundwater
contamination, destruction of the ozone layer) and the sustainabil-
ity of the process (the ability of recycling and the possibility of reuse)
(Alfonsi et al., 2008), meaning that green solvent should be chemically
and physically stable, with low volatility, easy to use and easy to recycle
with the possibility of reuse. Therefore, in the last several years in order
to minimize the use of the organic solvents, which, due to their toxic-
ity have undesirable effects on the environment and on food and other
final products’ quality and safety, the interest for green extraction tech-
nologies has been greatly increased. For that reason, modern extraction
technologies which use safe and non-toxic solvents (such are water,
carbon dioxide, and ethanol) have been introduced and applied for the
extraction of various materials and compounds. Some of these tech-
nologies are: microwave assisted extraction (MAE), ultrasound assisted
extraction (UAE), accelerated solvent extraction (ASE) and pressurized
technologies, such are supercritical fluid extraction (SFE) and subcriti-
cal water extraction (SWE), also called superheated water extraction
54 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73

Table 2 – Advantages and disadvantages of extraction processes.

Extraction technique Advantages Drawbacks

SC-CO2 extraction • Gentle treatment of heat-sensitive materials (its • High pressures

moderate critical temperature of 31.2 ◦ C is a key issue for • High investment cost (requires a careful business
the preservation of bioactive compounds in extracts) plan contemplating the cost/effective analysis of
• Solvent — free products the desired compounds to be extracted)
• CO2 as solvent does not cause environmental problems • Phase equilibrium of the solvent/solute system is
and is physiologically harmless, germicidal and not complex, making design of extraction conditions
flammable. difficult
• CO2 is a Generally recognized as safe (GRAS) solvent • High polar substances (sugars, amino acids,
• CO2 is inexpensive solvent inorganic salts, proteins, . . .) are insoluble
• Due to low viscosity and relatively high diffusivity, • The use of high pressures leads to capital costs for
supercritical CO2 have enhanced transport properties plant, and operating costs may also be high so the
than liquids, can diffuse easily through solid materials number of commercial processes utilizing
and can therefore give faster extraction rates. supercritical fluid extraction is relatively small,
• Fragrances and aromas remain unchanged due mainly to the existence of more economical
• Selective extraction and fractionated separation processes.
• Pure extracts by means of few process steps
• Changeable solvating power (possibility of modifying the
density of the fluid by changing its pressure and/or
temperature)
• High solubility for non/low polar substances (for example
volatile compounds)
• possibility of direct coupling with analytical
chromatographic techniques such as gas
chromatography (GC) or supercritical fluid
chromatography (SFC)

SWE • SWE use water as extraction solvent, which is safe,
non-toxic, non-flammable and environment friendly.
• Obtained extracts are safe, without trace of any toxic
solvents.
• SWE is characterized by higher diffusion into the plant
matrix and increased mass-transfer properties in
comparison to other extraction techniques.
• It is faster extraction technique in comparison to others.
• SWE can be applied for extraction of low-polar as well as
non-polar compounds.
• Application of low cost and easily available extraction
solvent and short extraction times minimize the cost of
extraction process.
• Uncomplicated equipment.
• The high investments costs.
• At elevated temperatures, the risk of unwanted
reactions (caramelization, Maillard reactions) is
increased and toxic compounds can be formed.
• Increased risk of tub clogging induced by
reactions of caramelization.
• At elevated temperatures risk of hydrolysis
reactionis increased as well as possible
degradation of temperature sensitive compounds
can be expected.
• At higher temperature extraction could be less
selective due to an increase of solubility of other
matrix compounds.
• Due to severe process conditions SWE equipment
need to be made of expencive high quality
materials with increases general corrosion
resistance and of increased strength at elevated
temperatures.

NADES • Simple and inexpensive preparation
• Sustainable production with 100% atom economy
production and theoretically does not generate waste
• NADES are tailor-made solvents and 108 combinations
are estimated
• It is possible to fine-tuned physicochemical
characteristics for the specific purpose.
• A wide polar range, with high degree of solubilisation
strength for different compounds
• Low toxicity and biodegradable
• Non-volatility and non-flammability
• The cost of NADES is comparable to conventional solvent
• The high viscosities of NADES could be a
restrictive (lower extraction efficiencies, the
energy required for stirring and pumping)
• NADES have almost zero vapor and recovery of
target compound could be difficult
• Problems with NADES recovery and/or recycling
• Currently, the application of NADES on an
industrial scale is possible only when the extract
is directly used without expensive downstream
purification steps.

or pressurized hot water extraction (PHWE). Apart from the advan-
tage which refers to the use of “green and safe” extraction solvent,
most of the mentioned extraction technologies are much more effi-
cient than the conventional ones. Selective extraction in the case of
most modern extraction technologies is enabled by the simple change
of the process parameters (temperature, pressure, flow, power, etc.),
which make them appropriate for the extraction of variety of differ-
ent bioactive compounds without the change of the applied extraction
solvent. Therefore, according to Gil-Chávez et al. (2013) they enable
the production of highly purified products which make them avail-
able for an extensive range of applications. Also, solvents based on
organic salts (ionic liquids and deep eutectic solvents), and agrosol-
vents (e.g. ethanol, glycerol, methyl esters of fatty acids of vegetable
oil, terpenes) are considered as well. However, a brief overview of the
up to date knowledge regarding most proposing green solvents includ-
ing supercritical and subcritical fluids (e.g. CO2 and water) and natural
deep eutectic solvents is presented herein, with a special emphasis on
green extraction of plant biologically active compounds. Some charac-
teristics with general and specific advantages and disadvantages of the
proposed methods are presented in Table 2.
 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73
2. Supercritical and subcritical solvents
2.1. Supercritical fluid extraction
SFE of plant biologically active compounds is a topic of grow-
ing interest. In our previous paper (Jokić et al., 2015) we
gave a detailed review about the design of SFE system. SFE
allows the processing of plant material at low temperatures,
hence limiting thermal degradation and also avoids harmful
toxic solvents. SFE utilizes supercritical fluids, which above
their critical point, exhibit liquid-like (solvent power, negligi-
ble surface tension), as well as gas-like (elevated diffusivity,
low viscosity) properties (Capuzzo et al., 2013). More than
90% of SFE have been performed with carbon dioxide (CO2 ),
as a supercritical solvent because it possesses low critical
constants (Tc = 31.1 ◦ C, Pc = 7.38 MPa) and inert nature; it is
non-toxic, non-explosive, inexpensive, readily available and
is easy removable from the product. CO2 is also generally
recognized as a safe (GRAS) solvent, so products extracted
with supercritical CO2 are safe with respect to human health
(Cvjetko Bubalo et al., 2015). Supercritical CO2 is a very nonpo-
lar solvent, has a polarity comparable to liquid pentane and is
compatible for the extraction of weakly polar compounds of
low molecular weight such as carotenoids, triglycerides, fatty
acids, aromas etc. (Herrero et al., 2006). The general rule is that
solubility of substances in supercritical CO2 decreases with the
increase in number of polar functional groups (e.g., hydroxyl,
carboxyl, amino, and nitro). So, supercritical CO2 polarity
index makes it hardly suitable for the extraction of polar sub-
stances (for example, phenolic compounds). To overcome this
problem, practical approaches involve the use of polar co-
solvents or co-modifiers/entrainers. Ethanol and methanol
are mainly used as co-solvents to change the polarity of the
supercritical fluid and to increase its solvating power with
respect to targeted biologically active compounds (Cvjetko
Bubalo et al., 2015). Water can also be added as a modifier,
but compared to methanol, only 0.3% (v/v) of water can be
completely miscible with CO2 and because of that fact, water
cannot sufficiently improve the polarity of CO2 as much as
methanol can. Modifiers can be introduced as mixed fluids
in the pumping system with a second pump and a mixing
chamber, or by simply injecting the modifier as a liquid into
sample before the extraction. The second way is less suc-
cessful because it leads to concentration gradients within
the sample. The third way, very rarely applied, is the usage
of a cylinder tank of the modified CO2 (Pourmortazavi and
Hajimirsadeghi, 2007). For example, if we look at grape seeds
(material that has been explored a lot in the last few years)
supercritical CO2 extraction with/without modifiers, it can be
seen that the modifier has a main influence on the SFE pro-
cess of grape seeds. Palma et al. (1999) showed that with the
increase of the polarity of CO2 using methanol, it is possible to
fractionate the extracted compounds. Using pure CO2 in the
extraction of grape seeds, authors obtained mainly fatty acids,
aliphatic aldehydes and sterols, while the addition of a mod-
ifier resulted in the obtainment of the phenolic compounds
(mainly catechin, epicatechin and gallic acid).
Every fluid can be used as a supercritical solvent. How-
ever, the technical viability (critical properties), toxicity, cost
and solvation power determine the best-suited solvent for a
particular application. Ethane, propane and dimethyl ether
have been used as supercritical solvents for the extraction
of plant biologically active compounds. These solvents have
55
critical points that are comparable with CO2 and have higher
polarity index than CO2 , resulting in the extraction of more
polar compounds. However, experimental results show that
supercritical CO2 offers a wider range for the fractionating of
the extracted compounds changing operative pressure in the
extractor or separators (Pereira et al., 2010). Some published
reports proposed nitrous-oxide, N2 O, as a choice of the extrac-
tion fluid for the analytical SFE (Alexandrou et al., 1992; Raynie,
1993). Unfortunately, this fluid has been shown to cause vio-
lent explosions when used for samples having high organic
content and should, therefore, be used only if necessary. Other
more exotic supercritical fluids, which have been used for SFE,
were sulfur hexafluoride (SF6) and freons, especially CHClF2
(Freon-22) (Levy et al., 1991). In some research, water (H2 O) in
supercritical state was also used as a solvent despite its high
critical temperature and pressure (Tc = 374 ◦ C, Pc = 22.1 MPa).
Furthermore, corrosive nature of H2 O under these critical
conditions has limited its practical applications (Ong et al.,
2006). Nevertheless, water as pretreatment of plant material
or added to supercritical CO2 as a co-solvent has shown the
influence on the qualitative and quantitative composition of
the extract (Nguyen et al., 1991; Mehr et al., 1996; Jokić et al.,
2017; Ivanović et al., 2011).
Today, SFE is not only used in laboratories, namely, it is,
even more often, also used on a large scale for a lot of industrial
applications. The most developed application od SFE is mainly
for food products (decaffeination of coffee and tea), food ingre-
dients (hops and aromas, colorants, vitamin-rich extracts,
specific lipids, etc.), nutraceuticals/phytopharmaceuticals and
removal of pesticides from rice. But also cleaning purposes
were tested such as the decontamination of soils the removal
of residual solvents from pharmaceutical products, the extrac-
tion of flame retardants from electronic waste or precision
degreasing and cleaning of mechanical and electronic parts.
The first industrial plant was built in Germany in 1978, since
the research on extraction of caffeine from coffee beans was
patented in 1964 (Zosel, 1964). Caffeine is soluble in pure CO2,
but for the decaffeination process of coffee and tea water
saturated CO2 has to be used, otherwise, the caffeine is imple-
mented too strong in the matrix of the raw material and
cannot be extracted. From the beginning of ‘70s to the begin-
ning of’ 90s nearly 50% of the whole production capacity
for the decaffeination of coffee and tea changed to SFE pro-
cess. Also in the last few decades, nearly all producers of
hop extracts changed to SFE process. Further applications on
a large scale are related to the extraction of nicotine from
tobacco, extraction of spices (oleoresins), medicinal herbs and
high value fats and oils. These plants are much smaller com-
pared to decaffeinated plants and the hop plants (Skala et al.,
2002). Also, SFE is used for the removal of pesticides from
material. The first industrial plant for the extraction of pes-
ticides from cereals was built in Taiwan in the end of 1999.
SFE had a wide application area and is capable of extracting a
wide range of diverse compounds from variety of raw material
matrices and it is very hard to present it in one paper. So we
collected the most important reviews about SFE of bioactive
compounds which are presented in Table 3.
For easier understanding, the process of SFE of certain
natural compounds can be divided into two categories: (1)
undesired substances which need to be removed from plant
material, (2) biologically active compounds that are desired
to be extracted from the plant material. In the first group,
the most common applications are: decaffeination of cof-
fee and tea, defatting or deoiling of press cakes, removal of
56 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73

Different factors, such as particle size, porosity, moisture,

Table 3 – The selected reviews on SFE of bioactive
compounds. nature of the matrix, as well as process parameters such as
pressure, temperature, solvent flow rate, can affect the SFE
Targeted group Reference
results.
Fatty acids Sanchez-Camargo et al. Raw material before extraction needs to be ground and
Carotenoids (2017) average particle size of the milled material should be between
Phenolics 0.4–0.8 mm. However, if the particles are too small, although
Terpenoids
better for mass transfer, they decrease the fluidized bed veloc-
Phytosterols
Tocopherols
ity, can cause clogging of filters and can tend to channeling
Tocotrienols inside the extraction bed, causing a loss of efficiency and yield
Phenolic compounds Da Silva et al. (2016) of the process. So, the physical structure of the matrix is of crit-
Fatty acids ical importance, as the extraction efficiencly is related to the
Carotenoids ability of the supercritical CO2 to diffuse within the matrix.
Volatiles
The extraction pressure is the main parameter that influ-
Resveratrol Barba et al. (2016)
ences the extraction efficiency. As a general rule, the solubility
Polyphenols
Fatty acids Herrero et al. (2013) of the desired compound increases with the increase of the
Essential oil extraction pressure, which is directly a result of the increased
Phenolic compounds solvent density. Consequently, the higher the extraction pres-
Alkaloids sure, the smaller the volume of fluid necessary for a given
Plant flavors and fragrances Capuzzo et al. (2013) extraction. However, high pressure is not always recom-
Fats, oils Temelli (2009)
mended for all material and desired compounds. For example,
Seed oils Catchpole et al. (2009)
it is a general rule to use lower pressures (from 9 to 10 MPa)
Polyunsaturated fatty acids
Carotenoids and mild temperatures (from 40 to 50 ◦ C) if we want to extract
Phospholipids essential oil from aromatic and medicinal herbs. In these pro-
Essential and volatile oils Pourmortazavi and cess conditions, all the essential oil components are largely
Hajimirsadeghi (2007) soluble in supercritical CO2 . Higher pressures result in higher
Vitamin additives Brunner (2005) solubility, but also in the complex total extract and difficult
De-alcoholised wine/beer
analysis, because at higher pressures, essential oil compo-
Defatted potato chips
Encapsulate liquids
nents are extracted together with cuticular waxes. Opposite
Seed oils Skala et al. (2002) to essential oil, seed oils need to be extracted at higher press-
Essential oils sures because tryglycerids forming seed oil are readily soluble
Volatile oils in supercritical CO2 at temperature of 40 ◦ C and pressures
Lipids/fatty acids Sahena et al. (2009) greater than 28 MPa (Reverchon and De Marco, 2006).
Fats, oils, lipids King (2002)
The effect of extraction temperature depends on the
applied pressure and is very complex, due to the combina-
pesticides from cereals, extraction of nicotine from tobacco, tion of two variables, density and vapour pressure. Briefly,
reduction of the alcohol content in beverages (de-alcoholised the effect of temperature on the extraction rate, at constant
beer and wine) and cholesterol from eggs. Such group of pro- pressure, is due to two mechanisms: an increase in the pro-
cesses requires a high selectivity for targeted compounds to cess temperature increases the solubility due to solute vapour
be removed in order to maintain flavour, appearance, smell pressure enhancement and reduces the solubility due to the
and shape of the treated raw material, which represent the decrease in the solvent density. At one point we have the
main product (Skala et al., 2002). The second group consists “crossover effect” where the solubility of solute is no longer
of biologically active compounds that we want to extract from dependent on the density of supecritical fluid (King, 1997). This
the raw materials: biologically active compounds of medici- crossover phenomena is generally reported for SFE of seed
nal herbs (antioxidants), essential oils (volatile compounds), oils. To summarize, temperature affects the volatility of the
nutraceuticals and pharmaceuticals (lycopene, astaxanthin, solute, and it is very difficult to predict its influence due to its
hyperforin etc.), seed oils (tocopherols etc.), oleoresins from dependence on the nature of raw material. For a non-volatile
spices, and natural colours (carotene, chlorophyll) etc. solute, a higher temperature would result in lower extraction
Firstly, for the extraction of the desired active compound, recovery. On the other hand, for a volatile solute, there is a
the compound must be soluble in supercritical CO2 at a mod- competition between its solubility in CO2 (which decrease as
erate pressure and temperature. The solubility can vary in a the temperature increases) and it volatility (which rises with
wide range by changing the extraction pressure and tempera- increasing temperature). Also, there is a lot of research where
ture. Furthermore, if small amount of a modifier (mentioned in temperature of the supercritical fluid did not influence the
the text above) is added to CO2 , it increases solubility, as well extraction efficiency. In Table 4 we listed some of the most
as improves the separation characteristics by controlling the commonly used applications of SFE (plant origin) together
solubility of the solvent. So, during the SFE, it is very important with the extraction parameters (temperature, pressure, co-
to understand the effects of the different parameters on the solvent).
yield and composition of the obtained extracts. The knowl-
edge of these effects is not only useful for the optimization 2.2. Subcritical water extraction
and economic evaluation of the process, but also for the abil-
ity to predict the SFE process, which is useful for scale-up, In the recent years, among modern extraction technologies,
as well as for the design and the optimization of an indus- SWE has attracted great attention due to its unique proper-
trial plant (Reverchon and De Marco, 2006; Pourmortazavi and ties and a wide variety of possible applications. A number of
Hajimirsadeghi, 2007; Mezzomo et al., 2009; Jokić et al., 2012). review articles have identified subcritical water as an effec-
 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73 57

Table 4 – Supercritical CO2 extraction of plant material (selected examples of plant origin).
Material Extract Modifier T (◦ C) P (bar) Reference

Almond Oil, tocopherols 35–50 350–550 Leo et al. (2005)

Angelica root Oil 40 120 Doneanu and Anitescu (1998)
Aniseed Essential oil 30 80–180 Rodrigues et al. (2003)
Annatto seed Bixin 40–60 200–300 (Degnan et al. (1991))
Aloe vera leaves ␣-Tocopherol Methanol 32,41,50 350,400,450 Hu et al. (2005)
Apricot seed Oil Ethanol 40–70 300–600 Özkal et al. (2005)
Basil (leaves and flowers) Total extract, linalool, 40–60 100–300 Zeković et al. (2014)
eugenol, d-cadinene
Black pepper Oleoresin, piperine 35–55 200–300 Dang and Phan (2014)
Borage seed Oil 40–60 200–300 Kotnik et al. (2006)
Canola seed Oil 40–60 200–250 Pederssetti et al. (2011)
Caraway seed Carvone, limonene 32–75 75–300 Baysal and Starmans (1999)
Carrots ␤-Carotene 57 250 Subra et al. (1998)
Cashew nut shell Oil 60 200–300 Patel et al. (2006)
Celery Essential oil 40 100 Mišić et al. (2008)
Chamomile ␣-Bisabolol, chamazulene, 30–40 100–250 Kotnik et al. (2007)
matricine
Cherry seed Oil 40–60 180–220 Bernardo-Gil et al. (2001)
Chia seed Oil 40–80 136–408 Uribe et al. (2011)
Chilli pepper Capsaicinoids 40–80 100–400 Perva-Uzunalić et al. (2004)
Citrus peel Naringin 60 95 Giannuzzo et al. (2003)
Cocoa beans Methylxanthines 70 200–400 Mohamed et al. (2002)
(caffeine,theobromine)
Cocoa butter
Cocoa shell Theobromine 50–85 150–450 Rossi (1996)
Coffee husk Caffeine, chlorogenic acid 40–60 100–300 Andrade et al. (2012)
Coriander seed Oil 35 200–300 Illésa et al. (2000)
Corn germ Oil 35–86 210–525 Rebolleda et al. (2012)
Cotton seed Oil 60–80 350–550 Bhattacharjee et al. (2007)
Egg yolk Phospholipids 40 517 Boselli and Caboni (2000)
Elderberry pomace Anthocyanins Ethanol, H2 O 40 210 Seabra et al. (2010)
Eucalyptus Essential oil 50 90 Della Porta et al. (1999)
Fennel Essential oil, trans-anethole, 40 81 Simándi et al. (1999)
fenchone
Flax seed Oil 50–70 300–500 Özkal (2009)
Ginger Oleoresin Ethanol, 25–35 200–250 Zancan et al. (2002)
isopropanol
Ginkgo leaves Terpenes, flavonoids 60–110 242–312 Chiu et al. (2002)
Grape seed Phenolic compounds Methanol 35 455 Palma et al. (1999)
Grape seed Oil 40,50,60 200,300,400 Jokić et al. (2016)
Grape skin Resveratrol Ethanol 40 150 Marti et al. (2001)
Guarana seed Caffeine Water 40–70 100–400 Saldaña et al. (2002)
Hemp seed Oil 40–60 300–400 Aladić et al. (2015)
Hiprose Total extract 35 250 Illés et al. (1997)
Hop Essential oil 40 150,300 Zeković et al. (2007)
Horsetail Oleoresin 30,40 120–300 Michielin et al. (2005)
Jojoba seed Oil Hexane 70–90 200–600 Salgin et al. (2004)
Lavender Essential oil, 40–60 100–300 Jerković et al. (2017)
monoterpenes, coumarin,
herniarin
Lemongrass Essential oil 23–50 85–120 Carlson et al. (2001)
Lovage Essential oil 40–50 80–350 Daukšas et al. (1999)
Marjoram leaves Essential oil 40–50 80–120 Reverchon (1992)
Marigold flowers Total extract 20–40 120–200 Campos et al. (2005)
Mate tea leaves Caffeine, theophylline, 40–70 138–255 Saldaña et al. (2000)
theobromine
Melon seed Oil 40–80 200–400 Nyam et al. (2011)
Neem seed Nimbin 35–60 100–260 Tonthubthimthong et al. (2001)
Nutmeg Oil 23 90 Spricigo et al. (1999)
Olive pomace Oil 40–50 100–300 De Lucas et al., 2003
Orange peel Essential oil 40 100 Jerković et al. (2015)
Oregano leaves Flavonoids Ethanol 40–60 150–350 Cavero et al. (2006)
Palm kernel Oil 40–80 345–483 Zaidul et al. (2007)
Paprika Carotenoids, tocopherol, 35–55 100–400 Daood et al. (2002)
capsaicinoids
Parsley seed Oil 35–45 100–150 Louli et al. (2004)
Passion fruit seed Oil 40–60 150–250 Cardoso De Oliveira et al. (2013)
Peach seed Oil Ethanol 30–50 100–300 Mezzomo et al. (2010)
Poppy seed Oil 50–70 210–550 Bozan and Temelli (2003)
 58 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73

– Table 4 (Continued)
Material Extract Modifier T (◦ C) P (bar) Reference

Pumpkin seed Oil 35–75 152–345 Mitra et al. (2009)

Rape seed Oil 40–60 250–350 Yu et al. (2012)
Rice brain ␥-Oryzanol, tocols 40–60 276–414 Yoon et al. (2014)
Rosehip seed Oil 40–80 150–450 Machmudah et al. (2007)
Rosemary carnosic acid, carnosol 100 355 Tena et al. (1997)
Safflower seed Oil 35–60 220–280 Han et al. (2009)
Sage Carnosolic acid Ethanol 100 250,350 Dauksas et al. (2001)
Sea buckthorn Tocopherols, lycopene, Methanol, 35–55 150–350 Kagliwal et al. (2011)
␤-carotene ethanol,
2-propanol
Sesame seeds Oil 40–60 190–250 Corso et al. (2010)
Soybean seeds Oil 40–60 300–500 Jokić et al. (2012)
Savory Total extract, carvacrol 40–60 100–350 Vladić et al. (2016)
Thyme Total extract, thymol, 40 80–400 Zeković et al. (2000)
carvacrol
Tomato skin and seed Carotenoids, tocopherols, 40–80 300–460 Vagi et al. (2007)
sitosterols
Walnut Oil Ethanol 40–60 300–500 Salgin and Salgin (2006)
Wheat germ Total extract, phenolics, 40–60 148–602 Gelmez et al. (2009)
tocopherols
Yarrow Essential oil 40–60 100 Bocevska and Sovová (2007)

tric constant of water accounts 27, while with the further

Table 5 – Properties of water at different conditions and
in different state (Brunner, 2014).
Property Water at normal Near-critical Supercritical
conditions water water
T (◦ C) 25 350 400
P (bar) 1 250 500
 (kg m−3 ) 997.45 625.45 577.79
ε (–) 78.5 14.86 12.16
pKw (–) 14.0 11.5 11.5
tive solvent, catalyst and reactant for hydrolytic conversions
and extractions (Brunner, 2009). SWE is an environmentally
friendly extraction technology, which uses water as an extrac-
tion solvent at temperatures between 100 ◦ C and 374 ◦ C, and
at high enough pressure to keep the water in the liquid state
(Ramos et al., 2002). At the temperature above 374 ◦ C and pres-
sure above 220 bar, water is considered to be in supercritical
state. The properties of water at normal conditions, subcriti-
cal/near critical state and supercritical state are presented in
Table 5. As can be seen from Table 5, with the change of extrac-
tion temperature and pressure the main properties of water,
as an extraction solvent, are changed.
SWE attracted great attention, especially due to a sig-
nificant change of water properties caused by altered
temperature. Namely, at ambient conditions water is con-
sidered an extremely polar solvent, and its polarity is
characterized by a dielectric constant of around 80. In this
state, water is suitable for the extraction of highly polar com-
pounds. But, at the temperature between 100 and 374 ◦ C, and
under high enough pressure to keep the water in the liq-
uid state, the polarity of water considerably decreases and it
becomes suitable for the extraction of both, polar and non-
polar compounds. This is caused by a dramatical drop of
the dielectric constant with increasing temperature. As an
example, in the subcritical state, the water dielectric constant
decreases to about 33 at 200 ◦ C and this value is similar to
some organic solvents, such as methanol (Herrero et al., 2006;
Ibañez et al., 2012; Gil-Chávez et al., 2013), which is often
used for the extraction of compounds of moderate polarity.
According to Jo et al., at the temperature of 250 ◦ C, the dielec-
increase of temperature to 300 ◦ C, it drops to 20 (Jo et al., 2013).
Therefore, by achieving low polarities at elevated tempera-
tures, the SWE technology is able to produce high extraction
yields and fast extraction times for a number of hydrophobic
organic compounds (Herrero et al., 2006). At elevated tempera-
tures in a subcritical state, surface tension, water viscosity and
density, aside from polarity, are significantly lowered too. At
elevated temperatures the surface tension of water decreases;
this enables enhanced water wetting of the extracting mate-
rial and the dissolution of targeted compounds in the solvent
much faster. Decreased water viscosity is enhancing its pen-
etration inside the extracting material and thus improving
the diffusion rate. The improved diffusion rate enables accel-
erated extraction as well. The density of water at saturated
pressure goes from 0.995 g mL−1 at 25 ◦ C, to 0.579 g mL−1 at
350 ◦ C. According to Plaza and Turner, in addition to the men-
tioned properties, the self-ionization properties of water also
vary with temperature. Thus, the dissociation constant (Kw )
of water increases with two units from 1.0 × 10−14 , at 25 ◦ C, to
1.2 × 10−12 , at 350 ◦ C, with the maximum value of 4.9 × 10−12
at 250 ◦ C. This implies that the pH changes from about 7.0 to
5.5 (Plaza and Turner, 2015).
These unique properties of subcritical water, as well as the
fact that water as a solvent is easily available, safe, low cost,
non-toxic, non-flammable, and environmentally friendly, lead
to a number of studies on the possibility of SWE application
for the extraction/separation/isolation of various compounds,
bioactive and many others. Until now, SWE has been applied
for the extraction of antioxidants (phenols and flavonoids),
essential oils, fatty acids, oils, carotenoids, sugars, manni-
tol, pectin, resorcinol, etc. Aside from that, the application
of SWE for the isolation of PAHs from soils has been stud-
ied intensively. Most studies on SWE are investigations on the
extraction of antioxidants, e.g. phenolic compounds, from a
wide variety of sources (herbs, fruits, seeds, roots, by-products,
waste etc.) (Table 6). They are relatively polar compounds and
compounds of different stability, and this should be taken into
account during the selection of the adequate extraction tech-
nology and during the set-up of the appropriate extraction
conditions. According to Plaza and Turner, optimal conditions
 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73 59

Table 6 – Application of SWE for phenolic compounds extraction.

Material for Targeted compound SWE operating conditions Reference
extraction/resource

Mango peels Total phenols Investigated range: Tunchaiyaphum et al.

Temperature: 60–220 ◦ C, (2013)
Extraction time: 30–120 min
Solid to water ratio: 1:10–1:50
pH of solution: 2–8
Optimal conditions/highest recovery:
180 ◦ C, 90 min, solid to water ratio 1:40 and pH 4
Pomegranate seed Total phenols Investigated range: He et al. (2012)
residues (Punica Temperature: 80–280 ◦ C
granatum L.) Extraction time: 15–120 min
Pressure: 60 bar
Solid to water ratio: 1:10–1:50
Optimal conditions/highest recovery:
220 ◦ C, 30 min, solid to water ratio was 1:40
Uva ursi herbal dust Total phenols and total Investigated range: Naffati et al. (2017)
flavonoids Temperature: 120–220 ◦ C
Extraction time: 10–30 min
Pressure: 30 bar
Added acidifier, HCl: 0–1.5%
Optimal conditions/highest recovery:
151.2 ◦ C, 10 min, 1.5% HCl
Potato peel Total phenols Investigated range: Singh and Saldaña
Chlorogenic acid, Temperature: 100–240 ◦ C (2011)
Caffeic acid, Gallic acid Extraction time: 30–120 min
Pressure: 60 bar
Optimal conditions/highest recovery:
160–180 ◦ C, 6 bar, 60 min
Cinnamon bark Total phenols Investigated range: Khuwijitjaru et al. (2012)
(Cinnamomum Temperature: 150 and 200 ◦ C
zeylanicum) Extraction time:10–60 min
Pressure: 60 bar
Optimal conditions/highest recovery:
200 ◦ C, 60 min, 60 bar
Wild garlic (Allium Total phenols and total Investigated range: Tomšik et al. (2017)
ursinum L.) flavonoids Temperature: 120–200 ◦ C
Extraction time: 10–30 min
Added acidifier, HCl: 0–1.5%
Optimal conditions/highest recovery:
180.92 ◦ C, 10 min, added acidifier 1.09%.
Citrus pomaces Total phenols Investigated range: Kim et al. (2009)
Temperature: 25–250 ◦ C
Extraction time: 60 min
Pressure: 10–50 bar
Optimal conditions/highest recovery:
200 ◦ C, 14 bar, 60 min
White grape pomace Total phenols Investigated range: Pedras et al. (2017)
Temperature: 170–210 ◦ C
Extraction time: 30 min
Pressure: 100 bar
Optimal conditions/highest recovery:
210 ◦ C, 100 bar, 30 min
Oregano leaves Total phenols Investigated range: Rodrıguez-Meizoso et al.
(Origanum vulgare L.) Temperature: 100–200 ◦ C (2006)
Extraction time: 15 and 30 min
Pressure: 103 bar
Optimal conditions/highest recovery:
150 ◦ C, 30 min, 103 bar
Winter savory (Satureja Total phenols and total Investigated range: Vladic et al. (2017)
montana L.) flavonoids Temperature: 79.15–220.5 ◦ C
Extraction time: 5.9–34.1 min
Pressure: 30 bar
Optimal conditions/highest recovery:
220 ◦ C, 20.8 min, 30 bar
Spent coffee grounds Total phenols Investigated range: Temperature: 110–190 ◦ C Xu et al. (2015)
(Coffea arabica L.) Extraction time: 15–75 min
Pressure: 50
Optimal conditions/highest recovery:
177.00 ◦ C, 55 min, 50 bar
 60 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73

– Table 6 (Continued)
Material for Targeted compound SWE operating conditions Reference
extraction/resource

Ginger (Zingiber Gingerol Investigated range: Yulianto et al. (2017)

officinale) Temperature: 130–140 ◦ C
Extraction time: 10–40 min
Pressure: 2 bar
Optimal conditions/highest recovery:
130 ◦ C, 20 min, 2 bar
Black tea Myrcetine and Investigated range: Cheigh et al. (2015)
Quercetin* Temperature: 110–200 ◦ C
Kampherol** Extraction time: 5–15 min
Pressure: 101 bar
Optimal conditions/highest recovery:
170 ◦ C, 15 min, 101 bar*
200 ◦ C, 15 min, 101 bar**
Celery powder Myrcetine and Investigated range: Cheigh et al. (2015)
Quercetin* Temperature: 110–200 ◦ C
Kampherol** Extraction time: 5–15 min
Pressure: 101 bar
Optimal conditions/highest recovery:
170 ◦ C, 15 min, 101 bar*
200 ◦ C, 15 min, 101 bar**
Ginseng leaf Myrcetine and Investigated range: Cheigh et al. (2015)
Quercetin* Temperature: 110–200 ◦ C
Kampherol** Extraction time: 5–15 min
Pressure: 101 bar
Optimal conditions/highest recovery:
170 ◦ C, 10 min, 101 bar*
200 ◦ C, 15 min, 101 bar**
Tumeric rhizomes Curcumin Investigated range: Kiamahalleh et al. (2016)
(Curcuma longa L) Temperature: 120–160 ◦ C
Extraction time: 6–22 min
Particle size: 0.6–2 mm
Pressure: 10 bar
Optimal conditions/highest recovery:
140 ◦ C, 10 bar, 14 min, 0.71 mm
Onion skin Quercetin Investigated range: Ko et al. (2011)
Temperature: 100–190 ◦ C
Extraction time: 5–30 min
Mixture ration of onion skin and diatomaceus
earth: 0.5:3.5–2:2
Pressure maintained from 90 to 131 bar
Optimal conditions/highest recovery:
165 ◦ C, 15 min, mixture ratio of 1.5:2.5, from
90to131 bar

*,** Correspond to optimal SWE operating conditions given in next column.

for different groups of phenolic compounds vary greatly, and
e.g. for flavonoids which are extremely labile phenolic com-
pounds, whose stability depends on pH, generally require
lower extraction temperatures in SWE (Plaza and Turner, 2015).
According to the same authors, in SWE, phenolic compounds
have usually been extracted up to temperatures of 150 ◦ C, and
for the extraction time from 1 to 60 min (Plaza and Turner,
2015). But, several studies have revealed that in the case of cer-
tain sources and certain phenolics even higher temperatures
and/or longer extraction time can be applied (Pedras et al.,
2017; Vladic et al., 2017; Tunchaiyaphum et al., 2013; He et al.,
2012; Khuwijitjaru et al., 2012; Kim et al., 2009).
Many studies revealed the higher efficiency of phenolic
compounds extraction using SWE over conventional extrac-
tion technologies. In the study by Ko et al., the efficiency
of SWE was compared with conventional extraction tech-
nologies; it was found that SWE yielded over eight, six- and
fourfold higher concentration of quarcetin in comparison to
extraction technologies using ethanol, methanol and water at
the atmospheric boiling point, respectively (Ko et al., 2011).
Pedras et al., in the study on SWE of white grape pomace,
explained the higher efficiency of SWE in comparison to con-
ventional technologies by ephasizing the fact that phenolic
compounds in white grape pomace are entrapped within a
lignocellulose structure, and their release requires hydroly-
sis of the lignocellulosic structure. On the other hand, lignin
is rich in polyphenols, and its partial degradation could also
contribute to the phenolic content (Pedras et al., 2017). Antho-
cyanins extraction from fruit berry substrates, investigated by
King et al., showed that SWE provided an equivalent or bet-
ter results than those obtained using conventional ethanol
extraction (King et al., 2003). According to Rangsriwong et al.
(2009) phenolic compounds were extracted from Terminute-
salia chebula Retz fruits also by application of SWE. In this
study the comparison was made between SWE and Soxhlet
extraction methods. The result revealed that, SWE hydrolysis
required only 37.5 min to recover highly substantial amount
of phenolic compounds while soxhlet extraction method
 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73
required more than 2 h reaction time to achieve maximum
yield of phenolic compounds.
In the study by Singh and Saldaña, where recovery of eight
phenolic compounds (gallic acid, chlorogenic acid, caffeic
acid, protocatechuic acid, syringic acid, p-hydroxyl benzoic
acid, ferulic acid and coumaric acid) from potato peel using
conventional and SWE technology was investigated, the use
of SWE resulted in higher amounts of phenolics (81.83 mg
100 g−1 ) than the amounts obtained with methanol extraction
(46.36 mg 100 g−1 ) or with ethanol extraction (29.52 mg 100 g−1 )
(Singh and Saldaña, 2011).
The efficiency of SWE differs from conventional extrac-
tion technologies not only by the total phenolic yield, but
also by the quality and number of extracted individual phe-
nolic compounds. Namely, in the study on SWE of phenolic
compounds from cinnamon bark, Khuwijitjaru et al. noticed
that obtained subcritical water extracts contained five pheno-
lic compounds (caffeic, ferulic, p-cumaric, protocatehuic and
vanillic acids), while only three compounds were identified in
the extract obtained by conventional organic solvent extrac-
tion (Khuwijitjaru et al., 2012). The study by Singh and Saldana,
on the recovery of eight phenolic compounds from potato peel,
revealed that two major phenolic compounds (gallic, 28.56 mg
100 g−1 , and caffeic, 12.22 mg 100 g−1 ) from potato peel were
more efficiently extracted with pure methanol, as their recov-
ery with ethanol and subcritical water was lower (8.62 and
5.18 mg 100 g−1 , and 9.23 and 14.59 mg 100 g−1 , respectively).
But, the recovery of gallic acid was low with either methanol
extraction (0.46 mg 100 g−1 ) or ethanol extraction (0.60 mg
100 g−1 ), while SWE yielded significantly higher yield, 29.56 mg
100 g−1 of this phenolic acid at 180 ◦ C (Singh and Saldaña,
2011).
Aside from its use for the extraction of antioxidant com-
pounds, SWE has been applied for the isolation of essential oils
from various plant materials (Table 7). Generally, in SWE, the
change in temperature will result in a change of components
and compositions of the extracted essential oils. According
to several studies (Gámiz-Gracia and Luque de Castro, 2000;
Ozel et al., 2003; Khajenoori et al., 2009), in SWE with the
increase of temperature, if the target compound is an essen-
tial oil, the increase of yield can be expected up to 150 ◦ C, after
that the yield decreases, and this is caused by the degradation
of the essential oil components. According to Gámiz-Gracia
and Luquede Castro, from 150 ◦ C to 175 ◦ C the yield of most
of the monoterpene compounds increased, while a decrease
inoxygenated compounds has been noticed (Gámiz-Gracia
and Luque de Castro, 2000). In the study by Khajenoori et al.,
on the extraction of essential oil from Zataria multiflora Boiss
by SWE, it has been noticed that the efficiency of thymol and
carvacrol extraction generally increased with the increase in
temperature up to 15 ◦ C, at 175 ◦ C it decreases (Khajenoori
et al., 2009). Miller and Hawethorne reported that the solu-
bility of d-limonene, carvone, eguenol, 1,8-cineole and nerol
increased with the increase in temperature up to 200 ◦ C in SWE
(Miller and Hawthorne, 2000).
SWE has several advantages over hydrodistilation, the
conventional extraction technology usually used for the
extraction of essential oils. Cleaner features, much shorter
extraction time and the cost of extraction are among its main
advantages. According to Soto Ayala and Luque de Castro, the
cost of extraction is clearly advantageous for SWE. Namely,
the energy cost required to perform hydrodistillation is ca. 20
times higher than that required for SWE. This feature is of
fundamental importance for the potential future implemen-
61
tation of this technique at an industrial scale (Soto Ayala and
Luque de Castro, 2001). Further, the possibility to manipulate
the composition of extracted essential oil by changing the pro-
cess temperature is one of the most important advantages of
SWE.Aside from that, according to several studies (Khajenoori
et al., 2013; Eikani et al., 2007), SWE enables the extraction
of a significantly higher amount of valuable oxygenated com-
ponents in comparison to conventional methods, Soxhlet and
hydrodistilation, and this has an impact on the obtained qual-
ity of extracts. On the other hand, hydrodistillation has a
distinct mechanism of extraction, whereas SWE and Soxhlet
extraction mainly consist of the dissolution and/or solubili-
sation of the essential oil in solvent (Khajenoori et al., 2009).
Therefore, a positive aspect of hydrodistillation is the spon-
taneous separation of the two immiscible phases; meanwhile
the SWE extract is an emulsion which mustbe broken by an
external agent (Soto Ayala and Luque de Castro, 2001). Aside
from thestudies on the extraction of antioxidant compounds,
e.g. phenols, and the extraction of essential oils, the appli-
cation of SWE for the isolation/separation/recovery of many
other compounds from different plant sources has been inten-
sively investigated (Table 8).
3. Natural deep eutectic solvents
Deep eutectic solvents (DES) were first introduced by Abbott
et al. (2003), who reported interesting properties of eutec-
tic mixtures of urea and a range of quaternary ammonium
salts. Today, DESs are widely recognized as a novel class of
sustainable solvents representing a green alterative to ionic
liquids (ILs). Due to the similar properties of DESs and ILs (non-
volatility, non-flammability, high viscosity, similar starting
materials), DESs are sometimes referred to as the fourth-
generation of ILs, even though they are not entirely composed
of ionic species. DESs are prepared simply by mixing two or
three components such as organic salts (quaternary ammo-
nium or phosphonium salt) and metal salts or hydrogen bond
donors (HBD), that are capable of associating with each other
through intramolecular hydrogen bonds. The charge delocal-
ization that occurs is hereafter responsible for the decrease in
the melting point of the resulting mixture, relative to the melt-
ing points of the starting materials (Paiva et al., 2014). However,
DESs have advantages over ILs, such as lower environmen-
tal and economic impact. This is especially true for DESs that
that are produced from primary metabolites common in liv-
ing cells, called natural deep eutectic solvents (NADES), that
are generally composed of components that are abundant in
our daily diet, such as choline, amines, sugars, polyalcohol
and carboxylic acids. Actually, NADESs fully fit the princi-
ples of green chemistry and offer many advantages, including
low cost, readily available component, simple preparation,
and a low toxicity profile. Aside from that, they show very
good physicochemical characteristics (e.g. negligible volatility,
liquid sate even at temperatures below 0 ◦ C, adjustable viscos-
ity, wide polar range, high degree of solubilisation strength
for different compounds) which can be fine-tuned for spe-
cific purposes due to their numerous structural possibilities
(Zhang et al., 2012). Moreover, NADESs probably occur in liv-
ing cells and are involved in the biosynthesis, solubilisation
and storage of various poorly water-soluble metabolites and
unstable compounds in cells (Choi et al., 2011). All those
properties provoke a number of ideas for the application of
NADESs in health related areas, such as drug delivery systems,
62 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73

Table 7 – Application of SWE for essential oil extraction.

Material for extraction SWE operating conditions Reference

Fennel (Foeniculum vulgare) Investigated range: Gámiz-Gracia and Luque de

Temperature: 50–200 ◦ C Castro (2000)
Pressure: 50 bar
Extraction time: 5–50 min
Optimal conditions/highest recovery:
150 ◦ C, 50 bar, 50 min
Wild thyme (Thymbra spuicata) Investigated range: Ozel et al. (2003)
Temperature: 100–175 ◦ C
Pressure: 20–90 bar
Extraction time: 30 min
Optimal conditions/highest recovery:
150 ◦ C, 60 bar, 30 min
Oregano leaves (Lippia graveolens) Investigated range: Soto Ayala and Luque de
Temperature: 100–175 ◦ C Pressure: 10–51 bar Castro (2001)
Extraction time: 30 min
Optimal conditions/highest recovery:
125 ◦ C, 20 bar, 30 min
Chamomilla (Matricaria chamomilla L.) Investigated range: Khajenoori et al. (2013)
Temperature: 100–175 ◦ C
Pressure: 20 bar
Extraction time: 120 min
Optimal conditions/highest recovery:
150 ◦ C, 20 bar, 120 min
Coriander (Coriandrum sativum L.) Investigated range: Eikani et al. (2007)
Temperature: 100–175 ◦ C
Pressure: 20 bar
Extraction time: 20 min
Optimal conditions/highest recovery:
125 ◦ C, 20 bar, 20 min
Shirazi thyme (Zataria multiflora Boiss) Investigated range: Khajenoori et al. (2009)
Temperature: 125–175 ◦ C
Pressure: 20 bar
Extraction time: 60 min
Optimal conditions/highest recovery:
150 ◦ C, 20 bar, 60 min
Pepermint (Mentha piperita) Investigated range: Kubatova et al. (2001)
Temperature: 100–200 ◦ C
Pressure: 60 bar
Extraction time: 6–40 min
Optimal conditions/highest recovery:
150 ◦ C, 30 min, 60 bar
175 ◦ C, 12 min, 60 bar

bone-therapy scaffolds, and other food, pharmaceutical and
cosmetics related applications (Faggian et al., 2016; Zainal-
Abidin et al., 2017; Li and Lee, 2016; Mbous et al., 2017). There
is also an increasing number of studies on the extraction of
biologically active compounds, including flavonoids, pheno-
lic acid, anthocyanin, terpenoids, alkaloids and saponins, that
indicate the possible utilization of NADESs in the extraction
of various polar, as well as non-polar, natural compounds
(Zainal-Abidin et al., 2017; Ruesgas-Ramón et al., 2017). Among
the biologically active compounds, phenolic compounds are
studied the most (Table 9). In order to design efficient extrac-
tion methods independently of target compounds by using
NADESs, the following steps should be included: (1) selection
and fine-tuning of physicochemical characteristics of NADESs,
(2) selection and optimization of the extraction method, and
(3) recovery of the target compounds form NADES, if it is nec-
essary.
NADESs’ capacity to extract biologically active compounds
varies considerably, due to the unique physiochemical prop-
erties of each NADES. In order to select the ideal NADES for
certain, Radošević et al. (2016) values polarity and pH among
others. The first step is the selection of a NADES component
which could later be modified by changing the molar ratio
between the components and/or by the addition of water.
Commonly, it is necessary to try several typical combina-
tions which considerably differ in physiochemical properties
in order to select a suitable NADES (Dai et al., 2013a; Nam
et al., 2015; Cvjetko Bubalo et al., 2016; Wang et al., 2016). For
example, Dai et al. (2013b) studied the extraction of aromatic
pigments with a wide range of polarity from Carthamus tinc-
torius L. by using seven NADESs, indicating that the NADES
with the lowest polarity showed the lowest efficiency for
polar compounds and high extractability for non-polar com-
pounds. This corresponds to the general principle of “like
dissolves like,” i.e., that polar compounds are r extracted bet-
ter by using a polar solvent, and vice versa. Similar conclusion
was also obtained for the extraction from grape skin phe-
nolic compounds (Jeong et al., 2015a; Cvjetko Bubalo et al.,
2016; Radošević et al., 2016). Radošević et al. (2016) applied
choline chloride-based NADESs containing organic acid, sugar
or polyalcohol as HBD. Organic acid-based NADESs are more
polar that sugar- and polyalcohol-based ones, with polarity
close to that of methanol. Moreover, NADESs with organic
acids are, by their nature, acidic, whereas sugars or polyal-
cohol containing NADESs belong in the group of solvents with
pH values higher than 6 (Dai et al., 2014; Radošević et al.,
 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73 63

Table 8 – Application of SWE for other compounds extraction.

Material for Targeted compound SWE operating conditions Reference
extraction/resource

Oil palm Monosaccharide Investigated range: Norsyabilah et al. (2013)

Temperature: 170–200 ◦ C
Pressure: 34–55 bar
Extraction time: 5–15 min
Optimal conditions/highest recovery:
190 ◦ C, 10 min, 41 bar
Ganoderma lucidum Polysaccharide Investigated range: Matsunaga et al. (2014)
Temperature: 100–220 ◦ C
Pressure: 40 bar
Optimal conditions/highest recovery:
170–220 ◦ C, 40 bar
Coconut meal Oligosaccharide Investigated range: Khuwijitjaru et al. (2012)
Temperature: 100–200 ◦ C
Extraction time: 30–240 min
Optimal conditions/highest recovery:
227 ◦ C, 3 min
Sunflower Oil Investigated range: Ravber et al. (2015)
Temperature: 100–160 ◦ C
Pressure: bar
Extraction time: 5–120 min
Solid: liquid ration: 1:10–1:30
Optimal conditions/highest recovery:
130 ◦ C, 30 min, 30 bar, solid liquid ration:1:20
Citrus peel Pectin Investigated range: Wang et al. (2014)
Temperature: 100–140 ◦ C
Extraction time: 5 min
Optimal conditions/highest recovery:
120 ◦ C, 5 min
Apple pomace Pectin Investigated range: Wang et al. (2014)
Temperature: 130–170 ◦ C
Extraction time: 5 min
Optimal conditions/highest recovery:
150 ◦ C, 5 min
Sugar beet pulp Pectin Investigated range: Chen et al. (2015)
Temperature: 110–130 ◦ C
Pressure: 80–120 bar
Extraction time: 20–40 min
Liquid solid ration: 30–50
Optimal conditions/highest recovery:
120.72 ◦ C, 30.49 min, 107 bar, solid–liquid ration 44.03
Olive leaves Mannitol Investigated range: Ghoreishi and Gholami
Temperature: 100–150 ◦ C Shahrestani, (2009)
Pressure: 30–110 bar
Optimal conditions/highest recovery:
100 ◦ C, 50 bar
Mahkota Dewa (Phaleria Mangiferin Investigated range: Kim et al. (2010)
macrocarpa) Temperature: 100–150 ◦ C
Pressure: 7–40 bar
Extraction time: 1–7 h
Optimal conditions/highest recovery:
100 ◦ C, 5 h, 40 bar

2015). Consequently, organic acid-based NADESs showed the
best extraction results for anthocyanin, while sugar based
NASEDs were a better choice for other phenolic compounds
(Radošević et al., 2016). This is not surprising since it is well
known that anthocyanins are highly polar compounds and
that an acidic environment favours their extraction and sta-
bility (Castañeda-Ovando et al., 2009). When the extraction
of anthocyanin from Catharanthus roseus was studied, organic
acid base- and polyalcohol-based NADESs showed the best
performance, indicating that the extraction efficiency is likely
to be correlated to the viscosity of NADESs rather than to
their polarity and pH value (Dai et al., 2016). However, further
NADES tailoring by changing the molar ratio of the selected
combination is possible (Wei et al., 2015; Li et al., 2015; Qi
et al., 2015; Wang et al., 2016). Wang et al. (2016) reported
that the extraction yield of the lipophilic compound tashinone
was increased when the choline chloride/HBD molar ratio
declined from 1:1 to 1:5, while a further decrease of the ratio
to 1:6 showed no significant changes. Similarly, a NADES with
choline chloride and lactic acid was selected for the extraction
of catehins from Camellia sinensis and the molar ratios from
1:1 to 1:4 were tested for the extraction efficiency. Extraction
yields of the target catechins were found to increase with the
change of choline chloride/lactic acid from 1:1 to 1:2, while a
sustained decrease was noticed with the change of the molar
ratio from 1:2 to 1:4. About 30% lower content of catechin was
noticed in NADESs with the molar ratio of 1:4, compared to
the ratio of 1:2. This could, probably, be due to a decrease in

Table 9 – Extraction of phenolic from natural sources using NADES.
Tested NADES
GlyGln
ChLa; LaSa; LaAa; LaGlnW
ChCit; ChOx; ChMa; ChGlc;
ChFru; ChXyl; ChGly
ChSuc; ChP; ChGlc;
ChSol; ProGlc;
LaGlc; ChGlycol; ChGly;
ChB1,3; ChBut1,4; ChHx1,6
ChGly; ChOx; ChMa; ChSor;
ChProMa
ChP; LaGlc; ProMa; ChMa;
ChGlc; FruGlcSuc
Method of extraction
Stirring [OC: 600 rpm;
120 min; 70 ◦ C; CDES = 80%
(w/v); RL/S = 32 mL g−1 ]
UAE [OC:140 W; 80 ◦ C;
90 min; CDES = 80% (v/v)]
UAE [OC:30.6 min, 341.5 W,
CDES = 64.6% (v/v)]
MAEa [600 W,
RL/S = 14 mL g−1 , 11 min,
80 ◦ C, CDES = 70%]
UAE
HRE
Microwave-assisted
extraction (MAE);
Ultrasound-assisted
extraction methods (UAE)a
[Optimal condtions (OC):
65 ◦ C, 50 min, CDES = 75%
(w/w), 35 kHz]
Mechanical stirringa [OC:
40 ◦ C, 30 min];
Ultrasound-assisted
extraction with heating
(UEH)
Sources
Olea europaea leaves
Native Greek medicinal
plants – dittany (DI), fennel
(FE), marjoram (MA), mint
(MI), sage (SA)
Wine lees
Pigeon pea roots
Grape skin
Catharanthus roseus
64
Compunds (the most promising solvent) References
−1
Total polyphenol yield (mg GAE g dw) (GlyGln) Athanasiadis et al. (2017)
Total polyphenol yield (mg GAE g−1 dw): Bakirtzi et al. (2016)
DI (LaGlnW)
FE (LaGlnW)
MA (LaGlnW)
MI (LaGlnW)
Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73
SA (LaGlnW)
Total flavonoid yield (mg RtE g−1 dw):
DI (LaGlnW)
FE (LaAa)
MA (LaAa)
MI (ChLa)
SA (LaGlnW)
Total anthocyanin (ChMa) Bosiljkov et al. (2017)
Genistin (ChHx1,6) Cui et al. (2015)
Genistein (ChHx1,6)
Apigenin (ChHx1,6)
Quercetin-3-O-glucoside (ChGly) Cvjetko Bubalo et al. (2016)
Malvidin-3-O-mono glucoside (ChOa)
Malvidin-3-O-acetylmonoglucosides (ChOa)
Malvidin-3-(6-O-p-coumaroyl) monoglucosides (ChOar)
Peonidin-3-(6-O-p-coumaroyl)monoglucosides (ChOa)
Petunidin-3-O-monoglucoside(ChOa)
Peonidin-3-O-monoglucoside(ChOa)
Cyanidin-3-O-monoglucoside (ChProMa)
Delphinidin-3-O-monglucoside (ChProMa)
(+)-Catechin (ChOa)
Hirsutidin 3-O-(6-O-p-coumaroyl) glucose (ChP/LaGlc) (Dai et al. 2016)
Petunidin 3-O-(6-O-p-coumaroyl) glucose (ChP/LaGlc)
Malvidin 3-O-(6-O-p-coumaroyl) glucose (ChP/LaGlc)
7-O-methylcyanidin (ChP/LaGlc)
7,3 -O-dimethylcyanidin (ChP/LaGlc)
LaGlc; CitGlc; CitFru
ChP; ChGly; ChGlc; ChSuc
ChXylol; ChSol; ProGly;
GlyGln; GlyAla; GlyHis;
GlyThr; GlyLys; GlyArg
ChMa; ChCit; ChGly; ChGlc;
ChFru; ChGal; ChRib; ChSuc;
ChCalt; ChCal;
CitMalt; CitMal
CitAdo; CitGlc; CitGal; CitPro;
CitB; ChMa;
Ch:Cit;ChCl:Xylol;
ChAdo;ChGlc;ChFru; ChGly;
GlyXylol; GlyPro; GlyB;
GlyMa; GlyFru; GlySuc;
ProSuc; BSuc; ChSuc;
GlyProSuc; GlyBSuc;
GlyChSuc
BSuc; BSol; BMalt; BGlc; BMal;
BXylol; BU; BGly; BCit; CitSuc;
CitSol; CitMalt; CitMal;
CitGlc; CitXylol; CitFru;
CitGly; GlySuc; GlySol;
GlyMalt; GlyMal; GlyGlc;
GlyXylol; GlyFru; GlyGal;
GlyU; BGlyMalt; BGlyMal;
BGlyU; BGlyCit; BGlyGlc;
CitGlyMalt; CitGlcMal;
CitGlyGlc; UGlyMalt;
UGlyMal; UGlyGlc; BGlyGlc
UAEa [OC:0–60 min; 40 ◦ C;
LaGlc, 5:1, CDES = 85%;
200 W]
UAE [20 kHz,
200 W CDES = 80%, w/w]
UAEa [OC:9.23 min,
CDES = 76.20% w/w,
RL/S = 7.3 mL g−1 ]
Stirring; heating; vortexing;
stirring − heating
Stirring; heating;
heating + stirring; UAEa
[21.5 min; CDES = 66.1% w/w;
RL/S = 19 mL g−1 ]
Stirring; heating;
heating + stirring; UAEa
[6.5 min; CDES = 81% w/w;
RL/S = 18 mL g−1 ]
Onion, olive, tomato and
pear industrial by- products
Tartary buckwheat hull
Grape skin
White ginseng
Camellia sinensis
Gallic acid (LaGlc) Fernández et al. (2018)
3-Hydroxytyrosol (LaGlc)
Tyrosol (LaGlc)
Catechin (LaGlc)
Caffeic acid (LaGlc)
Rutin (LaGlc)
Coumaric acid (LaGlc)
Trans-Ferulic acid (LaGlc)
Ooleuropein (LaGlc)
Cinnamic acid (LaGlc)
Quercetin (LaGlc)
Luteolin (LaGlc)
Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73
Naringenin (LaGlc)
Apigenin (LaGlc)
Rutin (ChGly) Huang et al. (2017)
Total anthocyanins (cyanidin-3,5-diglucoside equivalents; mg) Jeong et al. (2015a)
(CitMalt)
Ginsenosides (mg of five ginsenosides g−1 dw) (GlyProSuc) Jeong et al. (2015b)
Catechin (epicatechin, epigallocatechin, epicatechin-3-gallate, Jeong et al. (2017)
epigallocatechin-3-gallate; mg g−1 dw) (BGlyGlc)
65
 66
– Table 9 (Continued)
Tested NADES Method of extraction Sources Compunds (the most promising solvent) References
a ◦ −1
ChGly; GlySa; GlySatW UAE [OC:80 C, 90 min, Red grape pomace (RGP), Total polyphenol yield (mg GAE g dw): Mouratoglou et al. (2016)
140 W, 37 kHz, 35 W L−1 ] Olive leaves (OLL), LMP (ChGly)
Wheat bran (WB), OLL (ChGly)
Spent filter coffee (SFC), OSW (GlySatW)
Onion solid wastes (OSW), RGP (ChGly)
Lemon waste peels (LMP) SFC (ChGly)
WB(ChGly)
Total flavonoid yield (mg RtE g−1 dw):
LMP (ChGly)
OLL (GlySa)
OSW (ChGly)
RGP (ChGly)

Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73

SFC (GlySa)
WB (ChGly)
ChGly; ChXylol; ChGlc; UAEa [OC:45 min ◦ C, Flos sophorae Quercetin (ProGly) Nam et al. (2015)
ProGlc; CitGlc; CitAdo; BMa; CDES = 90% w/w; 330–450 W]; Kaempferol (ProGly)
ProGly; ProXylol Heat reflux extraction (HRE) Isorhamnetin glycosides (ProGly)
ChGly; ChB1,4; ChB1,3; BHgly; negative pressure Equisetum palustre L. Kaempferol- Qi et al. (2015)
BHb1,4; BHb1,3; ChEg; BHeg; cavitation-assisted 3-O-ˇ-d-glucopyranoside-7-O-ˇ-d-Glucopyranoside (ChBHeg)
ChBHeg extraction (NPCE)a Kaempferol-3-O-ˇ-d-rutinoside-7-O-ˇ-d-glucopyranoside
[−0.07 MPa, 60 ◦ C, (ChBHeg)
RL/S = 25 mL g−1 , 20 min, Luteolin-7-O-ˇ-d-glucopyranoside (ChBHeg)
CDES = 80% (v/v)]; Quercetin-3-O-ˇ-d-glucopyranoside (ChBHeg)
UAE Apigenin-5-O-␤-d-glucopyranoside (ChBHeg)
Genkwanin-5-O-␤-d-glucopyranoside (ChBHeg)
Luteolin (ChBHeg)
Apigenin (ChBHeg)
Genkwanin (ChBHeg)
ChGly; ChGlc; ChGal; ChPro; MAEa [OC: 64.46 ◦ C; Ficus carica L. leaves Caffeoylmalic acid (GlyXylolFru) Wang et al. (2016)
ChMa;ChXylol; ChFru; RL/S = 17.53 mL g−1 , Psoralic acid-glucoside (GlyXylolFru)
ChSuc;ChCit; GlyXylolFru GlyXylolFru 3:3:3CDES = 80% Rutin (GlyXylolFru)
(v/v); 24.34 min] Psoralen (GlyXylolFru)
UAE Bergapten (GlyXylolFru)
ChB1,4; ChGly; ChEg; ChCit; MAE [OC: 60 ◦ C; 12 min; Radix Scutellariae Baicalin (ChLa) Wei et al. (2015)
ChMa; ChLa; ChGlc; ChSol; RL/S = 15 mL g−1 CDES = 80% Wogonoside (ChLa)
ChSuc; ChMalt; CitSuc; (v/v) Baicalein (ChLa)
CitGlc; LaSuc Wogonin (ChLa)

OC — optimal conditions.
CDES — concentration of natural deep eutectic solvents.
RL/S — liquid/solid ratio.
Component abbreviations: Aa, ammonium acetate; Ala, alanine; Ado, adonitol; Arg, arginine; B, betaine; B1,3, 1,3-butanediol; B1,4, 1,4-butanediol; Cal, caltose; Calt, caltitol; Ch, choline chloride; Cit, citric acid; Eg,
ethylene glycol; Fru, fructose; Gal, galactose; Glc, glucose; Gln, glycine; Gly, glycerol; Glycol, glycol; H1,6, 1,6-hexanediol; Hb1,3, hydrochloride-1,3-butanediol; Hb1,4, hydrochloride-1,4-butanediol; Heg, hydrochloride-
ethylene glycol; Hgly, hydrochloride-glycerol; His, histidine; La, lactic acid; Lys, lysine; Ma, malic acid; Mal, maltitol; Malt, maltose; Ox, oxalic acid; P, 1,2-propanediol; Pro, proline; Rib, ribose; Sa,sodium acetate;
Sat, sodium–potassium tartrate; Sol, sorbitol; Sor, sorbose; Suc, sucrose; Thr, threonine; U, urea; W, water; Xyl, xylose; Xylol, xylitol.
a
The best extraction method.
 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73
the amount of choline chloride, which led to the reduction
of the proportion of hydrogen bond receptors in the NADES
system, negatively influencing the major mechanism of solu-
bility of bioactive compounds (Li et al., 2015; Wei et al., 2015).
Namely, NADESs have the ability of donating and accepting
protons and electrons, which confers them the ability to form
hydrogen bonds, thus increasing their dissolution capability
(Dai et al., 2013a,b; Nam et al., 2015).
A further improvement of the extraction efficiency could
be obtained by the optimization of NADESs water content
(Zainal-Abidin et al., 2017; Ruesgas-Ramón et al., 2017). The
addition of water leads to a decrease in the viscosity of
NADESs, thus enhancing the mass transfer from plant matri-
ces to a solution, and increasing the extraction efficiency. The
viscosity of NADESs is generally very high at room tempera-
ture, which is one of the major problems when using NADESs
as extraction solvents (Zhang et al., 2012). For example, some
NADESs cannot even be used for extraction without the addi-
tion of water, due to problems NADESs have with transferring
and filtering (Cvjetko Bubalo et al., 2016). On the other hand,
the addition of water causes a decrease in hydrogen bonding
interactions between the NADESs and the target components.
Moreover, a large excess of water in the NADESs could break
the halide-HBD supramolecular complex and a simple aque-
ous solution of the individual components could be obtained
(Dai et al., 2016). Aside from that, the water content influ-
ences the polarity of the NADES, thus, the addition of water
should be optimised for each NADES and target compound. In
general, NADESs with high water content are better for polar
compounds and NADESs with low water content are more
suitable for the extraction of less polar compounds (Dai et al.,
2013b). However, in many cases the addition of water between
20–30% (w/w) has a beneficial influence on the extraction yield
of both polar and non-polar compounds (Wei et al., 2015; Li
et al., 2015; Cvjetko Bubalo et al., 2016; Huang et al., 2017). Fur-
thermore, the stability of target compounds in NADESs should
be considered as an important factor for NADES selection
(Dai et al., 2014, 2016). Dai et al. (2014) studied the stabil-
ity of phenolic compounds in safflower extracts, indicating
that the stabilization of phenolic compounds in some typi-
cal NADESs was better than in conventional solvents such as
ethanol and water. The stabilisation ability of NADESs cor-
related with strong hydrogen bonding between solutes and
solvent molecules, while among the tested NADESs, sugar-
based ones showed the best results (Dai et al., 2014). This
interaction decreases the movement of solute molecules,
reducing their contact time with oxygen and the interface of
NADESs and air, and consequently reducing oxidative degra-
dation, which is the major degradation mechanism (Dai et al.,
2016). Data on bioactive compounds stability in NADESs are
scarce and extra work is necessary in order to provide further
understanding of the stabilizing ability of NADESs.
In addition, prior to the final selection of the NADES, the
evaluation of its environmental impact should be performed
(Radošević et al., 2015; Hayyan et al. 2016; Radošević et al.,
2016). The assumption that NADESs are benign is based on the
toxicity data for the components that make up the NADESs,
which are biomaterial-derived and pharmaceutically accept-
able. This theory does not take into account the possibility
of a synergetic effect of combining the compounds in the
NADES, which could have a significant impact on the biolog-
ical properties of such mixtures (Paiva et al., 2014; Radošević
et al., 2015; Hayyan et al., 2016). Also, many authors suggest
that the NADESs containing organic acids as the HBD (for
67
instance oxalic, citric, malic, or tartaric acids) exhibit greater
cytotoxicity in vitro than the NADESs containing sugars as
the HBD (for instance glucose, mannose, fructose, and xylose)
(Radošević et al., 2016; Paiva et al., 2014). Consequently, the
potential application of this solvent in the extraction of bio-
logically active compounds should be accompanied by the
evaluation of its environmental impact, in order to develop
a truly environmentally friendly process. Moreover, if the bio-
logical activity of a plant extract is one of the research goals,
possible antioxidative activity of the NADESs should be con-
sidered. Previous studies indicate that NADESs could enhance
the antioxidative activities of plant extracts, which could be
explained by the reactive oxygen species scavenging activi-
ties of the NADESs itself or NADES forming compounds (Nam
et al., 2015; Radošević et al., 2016). It has been proposed that
NADESs formed from compounds with proven pharmacolog-
ical effects, such as an amino acid or an organic acid, could
also have similar properties, indicating that not only physic-
ochemical characteristics of solvents, but also their biological
activity, could be fine-tuned (Radošević et al., 2016).
NADES choice is followed by the selection of an extraction
method, which also significantly contributes to the extraction
efficiency. When methods for green extraction are consid-
ered, the reduction of energy consumption by using innovative
technologies (e.g. ultrasound extraction (UAE), microwave
extraction (MAE), negative pressure cavitation method) should
be taken into account. These innovative technologies have
been recognized as an excellent energy source for promot-
ing extraction efficiency (Chemat et al., 2012). Several studies
showed that NADESs are compatible with those technolo-
gies and that the optimization of the process parameters by
experimental design based on response surface methodology
was conducted. Irrespective of extraction methods chosen,
the common optimised process parameters, were extraction
time, extraction temperature and solvent to solid ratio (Wei
et al., 2015; Qi et al., 2015; Li et al., 2015; Jeong et al., 2015a;
Cvjetko Bubalo et al., 2016; Bosiljkov et al., 2017). The decrease
in NADES viscosity at elevated temperatures facilitates the
penetration of the NADES into the plant matrix, leading to
more destruction of the intermolecular interaction, and thus
enhancing the dissolution of the target molecules (Li et al.,
2015; Wei et al., 2015). On the other hand, plant bioactive
compounds are usually thermosensitive, thus the optimiza-
tion of temperature, as well as time extraction, are necessary.
In addition, NADESs could also be used in headspace-solvent
microextraction as a solvent-minimized extraction technique
for the extraction of volatile compounds (Tang et al., 2015).
The compatibility of NADESs with other innovative technol-
ogy, such as supercritical fluids, as a two-phase separation
system should also be considered.
Based on the aforementioned, the green extraction of plant
bioactive compounds in a biorefinery could be based on the
utilization of NADESs. However, to our current knowledge
there are no such processes on the industrial scale. In order
to include NADESs in both new and existing processes, eco-
nomic and environmental aspects of NADESs should still be
considered. The cost of NADESs is comparable to conventional
solvents, and their production could be classified as a sustain-
able process (Bi et al., 2013; Paiva et al., 2014). Nonetheless,
several other issues should be taken into account, includ-
ing the recovery of target compounds and/or the recyclability
of NADESs, prior to the transfer of the methodology on a
larger scale. The almost zero vapour pressure of the NADESs
68 Food and Bioproducts Processing 1 0 9 ( 2 0 1 8 ) 52–73
could pose a huge problem when the recovery of the target
compounds is needed, especially on the industrial scale (De
Oliveira Vigier et al., 2015). So far, several approaches for the
recovery of target compounds, such as solid phase extrac-
tion and the application of anti-solvents, recrystallization and
adsorption chromatography have been reported (Dai et al.,
2013b; Nam et al., 2015; Jeong et al., 2015b; Huang et al., 2017).
Jeong et al. (2015b) used hydrophilic-lipophilic −based sorbent
to recover the extracted ginsenoside from NADESs using a sim-
ple procedure including the loading of extracts and washing
with water, followed by elution with ethanol with full recov-
ery. Solid phase extraction could be used for other interesting
plant bioactive compounds, using simple changes of the solid
phase for particular compounds (Li et al., 2015). A success-
ful application of anti-solvents method was also reported, by
using water as the most efficient anti-solvent with the recov-
ery of 95.1% of rutin (Huang et al., 2017). Also, the recyclability
of reused NADESs was reported using the simple evapora-
tion of water from NADESs following the recovery of rutin.
The extraction efficiency of choline chloride: glycerol recycled
once, twice, three times was 92%, 87% and 81%, respectively
of that of the original solvents. A similar result was obtained
for recycled NADESs by lyophilisation of the aqueous solu-
tion of NADESs produced during the recovery of ginsenoside
(Jeong et al., 2015b). However, recovery and/or recycling after
extraction and scale-up issues should be definitely studied in
more details if we want to use this solvent more widely on the
industrial scale.
4. Future trends
Nowadays, we cannot find a production process in the food,
cosmetic, pharmaceutical, perfume, or chemical industry
which does not use extraction processes. Recent trends in
extraction techniques have largely focused on finding solu-
tions that minimize the use of harmful solvents and allow the
use of alternative, so called “green” solvents, and renewable
natural products that ensure safe and high quality extracts.
Safety, environmental and economic aspects are forcing the
industry to turn to greener extraction techniques, such as SFE,
SWE, and NADES. The future of SFE is surely on the large
scale for a lot of new industrial applications (food, cosmetic,
pharmaceutical etc.), thanks to the many benefits of CO2 as a
solvent mentioned in this review.
SWE has many advantages over conventional technolo-
gies. Aside from that, the unique properties of subcritical
water, the possibilities for the selective extraction by alter-
ing temperature, and work with widely available and low cost
green extraction solvents, makes this extraction technology
the technology of the future. Challenges in SWE present today
should be focused on a scale up on the industrial level and
a decrease of investment costs. Furthermore, NADESs have
unique physicochemical properties and, thanks to the possi-
bility of designing their properties for a particular purpose,
their low ecological footprint and attractive prices, they have
become increasingly interesting to both the academia and the
industry. However, green solvents are undoubtedly the sol-
vents of future industry.
Acknowledgment
This work is supported by the Croatian Science Foundation
under the project No. 9550.
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