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Journal of Chromatography A 1651 (2021) 462295

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Journal of Chromatography A
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Green non-conventional techniques for the extraction of polyphenols

from agricultural food by-products: A review
Imma Pagano a, Luca Campone b,∗, Rita Celano a, Anna Lisa Piccinelli a, Luca Rastrelli a
Department of Pharmacy, University of Salerno, Via Giovanni Paolo II 132, Fisciano, (SA) 84084, Italy
Department of Biotechnology and Biosciences, University of Milano-Bicocca, Piazza Della Scienza 2, Milano 20126, Italy

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

Article history: Food processing industry is accompanied with the generation of a great production of wastes and by-
Received 16 December 2020 products exceptionally rich in bioactive compounds (especially phenolics), with antioxidant activity. The
Revised 22 May 2021
recovery of these health molecules constitutes a key point for the valorization of by-products, with the
Accepted 25 May 2021
possibility of creating new ingredients to be used for the formulation of food and cosmetic products. One
Available online 28 May 2021
of the main limitations to reuse by-products is linked to the high cost to obtain bioactive compounds,
Keywords: consequently in order to exploit these resources commercially valuable it is necessary to develop inno-
Agricultural food by-products vative, economic and environmentally friendly extraction strategies. These extraction methods should be
Polyphenols able to reduce petroleum solvents, energy consumption and chemical wastes, protecting both environ-
Green extraction ment and consumers and ensuring safe and high-quality final products. The purpose of this review is
SFE to summarize current knowledge and applications of the new extraction techniques such as supercritical
fluid extraction, pressurized liquid extraction, ultrasound assisted extraction applied to polyphenols ex-
traction from agricultural food by-products. Particular attention has been paid to theoretical background,
highlighting mechanisms and safety precautions. Authors concluded that relevant results of these tech-
niques represent an opportunity to industrial scale-up, improving the extraction yields, minimizing time,
costs and environmental impact.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction In the United Kindgom it is estimated that around 3.62Mt of

food is wasted in the primary production stage of food supply
The agricultural and food industries produce a large amount chain: vegetables and starchy roots contribute 37% (the majority
of by-products in the form of non-edible parts derived from the potatoes and cereals) mainly for quality and aesthetic standards
cultivation and processing of crops. It is estimated that 140 bil- [5].
lions of tons of biomass are generated each year from agricultural Agricultural residues can be defined as primary or secondary
by-products in liquid, solid and gaseous form [1,2]. Unfortunately depending on their origin. Primary residues are solid vegetal
there is a lack of comprehensive information about the produc- residues left in the field after harvesting or pruning. Secondary
tion of agriculture residue in the world and there is no statical residues are the portion derived from food processing industries
source [3]. In this context, by-product amount is established start- and discarded during the processing phase (hulls, husks, peels po-
ing from product yield and residue to crop ratios: i.e. for wheat mace, olive pits, nut shells, etc.) [1].
as straw 475.14, soybeans as straw and pods 392.7, tomatoes as The production of agricultural waste varies from country to
leaves and stems 72.87 millions metric tons per year (MMT/year) country, in Europe over than 40% of initial weight is disposed while
[1]. Food waste is the decrease in the quantity or quality of food in North Africa, East Central Asia and Latin America this percentage
resulting from decisions and actions by retailers, food services and is higher. For example the percentage amount of some agricultural
consumers, and FAO (2019) estimated amount of food loss to about by-products is for artichoke about 50–60% of initial weight and for
14% of food production at global level [4]. Value of waste are orange about 60% [6].
higher for fruits and vegetables than for cereals and pulses, espe- Although by-products consist in a promising feedstock for sev-
cially in sub-Saharan Africa [4]. eral uses, they are currently underutilised, and before starting a
valorisation process certain consideration must be address. First of
all, the raw materials are not homogenous and may come from dif-

Corresponding author.
ferent fields with differing cultivation procedures, conditions and
E-mail address: (L. Campone).
0021-9673/© 2021 Elsevier B.V. All rights reserved.
I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

processing; consequently, a standardization process is necessary. must be take into consideration to select the best extraction
Agricultural food by-products are characterized by their biological techniques.
instability due to their high microbial load that can affect prod- Conventional extraction techniques usually include Soxhlet and
uct safety and naturally accelerate microbial degradation and high- maceration. The main drawbacks of these techniques are: a large
water load which increases weight, leading to higher transporta- volume of solvents is required, the organic solvents used are of-
tion costs. High values of Chemical Oxygen Demand (COD) and ten hazardous, long extraction times, low selectivity and low yields
Biochemical Oxygen Demand (BOD) mostly due to their organic of extraction. Alternative techniques are currently in demand to
nature, also caused by the presence of compounds with antioxi- overcome all these disadvantages. These non conventional tech-
dant and antimicrobial activity, prevent disposal via the classical niques must provide short extraction times, and reduced volumes
wastewater treatment, irrigation and fertilization of fields [7]. Agri- of hazardous organic solvents; they are straightforward in execu-
cultural food by-products have been mainly utilized as animal feed, tion, with a decreased use of energy and water [14]. In line with
in fuel and energy production, but recently researchers have be- aim of Green Chemistry, the green extraction can be defined as
gun to explore the characteristics of these by-products as sources being “based on the discovery and design of extraction processes
of bioactive compounds (carotenoids, dietary fibers, minerals and which will reduce energy consumption, allows use of alternative
polyphenols) for pharmaceutical, cosmetic and nutraceutical sec- solvents and renewable natural product, and ensure a safe and
tors due to the great chemical heterogeneity [8]. high quality extract/product” [15]. Based on the above, the use
Amongst all the bioactive compounds that can be obtained from of alternative solvents, renewable raw materials for botanical ex-
agri-food by-products, in recent years, phenolic compounds have tracts, and decreased energy consumption by energy recovery are
attracted the attention of researchers due to their health bene- demanded.
fits [9]. Phenolic compounds are a large class of secondary plant Solvent selection depends on the format of the raw botanical
metabolites that are derivatives of pentose phosphate, shikimate material and its bioactive compounds, cost and availability. Almost
and phenylpropanoid pathway [10]. From the chemical point of all solvents originate in crude oil, with only ethanol derived from
view phenolic compounds showing a broad range of structure fermentation. Water represents the obvious solution, but only for
from rather simple phenolic molecules to high polymerised com- the extraction of polar compounds.
pounds; the simpler compound consists of an aromatic ring with Valorisation of by-products involves increasing the added value
one or more hydroxyl substituents e.g. phenolic acids. Despite this of these agricultural by-products, initially only used as fertilizers
wide range of chemical structures this class of compounds is of- or animal feed and recently under consideration for energy pro-
ten called polyphenols. However, in order to make their classifica- duction [16] or as potential sources of bioactive ingredients [17].
tion easier, it is possible to divide the polyphenols into two ma- Most of these products do not see further use due to the lack of
jor types, flavonoids and non-flavonoids. The flavonoids are built suitable extraction techniques [18]. Extracting bioactive compounds
around a C6-C3-C6 carbon skeleton (flavones, flavanones, flavonols, from by-products must follow standard and simple principles:
dihydroflavonols, flavan-3-ols, flavan-3,4-diols, chalcones, dihydro-
• maximization of extraction yield;
calchones and aurones). Non-flavonoids include phenolic acids, cin-
• adaptation to industry demands; clarification and removal of
namic acids, stilbenes and lignans [11]. Chemically, polyphenols
toxic impurities;
possess an aromatic and a benzene ring with one or more hydroxyl
• maintaining functionality and preventing deterioration as a
groups. Several studies have reported that a diet rich in these
consequence of extraction; maintaining the food grade of the
bioactive compounds correlates with the prevention of degenera-
final product [19].
tive and cardiovascular diseases [12,13]. Phenolic compounds ex-
hibit a wide range of physiological properties such as antioxi- In solid-liquid extractions, the compounds of interest should be
dant, anticarcinogen, antimutagen, antiallergen and antiaging ac- dissolved in the solvent while interfering compounds should re-
tivity, moreover, they can be used in functional foods as natural main in the matrix [20]. These ideal conditions are rarely reached,
antioxidants. so it is necessary to continue researching better extraction con-
Chemical determination of polyphenols involve combining ad- ditions for the improvement of recovery of these compounds, fo-
vanced separation tools with advanced sample preparation tech- cusing on solvent, particle size, temperature, pressure, time and
niques. Sample preparation is a vital step for the selective and effi- amount of matrix.
cient extraction of target compounds. It converts the plant matrix Qualitative and quantitative studies of bioactive compounds in
into a suitable sample for subsequent analytical techniques. Cur- plants are principally based on the selection of a correct method
rently the development and application of modern techniques for of extraction [18]. Green Chemistry is the conception of chemistry
sample preparation provide several advantages. acting with the aim to protect the environment by developing pro-
The preparation and extraction of bioactive polyphenols de- cedures which restrict the use and generation of hazardous sub-
pends on the individual structure of the sample matrix and also stances [21]. Green and non-conventional extraction techniques are
on chemical properties of desired compounds. For liquid samples, based on respecting the ideals of Green Chemistry: the most used
liquid-liquid extraction (LLE) is performed, whereas for solid sam- are supercritical fluid extraction (SFE), pressurized liquid extraction
ples, solid-liquid extraction (SLE) is carried out. Amongst all pa- (PLE) and ultrasound assisted extraction (UAE) [22].
rameters to consider, the chemical properties of target compounds
are important features in the selection of the most appropriate 2. SFE supercritical fluid extraction
extraction process. In particular, polarity, molecular structure, and
number of hydroxyl groups play a crucial role in polyphenols ex- Supercritical fluid extraction (SFE) is used at the laboratory and
traction, and so must be considered with great attention. Moreover, commercial scale to extract target compounds or to recover large
phenolic compounds in plant and foods are often associated by scale of bioactive compounds, for example the well-known decaf-
hydrophobic and/or hydrogen bonds with carbohydrates, proteins, feination of coffee beans. Supercritical fluid exceeds its specific
and lipids, resulting in the alteration of polarity of not bounded. critical pressure and temperature, and so possesses properties of
After the extraction drying steps such as air-drying, oven-drying both liquids (low surface tension, high solvent power) and gases
or freeze-drying, are often necessary in order to concentrate ex- (decreased viscosity, high diffusivity), and these may be modulated
tracted compounds or to avoid their degradation, preserving the by small variations in the pressure and temperature. Furthermore,
antioxidant activity of samples. For these reasons also drying steps supercritical fluids spread easily due to low viscosity and show

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

rapid penetration due to low surface tension within the solid ma- SFE can be divided into two steps: the solubilisation of bioac-
trix, increasing extraction efficiency [23]. The critical temperature tive compounds from the solid matrix, and their separation in Sc-
is defined as the hottest temperature allowing gases to transition CO2 solvent. The reduction of pressure and the increase of tem-
into liquids under high pressures, with the critical pressure be- perature at the end of extraction releases the extract from solvent
ing the greatest pressure under which liquids transition to gases [23]. Once the compounds are extracted, solvent can be easily re-
at high temperatures [23]. The most frequently used supercritical moved by evaporation [33].
fluid is carbon dioxide, CO2 , (Tc=31.1 °C and Pc=7.38 MPa) and rep- SFE aims to be highly selective, with quick extraction times,
resents the ideal solvent for SFE. It has generally recognized as safe prevention of pollution and use of non-toxic organic solvents [28].
(GRAS) status by the European Food Safety Authority and United SFE is more environmentally friendly than conventional solvent ex-
States Food and Drug Administration [24–27]. CO2 is non-toxic, in- traction, is rapid, automatable, and selective; it avoids using large
ert, inexpensive, non-carcinogenic, not flammable, harmless, and volumes of toxic solvents and has tunable solvent density. Fur-
food-grade. The supercritical region lies above the critical pressure thermore the lack of light and air in the course of extraction de-
and temperature, and under these conditions CO2 exists in a phase creases the degradation of compounds [34]. In addition, the re-
with gas and liquid properties. peat reflux of the supercritical fluid around samples allows for
Carbon dioxide allows for minimal alteration of bioactive com- complete extraction. SFE is an environment-friendly technique as
pounds, preserving their functional and biological properties, and it uses minimal amount of organic solvents, the supercritical fluid
is easily dispersed from samples as a gas at room temperature[28]. can be reused and recycled, thus minimizing waste and materials
Sc-CO2 provides a gentle treatment for heat-sensitive materials [22]. Another advantage is the coupling of SFE and analytical chro-
[25]. matographic techniques including gas chromatography (GC) or su-
The main parameters that affect the extraction are: tempera- percritical fluid chromatography (SFC) [35]. The principal disadvan-
ture, pressure, time, solvent-to-feed ratio, and co-solvent concen- tages of SFE are the high cost of equipment and setup [35]. More-
tration [29]. A unique characteristic of a supercritical fluid (SCF) over, optimising SFE involves awareness of thermodynamic data
solvent is the sharp variability of density, with the variation of (solubility, selectivity) as well as kinetic data (mass transfer coef-
pressure and temperature, on which also depends the solvent ca- ficients) [35]. Ultrasound assisted SFE is another technique which
pacity at the supercritical fluid state. The increase of temperature provides decreased extraction time and increased extraction yields
leads to a decrease of density, facilitating analyte diffusion, favour- over regular SFE [33].
ing mass-transfer kinetics, and decreasing surface tension [30]. In SFE technology preserves the bioactivity of the recovered com-
order to optimize transport properties, it’s possible to vary sol- pounds improving the functional characteristics of final extract. In
vation power by adjusting pressure and temperature [28]. In ap- fact the low temperature allows to recover thermolabile and oxid-
proaching the critical point, the properties of the solvent begin to able compounds [36].
change quickly in response to small pressure variations. Sc-CO2 has A further application of SFE is Supercritical Antisolvent Frac-
a particular and easily tunable density range that allows selective tionation (SAF). In this case, carbon dioxide is used as an anti-
extractions of target compounds [31]. Supercritical carbon diox- solvent. SAF involves a flow of Sc-CO2 and a flow of a polar mix-
ide is intrinsically non-polar and it is an excellent solvent for ex- ture of liquids, in continuous contact as they traverse a pressurized
traction of non-polar compounds and some low molecular weight, chamber. Usually, the polar mixture consists of a sample extracted
volatile, and less effective in the extraction of polar compounds from raw material with an ethanol/water mixture. Polar compo-
such as polyphenols. Low polarity is the main drawback of this nents in the liquid mixture are insoluble in Sc-CO2 and thus pre-
technique. To overcome this the addition of small amounts of a cipitate, while less polar compounds and ethanol dissolve into the
cosolvent can be used. A cosolvent is an organic substance i.e. Sc-CO2 flow and may be recovered later through reducing pressure
ethanol, acetonitrile, acetone, methanol or water, which is often downstream [37]. Technical parameters are critical, such as pres-
added in a small concentration (1 to 5 mol%) to the supercritical sure, mass percentage of water in feed and mass ratio of feed: sc-
fluid in order to change the solvent characteristics, such as polarity CO2 [38]. The lipophilic nature of CO2 is the main advantage of
and specific interactions, without changing the density and com- SAF, as it allows polar compounds present in organic extracts to be
pressibility of the original SCF solvent [31].ì. By selecting a cosol- separated and concentrated.
vent or just simply changing the molar ratio of a selected modifier,
the properties of the fluids can be drastically modified. Although 2.1. Applications SFE
water could be the solvent that attracts the most interest as a co-
solvent in the SFE process the most common polar solvents used The focus of this review is the use of Sc-CO2 to extract polyphe-
as a modifier in SFE remain ethanol and methanol. The main draw- nols from various by-products. Table 1 lists the main polyphenols
back of water as cosolvent in SFE, compared to other polar solvents and the experimental conditions of extraction provided by recent
such as methanol and ethanol, is the low solubility since only 0.3% studies.
(v/v) of water can be completely miscible with CO2 . This low sol- The by-products receiving most attention include grape
ubility could not sufficiently improve the polarity of CO2 as much residues, guava seeds, onion skins, and cacao hulls. It is possi-
as methanol and other polar solvents [32]. Ethanol represents the ble to use low concentrations of a solvent modifier (ethanol in
best choice due to its lower toxicity [24]. Addition of ethanol in- most cases) to extract polar compounds. Temperature, pressure,
creases the critical temperature, so the extraction temperature and and extraction time are the main independent variables that can
pressure must be increased to keep the solvent mixture in its crit- be changed. The efficiency of extraction is measured in terms of
ical region. A solvent modifier can be introduced and mixed with extraction yield or percentage total phenols. A wide range of tem-
CO2 by installing a second pump feeding into a mixing chamber, peratures (40–90 °C) is reported (Table 1). The recommended ex-
or it can be injected directly into sample before extraction [25]. traction pressure varies between 20 and 30 MPa; at high pres-
Compounds must be soluble in Sc-CO2 but it is possible to vary sures there is an increase in solvent density. A recent study in-
solubility by varying the temperature and pressure during extrac- vestigated response surface methodology, with the aim of opti-
tion. Moreover, modifiers can further increase solubility. Generally, mizing extraction of nutraceutical compounds from the by-product
when the pressure increases, solvent density and solubility of de- of brown onion skin, using supercritical carbon dioxide/cosolvent.
sirable compounds increase. In this case, a smaller volume of sol- Onion skins are rich in polyphenols but remain under-explored as
vent is thus required for each extraction [25]. a by-product. The study optimized pressure, temperature and sol-

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

Table 1
Extraction conditions used to extract polyphenols from agricultural food by-products using supercritical fluid extraction.

By-product Target compounds Extraction conditions References

Elder berry and Anthocyanins, Modifier ethanol with CO2, Tc 40 °C at 15, 35 MPa [39]
grape marc phenols
Wheat germ Phenolic 10, 60 min extraction time, Tc (40, 60 °C) at 14.8, 60.2 MPa [40]
Canola Phenolic Modifier ethanol (95%) with CO2, 60 min extraction time, flow rate of CO2 70 g/min, Tc 50 °C [41]
compound and Pc 40 MPa
Strobilanthes Flavonoids Modifier ethanol with CO2 , 40, 60, 80 min extraction time, Tc (40, 50, 60 °C) at 10, 15, 20 MPa [42]
Psidium guajava L. Phenolic Modifier ethylacetate and ethanol with CO2, 120 min extraction time, Tc (40, 50, 60 °C) at 10, [43]
seed compounds 20, 30 MPa
Grape residues Polyphenols, Supercritical antisolvent extraction: methanol, Tc 40 °C, 11 MPa [44]
Arbutus unedo Phenolic Modifier ethanol (0% to 20%) with CO2 , 60 min extraction time, flow rate of CO2 at 15 g/min, Tc [45]
fruits compounds 30 °C, 5 MPa
Spearmint leaves Flavonoids, Modifier ethanol with CO2 , 30, 60, 90 min extraction time, Tc (40, 50, 60 °C) at 10, 20, 30 MPa [46]
Wine grapes Flavonoids, 99.9% pure CO2 as solvent at Tc/Pc of 40 °C/35 MPa, S/F ratio of 6.6 [47]
phenolic acids
Coffee Phenolic Pc of 20 (husk) and 10 MPa (spent coffee), 4% and 8% ethanol (w/w) as solvents, Tc 50 (coffee [48]
compounds husks) and 60 °C(coffee grounds)
Bitter melon Flavonoids Modifier ethanol with CO2 40, 50, 60 min extraction time, Tc (30, 40, 50 °C) at 25, 30, 35 MPa [49]
Grape seeds Phenolic Temperature 44–46 °C, pressure 1.53–16 MPa [50]
Grape bagasse Anthocyanins, 20 g of bagasse as feed material, CO2 + 96% ethanol 10% (w/w) as modifier, Tc40 °C, 2 extraction [51]
catechins, flavonols cycles at Pc 2 and 35 MPa, S/F ratio 80 and 115, respectively
Blackberry bagasse Anthocyanins Modifier ethanol (10%) with CO2 , 55 min extraction time, flow rate of CO2 at 10 mL/min, Tc [52]
(Rubus sp.) 60 °C, 15 MPa
Punica granatum L. Flavonoids Modifier ethanol (80%) with CO2 , 120 min extraction time, flow rate of CO2 at 2 g/min, Tc 55 °C, [53]
peel 30 MPa
Cacao pod husk Phenolic Modifier ethanol with CO2 , 2.5 h extraction time, Tc 50 °C, 20 MPa [54]
Onion skin Flavonoids Modifier ethanol (85%) with CO2 , 120 min extraction time, flow rate of CO2 at 10 mL/min, Tc [55]
40 °C, 10 MPa
Wine-making Polyphenols Modifier ethanol (20%) with CO2 , 60 °C, 25 MPa, flow rate of CO2 at 2 mL/min, flow rate of [56]
by-products ethanol at 0.4 mL/min
Grape marc Polyphenols Modifier ethanol (10%) with CO2 , 40 °C, 8 MPa, flow rate of CO2 at 6 Kg/h, ethanol 449.73 g/L [57]
Apple pomace Phenolic Modifier ethanol (5%) with CO2 , 45 °C, 30 MPa, flow rate of CO2 at 2 L/h, 120 min [58]

vent modifier and in order to improve the efficiency of extraction a 20–35 MPa. These results indicate that an industrial SFE plant is
response surface Box–Behnken design was applied. Optimized con- feasible with a capacity of 0.5m3 , yielding an extract with a phe-
ditions calculated from chemometric analysis (40 °C, 10 MPa and nolic concentration expected to be close to 23 g/kg of extract,
with 85% ethanol as solvent) yielded desirability levels of 87% with with the estimated cost of manufacture of US$ 133.16/kg. SFE pro-
a 16% extraction yield [55]. This work represents the first time that cess was more efficient than Soxhlet to extract target compounds
SFE was applied to extract bioactive compounds from dried onion (23 vs 1.8 g/Kg extract), even if the extraction yield was lower
skins, recovering 18 compounds, and furthermore this process can [51]. Another interesting application was performed by Aresta and
be scaled up to industrial levels. collaborators. SFE was successfully employed for the extraction of
Another recent example of valorisation was demonstrated with polyphenols from wine-making by-products (pomace, skins, and
cacao pod husk, extracting phenolic compounds by means of su- seeds). Final extract was characterized in terms of the total an-
percritical fluid. This by-product is derived from the chocolate in- tioxidant capacity and polyphenol content. A comparison with con-
dustry. A Box-Behnken design is used here as well, to find the best ventional technique was performed (solid-liquid extraction with
extraction conditions to obtain a phenolic compound enriched ex- ethanol 70%). The SFE approach may represent a friendly strategy
tract. As in the previous example, temperature, pressure, and use due to the very limited used volume of ethanol for the extraction
of ethanol as a co-solvent were the main variables under investi- of polyphenols [56].
gation. dependant variables consisted of yield, total phenolics and Da Porto et al., developed a combined process based on ultra-
total antioxidant capacity (ABTS assay). Under the optimized condi- sounds coupled to SFE for the recovery phenolic compounds from
tions (60 °C, 29.9 MPa and 13.7% ethanol) the extraction yield was grape marc. This study revealed an increase of the recovery of
0.52%, with the resulting extract possessing 12.97 mg GAE/g and polyphenols of 28% than traditional SFE [57]. Ferrentino et al., re-
0.213 mmol TE/g. SFE is highly selective towards antioxidant com- ported the recovery of polyphenols from apple pomace. SFE extract
pounds, and moreover it can be considered as a potential method presents an antioxidant activity 2.74 times greater than Soxhlet ex-
for the valorisation of low cost, easily available and underexploited traction besides was obtained in shorter time (2 vs 6 h) [58].
cacao pod husk by-product [54].
The economic feasibility of large-scale SFE operation was eval- 3. Pressurized liquid extraction (PLE)
uated by Farías-Campomanes et al., this study reports extraction
of phenolics form grape bagasse. Kinetic parameters for extrac- At elevated pressures and temperatures solvents possess differ-
tion and costs of extract preparation were estimated. Chosen ex- ent characteristics which can improve extraction speed. Ideally, de-
perimental conditions: CO2 with 10% ethanol (w/w) at 40 °C and sired compounds would show higher solubility in the chosen sol-
vent and interfering compounds should remain insoluble in the

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

solid matrix [20]. In order to realize this effect, some parameters

must be optimized, including solvent to feed ratio, size of particles,
concentration of solvent modifiers, time, and temperature. Conven-
tional techniques, for example Soxhlet and maceration, are expen-
sive in terms of consumption of time and solvents. Furthermore,
parameters such as diffusivity, viscosity and density may be mod-
ulated by adjusting temperature and pressure.
During PLE, pressure is applied, and temperatures may thus ex-
ceed the boiling point of solvent. This technique allows solutes to
be transferred from a solid matrix, obtaining a fast extraction rate
due to: interactions between the liquid solvent and molecules in
the matrix; high temperatures and pressures increasing extraction Fig. 1. Change in dielectric constant of water as a function of temperature.
At high temperatures (50–200 °C) an increased mass transfer
and extraction rate occur: the dissolution process is favoured, dif- [28,61–64]. In avoiding toxic solvents, the resulting extracts can be
fusion rate is increased, destruction of the solute-matrix linkage is certifiably safe. This technique presents some drawbacks: high in-
easier, solvent viscosity and surface tension are decreased, lead- vestment cost, risks of unwanted reactions at elevated tempera-
ing to an enhanced wetting of plant matter. A decrease in sur- tures (caramelization, Maillard reaction) and subsequent tub clog-
face tension leads to the generation of solvent cavities, with con- ging due to caramelization [22].
sequent dissolution of compounds [24,28]. Increasing temperature
decreases the dielectric constant, lowering the polarity of the sol- 3.1. Applications PLE
vent [28]. Application of pressure (range 10–15 MPa) keeps the
solvent in its liquid state [28]. The pressure allows the solvent As mentioned previously, polyphenols are very interesting com-
to penetrate the pores of the matrix. This pressure is most often pounds due to their antioxidant activities. This is reflected in the
10 MPa for PLE. Pressurized solvent is very versatile, but an ap- literature, where there are several studies on the development of
propriate combination of solvent and solutes is necessary [24]. Ob- new extraction methods with some examples reported in Table 2.
viously, food grade solvents must be employed, such as water or Recently Pagano and co-workers studied the by-products of
ethanol or mixture of both. Ethanol is cheap and possesses GRAS agro-industrial artichokes with the aim of extracting flavone gly-
status. If ethanol is completely eliminated, regulations on organic cosides (FLs) and caffeoylquinic acids (CQAs). The primary vari-
solvents can be avoided and costs involved in evaporating solvent ables influencing the efficiency of PHWE and isomerization of CQA
can be removed. Furthermore, there are some advantages in us- (number of cycles, solvent modifier, temperature, and extraction
ing an ethanol-water mixture: ethanol improves the solubility of period) were optimized using response surface design. The opti-
solutes while water helps desorption of solutes from matrix. The mized extraction method thoroughly extracts 93–105% of CQAs and
addition of ethanol lowers the boiling point and can improve effi- 90–105% of FLs from the external bracts and leaves of artichokes.
ciency yield too. The high temperatures did not significantly generate artefacts in
Elevated temperatures can also affect extraction yield due to in- this case. The PHWE extracts had antioxidative effects (EC50 11–
creased mass transfer and extraction rate. The temperature range 83 μg/mL) on human hepatocarcinoma HepG2 cells, as measured
usually falls in the range of 100–180 °C, as temperature higher by a cellular antioxidant activity assay [85].
than 140–150 °C, may cause degradation of thermo-labile com- PLE was employed in extracting the polyphenols and antioxi-
pounds or formation of undesirable products due to Maillard re- dants present in industrial apple pomace: temperatures were ap-
action [29]. Matrix characteristics can influence PLE, as the nature plied in two ranges, between 160 and 193 °C, or 75 and 125 °C.
of target compounds, particle size and moisture are unique to each A DPPH assay was used to measure antioxidant activity, and total
vegetal sample [24]. phenol content was measured. Response values were maximised
PLE may run in static mode, dynamic mode or in combination. through response surface methodology. The highest antioxidant ac-
Extraction enhancers can be used to increase extraction efficiency, tivity was provided by a 200 °C temperature, but unavoidable for-
and these include drying agents, dispersing agents and other addi- mation of unwanted compounds including hydroxymethylfurfural
tives [59]. was observed. To overcome this limitation, lower temperatures
This advanced green technique allows for quicker extraction were recommended between 75 and 125 °C. Under these condi-
and higher yield compared to other solid extraction techniques, tions, the highest level of antioxidant activity was provided by 60%
leading to commercial viability as an alternative technique to ob- ethanol at 102 °C. PLE extracts showed 2.4 times greater activity
tain valuable bioactive molecules from by-products [29]. In the than in traditional solid-liquid extraction. Therefore, this technique
case where the chosen solvent is water at 100%, PLE is known could represent an improvement over conventional techniques for
as pressurized hot water extraction (PHWE) or subcritical water the extraction of antioxidants [67].
extraction (SWE). Under these conditions, water possesses polar- Temperature can affect extraction yield. Monrad and co-authors
ity comparable to alcohols, and represents a good solvent for a demonstrated that a high temperature is necessary to extract pro-
broad base of analytes, due to its dielectric constant decreasing cyanidins from red grape pomace efficiently. Experimental condi-
as temperature is increased. PHWE allows the reduction of or- tions were 80 °C and 6.8 MPa. The study aimed to optimize the
ganic solvent consumption, quick extraction time, low costs, it is recovery of procyanidins from dried Sunbelt red grape pomace us-
environmentally-friendly due to the nature of water (non-toxic, re- ing GRAS solvents, optimising the temperature and solvent used.
cyclable, readily available) and thus, it constitutes a suitable tech- Results revealed the potential value of this technique for the grape
nique for industrial applications [60]. At room temperature, wa- juice industry as a innovative method for extracting procyanidins
ter has a dielectric constant approaching 80, but this drops to from grape by-products with subsequent uses as nutraceuticals or
the region of 30 at 250 °C, becoming comparable to methanol food supplements [66].
(Fig. 1) promoting the solubilisation of less polar compounds. In New insight into the efficacy of PLE was evaluated by García
this way, PHWE can be used to extract low polar and non-polar and collaborators on the recovery of bioactive compounds from
compounds, i.e. carotenoids, curcuminoids, lipids, and essential oils pomegranate peel as material recycling. Pomegranate peel repre-

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

Table 2
Extraction conditions used to extract polyphenols from agricultural food by-products using pressurized liquid extraction.

By-product Target compounds Extraction conditions References

Bitter melon Phenolic acids and 1 g, water, 10 MPa, 200 °C, 2 mL/min flow rate, 60 min, 120 mL solvent volume [65]
(Momordica catechins
Red grape pomace Procyanidins 50% ethanol, pressure 6.8 MPa, temperature 80–140 °C, 0.5 g [66]
Apple pomace Phenolic acids, 60% ethanol, pressure 10.3 MPa, temperature 102 °C, 5 min, 1 g [67]
flavonols and
Citrus pomaces Flavones Temperature 200 °C, pressure 1.4 MPa, 60 min [68]
Pomegranate peel Hydrolyzable 10 g, 100% water, pressure 10.2 MPa, temperature 40 °C, 5 min [69]
Red grape pomace Anthocyanins 0.5 g, 50 and 70% ethanol, pressure 6.8 MPa, temperature 40–140 °C [70]
Oregano, tarragon Phenolic acids, 1.5 g, ethanol and water and mixture 25/75- 50/50- 75/25, 10.34 MPa, 20 min, 50–200 °C [71]
and wild thyme flavones,
flavanones and
Onion skin Flavonols 100% water, pressure 9–13.1 MPa, temperature 165 °C, 15 min, 1.5:2.5 sample: DE [72]
Potato peel Phenolic acids 100% water, pressure 6 MPa, temperature 180 °C, 30 min, 2 mL/min [73]
Abuticaba (Plinia Anthocyanins Pressure 5 MPa, temperature280 °C, 9 min (static mode), 4.5 g, ethanol [74]
cauliflora) skin
Citrus (Citrus Flavanones 1 cycle of PHWE at 170 °C temperature and pressure 10.13 MPa, 10 min [75]
Pomegranate seeds Phenolic acids Temperature 220 °C, 30 min, pressure 6 MPa, solid to water ratio 1:40 [76]
Potato peels Anthocyanins 10 g/min, time 3 h, pressure 20 MPa, temperature 80 °C, ethanol 80% pH 2.6 [77]
Mango peels Phenolic Temperature 180 °C, 90 min, solid to water ratio 1:40 and pH 4 [78]
Mango peel Polyphenols Ethanol, 330 min [79]
Spent coffee Phenolic acids Temperature 177 °C, 55 min, pressure 5 MPa, 14.08 g/L [80]
Raspberry pomace Polyphenols Temperature 80 °C, pressure 10,3 MPa; ethanol/water (50:50), 15 min [81]
White grape Phenolic Temperature 210 °C, pressure 10 MPa, 30 min, 5–10 mL/min [82]
pomace compounds
Grape pomace Proanthocyanidins Temperature 90 °C, pressure 10.3 MPa, water/ethanol (85:15) [83]
Cocoa bean hulls Phenolic Temperature 70 °C, pressure 10 MPa, ethanol, 20 min [84]
Artichoke bracts Phenolic acids and Temperature 93 °C, number of cycles 2, ethanol 10% v/v, static time 5 min, 1 g, 10.34MPa [85]
and leaves flavones
Grape marc Anthocyanins Temperature 40 °C, pressure 10 MPa, acidified ethanol/water (50:50), 40 min [86]
Wine-making Catechins, tannins, Temperature 100 °C, number of cycles 2, ChClUl 30% (Choline chloride combined with urea), [87]
by-products flavonols, static time 10 min, 2 g, 10.34MPa
Pomegranate peel Phenolic acids, Temperature 200 °C, ethanol 77% v/v, 10.34MPa [88]

sents 10.5% of the pomegranate fruit fresh weight. PLE method tures, DESs are known as NADESs (natural deep eutectic solvents).
was developed using a mixture of ethanol:water and under opti- A modern methodology was applied to extract valuable phenolic
mal conditions (after experimental design) total phenolic content compounds from wine-making by-products by NADESs as cosol-
(TPC) content was 164.3 ± 10.7 mg gallic acid equivalent (GAE)/g vent. Choline chloride combined with urea 30% at temperature of
DW, in terms of phenolic acids, flavonoids, and hydrolysable tan- 100 °C led to an efficient and superior extraction compared to only
nins [88]. subcritical water in terms of significant increase of phenolic con-
Sequential PLE process with change of solvent and increase of tent (i.e. for catechin an increase of 45.05% and for epicatechin of
temperature in the second step was performed to extract antho- 47.98%). The temperature rise allowed an increase in the phenolic
cyanins from grape marc [86]. content (40–120 °C). The implementation of subcritical water with
In recent years, the use of alternative solvents, DESs (deep eu- NADESs to recover phenolic compounds from winery by-products
tectic solvents) has been emerging for the green extraction of phe- had never be done before [87].
nolic compounds from agricultural by-products. DES is a mixture
of a halide salt or another hydrogen bond acceptor (HBA) and one 4. Ultrasound assisted extraction (UAE)
or two hydrogen bond donors (HBDs). DESs are usually formed
by choline chloride (quaternary ammonium salt) as HBA and un- Ultrasounds are a form of sound wave beyond the frequencies
charged compounds, such as sugars, amines, carboxylic acids, alco- humans are able to perceive; as sound waves, they travel through
hols as HBDs [89]. This new generation of solvents possesses excel- media as a compression and expansion. At high enough frequen-
lent biocompatibility and low toxicity. Unfortunately, the high vis- cies this leads to cavitation, in which bubbles are formed, grow
cosity of these solvents results in time-consuming solvent transfer and then collapse due to high pressure and temperature (4726 °C
operations and slow mass transfer. Adding water to DES helps to and 101 MPa). In a plant matrix, cavitation facilitates leaching from
overcome these problems. If natural components (choline chloride, the matrix by increasing mass transfer and solvent diffusivity; af-
sucrose, trehalose) are used for the formulation of eutectic mix- ter breaking cell wall, solutes diffuse and are captured. A study of

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

the matrix reported fragmentation under irradiation, with an en- lent/100 g FW), as was flavanone concentration (70.3 mg naringin
hanced hydration matrix [90]. Some authors observed erosion of and 205.2 mg hesperidin/100 g FW) and extraction yield (10.9%),
the raw plant material after ultrasound treatment, resulting in en- proving the efficiency of UAE in comparison with conventional
hanced extraction [90]. techniques. Furthermore, studies on antioxidant activity ((2,2 -
This technique is not time consuming and does not consume diphenyl-1-picrylhydrazyl radical) DPPH• and (Oxygen Radical ab-
solvent [22]. sorbance Capacity) ORAC assays) demonstrated that UAE is suitable
UAE uses ultrasonic energy (>20 kHz), it makes cavitation bub- for preparing antioxidant-rich extracts from by-products.
bles, which collapse producing high shear. This mechanism ensures There has been much recent demand for new extraction meth-
a complete extraction. In particular, the suspended powdered sam- ods to be developed, to reduce extraction time and obtain extracts
ple induces asymmetric bubble collapse [91]. Bubbles absorb en- with high yield and biological activity. Some researchers have
ergy until this reaches an unsustainable limit before collapsing: performed studies on dried peel from pomegranate marc, aim-
this collapse is called cavitation in sonochemistry [24] . ing to improve antioxidant yields, activities and extraction kinet-
UAE combines the merits of acoustic excitation and solvents ics by continuous ultrasound-assisted extraction (CUAE) and pulsed
to extract desirable compounds. Ultrasounds provide instantaneous ultrasound-assisted extraction (PUAE). For CUAE, the major factors
formation and collapse of cavitation bubbles, generating instanta- studied were treatment time and intensity level, whereas for PUAE
neous high pressure and temperature. Thus, solvent penetration intensity level, number of repeat pulses, pulse duration and inter-
into cellular parts, cell wall disruption, and the subsequent release val were the deciding elements. The results show that treatment
of analytes are very efficient [33]. Ultrasound is applied directly by time is the only one of these variables with significant effects on
a probe system or indirectly by a water bath [23]. the activity of extracted antioxidants. All factors were found to sig-
Temperature and pressure change after implosions, causing nificantly affect the antioxidant yield; with a 59.2 W/cm2 intensity,
shear disruption, cell membrane thinning and breakdown of cells. PUAE at a pulse duration of 5 s and interval of 5 s was found to
The penetration of solvent into cells is thus enhanced and the have similar antioxidant yields as CUAE (14.5% and 14.8%) and sim-
mass transfer of desired compounds into solvent is increased. The ilar DPPH scavenging activities (5.8 and 5.5 g/g) with a 60 min ex-
implosions accelerate the diffusion by causing turbulence. Ultra- traction time, at 25 ± 2 °C with a water/peel ratio of 50/1, w/w.
sonic wave implosions provide easier hydration and subsequent CUAE and PUAE improved antioxidant yield by 24% and 22% and
swelling of the matrix. Some parameters are fundamental: fre- decreased time of extraction by 90% and 87%, respectively, when
quency and intensity of ultrasound, viscosity and surface tension compared to conventional extraction [109].
of the medium, pressure and temperature. As agricultural and industrial by-products, olive leaves repre-
UAE acts in two steps: solvent enters the matrix following dis- sent an inexpensive, renewable and abundant source of polyphe-
ruption of the cellular matrix, particle size is reduced, with me- nols. Şahin and Şamlı, optimised ultrasound-assisted extraction
chanical effects; extracts are washed out of the matrix with the of olive leaf extract, by means of a response surface methodol-
increase of surface area of contact between solid and liquid phases ogy [111]. The ideal combination of solvent concentration (0–100%
[92]. A suitable solvent is mixed with the sample and sonicated at ethanol (EtOH), v/v), solid to solvent ratio (25–50 mg/mL) and ex-
a specific temperature for a precise amount of time. This technique traction time (20–60 min) were investigated by response surface
has been used in both static and dynamic mode [14]. To increase methodology (RSM). The final settings were found to be 500 mg
the extraction efficiency ultrasounds are also used in conjunction solid to 10 mL solvent ratio, extraction time of 60 min and a 50%
with another innovative extraction technique [93]. UAE can de- EtOH solvent. Solvent concentration was the most significant pa-
grade active principles from plant matrices, as a result of oxidative rameter in affecting extraction performance of UAE of those inves-
pyrolysis caused by hydroxyl radicals under cavitation. tigated. During the production of olive oil, olive pomace contains
UAE represents an inexpensive green extraction technique and also high-added value compounds. Ultrasound increases the aque-
it is very simple; it allows rapid extraction of thermo-labile com- ous extraction of phenolic compounds with high antioxidant activ-
ponents at low/mild temperature. In the last decade, some patents ity, improving the extraction efficiency of water and yielding ex-
have been registered regarding the use of ultrasounds for the ex- tracts at these conditions: 250 W power, extraction time 75 min,
traction of ingredients. In particular, Mitchell and collaborators in- 2 g dried pomace/100 mL water as recently reported by Goldsmith
vented a process for the fractionation and extraction of new ac- and co-authors [117]. Quercetin is the most abundant compound of
tive compounds from plant material [94,93] and several processes onion by-products and UAE was successfully employed to extract
for isolating lignin, cellulose and water-insoluble compounds from this important bioactive compound [104,113].
biomass [95–97], without degrading them. These patents demon- Several studies demonstrated as main advantages of UAE reduc-
strate the potential industrial applicability of this extraction tech- tion of time and energy. For example, this technique was success-
nique using high frequency pulses and shear forces, with the cor- fully applied for the extraction of phenolic compounds from red
related advantages. araçá peel, with an increase of 12% in the content of anthocyanins
and a 25% reduction time of extraction compared to maceration
4.1. Application UAE [123].
In the last years, DES solvents have emerged as new sustainable
The potential of UAE has been explored by several studies in eco-friendly extractants.
recent years: Table 3 presents some examples of ultrasound being To enhance the extraction efficiency, DES can be combined with
used to extract polyphenols from by-products. UAE. The heat generated by ultrasounds decreases the DES viscos-
Some authors investigated extraction of polyphenols from or- ity, enhancing its penetration into vegetable matrix. For example,
ange (Citrus sinensis L.) peel (an abundant food by-product), with an environmentally friendly method for the extraction of phenolic
a focus on flavanones, by means of ethanol used as a food compounds was developed by de los Ángeles Fernández and col-
grade solvent [100]. A response surface methodology (RSM) was laborators. The combination of lactic acid, glucose and 15% water
used to evaluate process settings, feeding into a central com- (LGH-15) were utilized in onion, tomato, olive and pear industrial
posite design (CCD) approach. Statistical analysis showed opti- by-products. A high-efficiency and very versatile UAE method was
mised conditions of a 40 °C process temperature, sonication power developed. To demonstrate the potential of LGH-15, comparison of
of 150 W and an ethanol: water ratio of 4:1 (v/v). The re- extraction efficiency was made with methanol and water, and re-
sulting phenolic content was high (275.8 mg gallic acid equiva-

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

Table 3
Extraction conditions used to extract polyphenols from agricultural food by-products using ultrasound assisted extraction.

By-product Target compounds Extraction conditions References

Grape seeds Phenolic compounds, US bath (40 kHz, 250 W, 10 L), temperature [98]
anthocyanins 33–67 °C, time 16–34 min, 2 g, 100 mL ethanol,
ethanol concentration: 33–67%
Orange peel Polyphenols 30 W, temperature 30 °C, time 40 min, and 30 W, [99]
temperature 40 °C, time 10 min, 2 g in 80%
Orange peel Flavonoids Ethanol:water ratio 4:1 (v/v), 40 °Cand 150 W UP, [100]
extraction time 30 min
Citrus peel Flavonoids 60 kHz, temperature40 °C, water as solvent, [101]
extraction time 30 min, citrus peel:water ratio
1:10 g/mL
Rice bran Polyphenols US bath (35 kHz, 140 W), temperature 51–54 °C, [102]
time 40–45 min, ethanol 65–67% (v/v)
Prunella vulgaris L. plant Flavonoids Ethanol 41% (v/v), temperature 79 °C, time [103]
30.5 min, liquid to solvent ratio 30:1 (mL/g)
Onion skin Quercetin 43.8% ethanol (v/v), 21.7 min, 606.4 W [104]
Grapes Flavonoids Water–ethanol (50:50), extraction temperature [105]
10 °C, 200 W and 24 kHz, extraction time 6 min,
Marjoram Flavone, phenolic acid, US probe (20 kHz, 19 mm), 0.5 g, 25 mL, [106]
diterpene MeOH/H2 O 80/20% (v/v), time 5– 15 min,
temperature 15–35 °C
Apple pomace Flavans, flavonols, phenolic Solid liquid ratio 150 mg/mL, US bath (25 kHz, [107]
acids 150 W), temperature 40 °C, time 40 min, 50 mM
malate buffer pH 3.8
Black chokeberry Polyphenols US bath (30 kHz, 100 W), temperature 20–80 °C, [108]
time 0–255 min, ethanol:water ratio 50:50 (v/v)
Pomegranate peel Polyphenols US bath (20 kHz, 2.4–59.2 W), temperature 25 °C, [109]
time 60 min, water/peel ratio 50:1 w/w
Hawthorn seed Flavonoids Ethanol 72% (v/v), temperature 91 °C, time [110]
37 min, 40 W, solid to liquid ratio 1:18
Olive leaves Flavonoids 50% ethanol, sample/solvent ratio (500 mg dried [111]
leaf to 10 mL), 220 V and 50 Hz, extraction time
60 min
Grape seeds Flavonols, tannins, US bath (20 kHz, 150 W), temperature 30 °C, time [112]
anthocyanins 30 min, methanol
Onion Quercetin US bath (40 kHz, 469 W), temperature 49 °C, time [113]
15–35 min, ethanol 59% (v/v)
Wheat dried distiller’s grain Total polyphenols US bath (24 kHz, 400 W), temperature 20 °C, time [114]
0–20 min, water
Chilean papaya Isothiocyanates, phenolic 5 g papaya seeds + 250 mL of 80% aqueous [115]
acids, and flavanols methanol, 42 kHz and 130 W of ultrasound bath
extractor, extraction time 10 min, solid liquid
ratio of 1:2
Riceberry bran Phenolic acids, flavonoids, 5 g powder + 100 mL of 65% aqueous ethanol, [116]
anthocyanins 43 kHz of ultrasound bath extractor, extraction
time 40 min, temperature 51 °C
Olive pomace Phenolic compounds 250 W, 75 min, 2 g/100 mL water [117]
Potato (peel and outer layer) Caffeoylquinic acid 55% (v/v) ethanol/water ratio, 34 kHz, extraction [118]
time 35 min, temperature 35 °C, solid liquid ratio
of 1/10 (w/v)
Olive leaves Oleuropein, phenolic acids, 250 mg powder olive leaves + 20 mL of 50% [119] [115] [115] [115]
flavonoids acetone, 37 kHz ultrasound bath extractor,
extraction time 10 min, 60 °C, solid liquid ratio of
Onion, tomato, olive and pear by-products Phenolic compounds lactic acid, glucose and 15% water NADES [120]
(LGH-15), 200 W, 20 kHz, 30–60 min, 40 °C
Spent coffee grounds Phenolic compounds 1,6-hexanediol:ChCl molar ratio of 7:1 (HC-6) [121]
67.5% w/w, 10 min, 60 °C
Spent coffee grounds Chlorogenic acid, 244 W, 40 °C, 40 min, 1.17 g/mL SL, ethanol [122]
protocatechuic acid
Red araçá peel Anthocyanins 154 W, 90 min, 40 KHz, ethanol 90%+0.1% HCl [123]

sults confirm a good extractability both for polar and weak polar capacity. However, in large scale application, for the recovery of
compounds compared to traditional solvents [120]. valuable compounds from agricultural by-products, further studies
DESs show promising uses due to their many advantages: their are mandatory.
synthesis is cheap and simple; are tailor-made solvents, they in-
volve low toxicity and biodegradability and therefore represent ex-
cellent alternative to commonly green solvents. Moreover, these 5. Conclusions and future perspective
solvents present the possibilities over the conventional solvents to
design them for specific aims, low volatility and higher extraction With the increase in environmental awareness, there is grow-
ing interest in circular economy and on the valorisation of food

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

by-products which are still underestimated. Agricultural and food Declaration of Competing Interest
by-products are usually considered a great problem for industry
in terms of cost and environmental effects induced by their dis- The authors declare that they have no known competing finan-
posal. Nowadays, these matrices are considered as a cheap source cial interests or personal relationships that could have appeared to
of bioactive compounds usable as functional additives in different influence the work reported in this paper. The authors declare no
products, leading at same time benefits for environment. However, conflict of interest.
in order to make food by-products interesting and economically
sustainable source of bioactive compounds, the selection and op- CRediT authorship contribution statement
timization of a suitable environmentally friendly extraction tech-
nologies which allow the recovery and sustainability of target ana- Imma Pagano: Writing – review & editing. Luca Campone:
lytes is indispensable. Sustainability and circularity of processes are Conceptualization, Writing – review & editing, Supervision. Rita
key words for industrial sector, reducing postharvest losses, val- Celano: Software, Writing – review & editing. Anna Lisa Piccinelli:
orizing by-products, and extracting bioactive compounds. Writing – original draft, Writing – review & editing. Luca Rastrelli:
The large amount of agricultural by-products determines the Project administration, Funding acquisition, Supervision.
need to develop scalable technology for industrial application able
to rapid, applicable, efficient, with high recovery, short process Acknowledgement
time, low costs, and allow the use of small volume of organic sol-
vent. Financial support from the Italian Ministry of University and
Conventional extraction techniques to obtain these high added Research (MIUR) through grant “Dipartimenti di Eccellenza 2017
values ingredients which are time, and energy consuming, labo- to University of Milano Bicocca, Department of Biotechnology and
rious, employ large amount of toxic solvents have been consid- Biosciences is also acknowledged.
ered the limiting factor until now. At present, development and
the improvement of innovative extraction techniques such as UAE,
PLE and SFE which are characterized by low organic solvent con- [1] O. Santana-Méridas, A. González-Coloma, R. Sánchez-Vioque, Agricultural
sumption, short time extraction, high selectivity, and good extrac- residues as a source of bioactive natural products, Phytochem. Rev. 11 (2012)
tion yields open new perspectives in the recycling of agricultural
[2] V.G. Zuin, L.Z. Ramin, Green and sustainable separation of natural products
food by-products. These techniques may be easily scalable, pro- from agro-industrial waste: challenges, potentialities, and perspectives on
viding interesting advantages for the industrial applications aimed emerging approaches, in: Lin C. (Eds), Chemistry and Chemical Technologies
to produce new ingredients for both food supplements and func- in Waste Valorization Topics in Current Chemistry Collections. Springer, Cham
(2018) 229–282, doi:10.1007/978- 3- 319- 90653- 9_8.
tional foods. Some of the applications reported in the previous [3] L. Chen, L. Xing, L. Han, Renewable energy from agro-residues in China: solid
section highlighted that these non-conventional extraction tech- biofuels and biomass briquetting technology, Renew. Sustain. Energy Rev. 13
nologies possess a great prospective for the efficient extraction of (2009) 2689–2695.
[4] FAOThe State of Food and Agriculture 2019. Moving forward on food loss and
bioactive compounds from agricultural food by-products. The cor- waste reduction, CC BY-NC-SA 3.0 IGO, Rome. Licence, 2019.
rect use of these extraction techniques is closely related to under- [5] H.K. Jeswani, G. Figueroa-Torres, A. Azapagic, The extent of food waste gen-
standing of the extraction mechanism and to the selection of ex- eration in the UK and its environmental impacts, Sustain. Prod. Consum. 26
(2021) 532–547.
traction conditions. Several instrumental parameters influence di- [6] I. Goñi, D. Hervert-Hernández, By-products from plant foods are sources of
rectly and indirectly the extraction process, so finding the right dietary fibre and antioxidants, Phytochemicals - Bioactivities and Impact on
extraction conditions is not easy and often require a multivariate Health, IntechOpen, 2011.
[7] C.A. Ledesma-Escobar, M.D. Luque de Castro, Coverage exploitation of
analysis. For these reasons in order to obtain the best extraction
by-products from the agrofood industry, Green Extraction of. Natural Prod-
parameters the use of multivariate experimental design strategies ucts: Theory and Practice, Wiley-VCH, Weinheim, 2015.
(Design of Experiments, DOE) that simultaneously change variables [8] Á. Peralbo-Molina, M.D.L. de Castro, Potential of residues from the Mediter-
ranean agriculture and agrifood industry, Trends Food Sci. Technol. 32 (2013)
in different experiments are preferable if not even mandatory.
The extraction techniques are in continuous and constant de- [9] F.J. Barba, Z. Zhu, M. Koubaa, A.S. Sant’Ana, V. Orlien, Green alternative
velopment: i.e. the use of alternative solvents, such as ionic liq- methods for the extraction of antioxidant bioactive compounds from win-
uids and DESs, can reduce the environmental impact. Further the ery wastes and by-products: a review, Trends Food Sci. Technol. 49 (2016)
combination of ultrasound with SFE processes, that can be a feasi- [10] N. Balasundram, K. Sundram, S. Samman, Phenolic compounds in plants and
ble mean to enhance the extraction kinetics, increases the global agri-industrial by-products: antioxidant activity, occurrence, and potential
extraction yield and reduces the extraction time and thus oper- uses, Food Chem. 99 (2006) 191–203.
[11] D.R. Kammerer, J. Kammerer, R. Valet, R. Carle, Recovery of polyphenols from
ational costs, without compromising the quality of the final ex- the by-products of plant food processing and application as valuable food in-
tracts. There are many other possibilities from combination of ex- gredients, Food Res. Int. 65 (2014) 2–12.
traction processes or using of several technologies in parallel in or- [12] F. Potì, D. Santi, G. Spaggiari, F. Zimetti, I. Zanotti, Polyphenol health effects on
cardiovascular and neurodegenerative disorders: a review and meta-analysis,
der to promote the production of bioactive ingredients from food Int. J. Mol. Sci. 20 (2019) 351.
by-products. Another application that could increase extraction ef- [13] A. Alesci, N. Cicero, A. Salvo, D. Palombieri, D. Zaccone, G. Dugo, M. Bruno,
ficiency is the combination of an enzymatic hydrolysis (at high R. Vadalà, E.R. Lauriano, S. Pergolizzi, Extracts deriving from olive mill waste
water and their effects on the liver of the goldfish Carassius auratus fed with
pressure) with the supercritical fluid extraction or with pressurized
hypercholesterolemic diet, Nat. Prod. Res. 28 (2014) 1343–1349.
liquid extraction. [14] A. Khoddami, M.A. Wilkes, T.H. Roberts, Techniques for analysis of plant phe-
Finally, one of the last aspects to consider, concerns the pos- nolic compounds, Molecules 18 (2013) 2328–2375.
[15] F. Chemat, M.A. Vian, G. Cravotto, Green extraction of natural products: con-
sibility of scaling up the extraction method. Currently, only a few
cept and principles, Int. J. Mol. Sci. 13 (2012) 8615–8627.
SFE applications have been used on a industrial scale, while in the [16] K.M. Kibler, D. Reinhart, C. Hawkins, A.M. Motlagh, J. Wright, Food waste and
case of PLE, although the scale-up process is easy, it is not very the food-energy-water nexus: a review of food waste management alterna-
widespread. tives, Waste Manag. 74 (2018) 52–62.
[17] F. Chemat, N. Rombaut, A.-.S. Fabiano-Tixier, J.T. Pierson, A. Bily, Green extrac-
Agricultural by-products can be used as an extraction material tion: from concepts to research, education, and economical opportunities, in:
and phenolic compounds recovered by advanced techniques could Green Extraction of Natural Products: Theory and Practice, Wiley CH, 2015,
be introduced again into the production chain in order to con- pp. 1–36.
[18] R. Gallego, M. Bueno, M. Herrero, Sub-and supercritical fluid extraction of
tribute to required circular and sustainable economy. bioactive compounds from plants, food-by-products, seaweeds and microal-
gae–an update, TrAC Trends Anal. Chem. 116 (2019) 198–213.

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

[19] C.M. Galanakis, Recovery of high added-value components from food wastes: [45] S. Akay, I. Alpak, O. Yesil-Celiktas, Effects of process parameters on supercriti-
conventional, emerging technologies and commercialized applications, Trends cal CO2 extraction of total phenols from strawberry (Arbutus unedo L.) fruits:
Food Sci. Technol. 26 (2012) 68–87, doi:10.1016/j.tifs.2012.03.003. an optimization study, J. Sep. Sci. 34 (2011) 1925–1931.
[20] C. Pronyk, G. Mazza, Design and scale-up of pressurized fluid extractors for [46] M. Bimakr, R.A. Rahman, F.S. Taip, A. Ganjloo, L.M. Salleh, J. Selamat,
food and bioproducts, J. Food Eng. 95 (2009) 215–226. A. Hamid, I.S.M. Zaidul, Comparison of different extraction methods for the
[21] M. De la Guardia, S. Armenta, Origins of green analytical chemistry, in: Com- extraction of major bioactive flavonoid compounds from spearmint (Mentha
prehensive Analytical Chemistry, Elsevier, 2011, pp. 1–23. spicata L.) leaves, Food Bioprod. Process. 89 (2011) 67–72.
[22] J. Azmir, I.S.M. Zaidul, M.M. Rahman, K.M. Sharif, A. Mohamed, F. Sahena, [47] J.M. Prado, I. Dalmolin, N.D.D. Carareto, R.C. Basso, A.J.A. Meirelles,
M.H.A. Jahurul, K. Ghafoor, N.A.N. Norulaini, A.K.M. Omar, Techniques for ex- J.V. Oliveira, E.A.C. Batista, M.A.A. Meireles, Supercritical fluid extraction of
traction of bioactive compounds from plant materials: a review, J. Food Eng. grape seed: process scale-up, extract chemical composition and economic
117 (2013) 426–436, doi:10.1016/j.jfoodeng.2013.01.014. evaluation, J. Food Eng. 109 (2012) 249–257.
[23] M.B. Soquetta, L. de M. Terra, C.P. Bastos, Green technologies for the extrac- [48] K.S. Andrade, R.T. Gonçalvez, M. Maraschin, R.M. Ribeiro-do-Valle, J. Martínez,
tion of bioactive compounds in fruits and vegetables, CyTA-J. Food 16 (2018) S.R.S. Ferreira, Supercritical fluid extraction from spent coffee grounds and
400–412. coffee husks: antioxidant activity and effect of operational variables on ex-
[24] K. Ameer, H.M. Shahbaz, J. Kwon, Green extraction methods for polyphenols tract composition, Talanta 88 (2012) 544–552.
from plant matrices and their byproducts: a review, Compr. Rev. Food Sci. [49] B. Shan, J.H. Xie, J.H. Zhu, Y. Peng, Ethanol modified supercritical carbon diox-
Food Saf. 16 (2017) 295–315. ide extraction of flavonoids from Momordica charantia L. and its antioxidant
[25] M.C. Bubalo, S. Vidović, I.R. Redovniković, S. Jokić, New perspective in extrac- activity, Food Bioprod. Process. 90 (2012) 579–587.
tion of plant biologically active compounds by green solvents, Food Bioprod. [50] K. Ghafoor, F.Y. AL-Juhaimi, Y.H. Choi, Supercritical fluid extraction of phenolic
Process. 109 (2018) 52–73. compounds and antioxidants from grape (Vitis labrusca B.) seeds, Plant Foods
[26] E.U. Commission, Commission Regulation (EU) No 1129/2011 of 11 November Hum. Nutr. 67 (2012) 407–414.
2011 amending Annex II to Regulation (EC) No 1333/2008 of the European [51] A.M. Farías-Campomanes, M.A. Rostagno, M.A.A. Meireles, Production of
Parliament and of the Council by establishing a Union list of food additives, polyphenol extracts from grape bagasse using supercritical fluids: yield, ex-
Off. J. Eur. Union L. 295 (2011) 11–12. tract composition and economic evaluation, J. Supercrit. Fluids 77 (2013)
[27] R.A.S. Safe, Title 21–food and Drugs Chapter I–Food and Drug Administration 70–78.
Department of Health and Human Services Subchapter B–Food For Human [52] J.L.P. Reátegui, A.P. da Fonseca Machado, G.F. Barbero, C.A. Rezende,
Consumption (continued), (2011). J. Martínez, Extraction of antioxidant compounds from blackberry (Rubus sp.)
[28] G. Joana Gil-Chávez, J.A. Villa, J. Fernando Ayala-Zavala, J. Basilio Heredia, bagasse using supercritical CO2 assisted by ultrasound, J. Supercrit. Fluids 94
D. Sepulveda, E.M. Yahia, G.A. González-Aguilar, Technologies for extraction (2014) 223–233.
and production of bioactive compounds to be used as nutraceuticals and food [53] M. Mushtaq, B. Sultana, F. Anwar, A. Adnan, S.S.H. Rizvi, Enzyme-assisted su-
ingredients: an overview, Compr. Rev. Food Sci. Food Saf. 12 (2013) 5–23. percritical fluid extraction of phenolic antioxidants from pomegranate peel, J.
[29] H. Wijngaard, M.B. Hossain, D.K. Rai, N. Brunton, Techniques to extract bioac- Supercrit. Fluids 104 (2015) 122–131.
tive compounds from food by-products of plant origin, Food Res. Int. 46 [54] L. Valadez-Carmona, A. Ortiz-Moreno, G. Ceballos-Reyes, J.A. Mendiola,
(2012) 505–513, doi:10.1016/j.foodres.2011.09.027. E. Ibáñez, Valorization of cacao pod husk through supercritical fluid extrac-
[30] A.I. Talmaciu, I. Volf, V.I. Popa, A comparative analysis of the ‘green’techniques tion of phenolic compounds, J. Supercrit. Fluids 131 (2018) 99–105.
applied for polyphenols extraction from bioresources, Chem. Biodivers. 12 [55] L. Campone, R. Celano, A.L. Piccinelli, I. Pagano, S. Carabetta, M. Russo,
(2015) 1635–1651. E. Ibañez, A. Cifuentes, L. Rastrelli, Response surface methodology to opti-
[31] K.Y. Khaw, M.O. Parat, P.N. Shaw, J.R. Falconer, Solvent supercritical fluid mize supercritical carbon dioxide/co-solvent extraction of brown onion skin
technologies to extract bioactive compounds from natural sources: a review, by-product as source of nutraceutical compounds, Food Chem. 269 (2018)
Molecules 22 (2017) 1186. 495–502.
[32] S.M. Pourmortazavi, S.S. Hajimirsadeghi, Supercritical fluid extraction in plant [56] A. Aresta, P. Cotugno, N. De Vietro, F. Massari, C. Zambonin, Determination of
essential and volatile oil analysis, J. Chromatogr. A 1163 (2007) 2–24. polyphenols and vitamins in wine-making by-products by supercritical fluid
[33] X. Ran, M. Zhang, Y. Wang, B. Adhikari, Novel technologies applied for recov- extraction (SFE), Anal. Lett. 53 (2020) 2585–2595.
ery and value addition of high value compounds from plant byproducts: a [57] C. Da Porto, A. Natolino, D. Decorti, The combined extraction of polyphenols
review, Crit. Rev. Food Sci. Nutr. 59:3 (2019) 450–461, doi:10.1080/10408398. from grape marc: ultrasound assisted extraction followed by supercritical CO2
2017.1377149. extraction of ultrasound-raffinate, LWT-Food Sci. Technol. 61 (2015) 98–104.
[34] I. Ignat, I. Volf, V.I. Popa, A critical review of methods for characterisation [58] G. Ferrentino, K. Morozova, O.K. Mosibo, M. Ramezani, M. Scampicchio, Biore-
of polyphenolic compounds in fruits and vegetables, Food Chem. 126 (2011) covery of antioxidants from apple pomace by supercritical fluid extraction, J.
1821–1835. Clean. Prod. 186 (2018) 253–261.
[35] R.P.F.F. da Silva, T.A.P. Rocha-Santos, A.C. Duarte, Supercritical fluid extraction [59] A. Mustafa, C. Turner, Pressurized liquid extraction as a green approach in
of bioactive compounds, TrAC Trends Anal. Chem. 76 (2016) 40–51. food and herbal plants extraction: a review, Anal. Chim. Acta 703 (2011) 8–
[36] J. Zhou, B. Gullón, M. Wang, P. Gullón, J.M. Lorenzo, F.J. Barba, The application 18, doi:10.1016/j.aca.2011.07.018.
of supercritical fluids technology to recover healthy valuable compounds from [60] M. Plaza, C. Turner, Pressurized hot water extraction of bioactives, TrAC
marine and agricultural food processing by-products: a review, Processes 9 Trends Anal. Chem. 71 (2015) 39–54, doi:10.1016/j.trac.2015.02.022.
(2021) 357. [61] D.B. Kovačević, F.J. Barba, D. Granato, C.M. Galanakis, Z. Herceg,
[37] O.J. Catchpole, N.E. Durling, J.B. Grey, W. Eltringham, S.J. Tallon, Supercriti- V. Dragović-Uzelac, P. Putnik, Pressurized hot water extraction (PHWE)
cal antisolvent fractionation of plant extracts, in: Current Trends of Supercrit- for the green recovery of bioactive compounds and steviol glycosides from
ical Fluid Technology in Pharmaceutical, Nutraceutical and Food Processing Stevia rebaudiana Bertoni leaves, Food Chem. 254 (2018) 150–157.
Industries, Bentham Science Publishers, Sharjah, United Arab Emirates, 2009, [62] H.L. Kwon, M.S. Chung, Pilot-scale subcritical solvent extraction of curcumi-
pp. 71–79. noids from Curcuma long L., Food Chem. 185 (2015) 58–64.
[38] A. Gonzalez-Coloma, L. Martín, A.M. Mainar, J.S. Urieta, B.M. Fraga, V. Ro- [63] H.K. Reddy, T. Muppaneni, Y. Sun, Y. Li, S. Ponnusamy, P.D. Patil, P. Dailey,
dríguez-Vallejo, C.E. Díaz, Supercritical extraction and supercritical antisol- T. Schaub, F.O. Holguin, B. Dungan, Subcritical water extraction of lipids from
vent fractionation of natural products from plant material: comparative re- wet algae for biodiesel production, Fuel 133 (2014) 73–81.
sults on Persea indica, Phytochem. Rev. 11 (2012) 433–446. [64] S.C. Ndlela, J. De Moura, N.K. Olson, L.A. Johnson, Aqueous extraction of oil
[39] T. Vatai, M. Škerget, Ž. Knez, Extraction of phenolic compounds from elder and protein from soybeans with subcritical water, J. Am. Oil Chem. Soc. 89
berry and different grape marc varieties using organic solvents and/or super- (2012) 1145–1153.
critical carbon dioxide, J. Food Eng. 90 (2009) 246–254. [65] P. Budrat, A. Shotipruk, Enhanced recovery of phenolic compounds from bit-
[40] N. Gelmez, N.S. Kıncal, M.E. Yener, Optimization of supercritical carbon diox- ter melon (Momordica charantia) by subcritical water extraction, Sep. Purif.
ide extraction of antioxidants from roasted wheat germ based on yield, total Technol. 66 (2009) 125–129.
phenolic and tocopherol contents, and antioxidant activities of the extracts, J. [66] J.K. Monrad, L.R. Howard, J.W. King, K. Srinivas, A. Mauromoustakos, Subcriti-
Supercrit. Fluids 48 (2009) 217–224. cal solvent extraction of procyanidins from dried red grape pomace, J. Agric.
[41] H. Li, J. Wu, C.B. Rempel, U. Thiyam, Effect of operating parameters on oil and Food Chem. 58 (2009) 4014–4021.
phenolic extraction using supercritical CO2, J. Am. Oil Chem. Soc. 87 (2010) [67] H. Wijngaard, N. Brunton, The optimization of extraction of antioxidants
1081–1089. from apple pomace by pressurized liquids, J. Agric. Food Chem. 57 (2009)
[42] M.S. Liza, R.A. Rahman, B. Mandana, S. Jinap, A. Rahmat, I.S.M. Zaidul, 10625–10631.
A. Hamid, Supercritical carbon dioxide extraction of bioactive flavonoid from [68] J.W. Kim, T. Nagaoka, Y. Ishida, T. Hasegawa, K. Kitagawa, S.C. Lee, Subcritical
Strobilanthes crispus (Pecah Kaca), Food Bioprod. Process. 88 (2010) 319–326. water extraction of nutraceutical compounds from citrus pomaces, Sep. Sci.
[43] H.I. Castro-Vargas, L.I. Rodríguez-Varela, S.R.S. Ferreira, F. Parada-Alfonso, Ex- Technol. 44 (2009) 2598–2608.
traction of phenolic fraction from guava seeds (Psidium guajava L.) using [69] M. Çam, Y. Hışıl, Pressurised water extraction of polyphenols from
supercritical carbon dioxide and co-solvents, J. Supercrit. Fluids 51 (2010) pomegranate peels, Food Chem. 123 (2010) 878–885.
319–324. [70] J.K. Monrad, L.R. Howard, J.W. King, K. Srinivas, A. Mauromoustakos, Subcriti-
[44] T. Floris, G. Filippino, S. Scrugli, M.B. Pinna, F. Argiolas, A. Argiolas, M. Murru, cal solvent extraction of anthocyanins from dried red grape pomace, J. Agric.
E. Reverchon, Antioxidant compounds recovery from grape residues Food Chem. 58 (2010) 2862–2868.
by a supercritical antisolvent assisted process, J. Supercrit. Fluids 54 (2010) [71] T.L. Miron, M. Plaza, G. Bahrim, E. Ibáñez, M. Herrero, Chemical composition
165–170. of bioactive pressurized extracts of Romanian aromatic plants, J. Chromatogr.
A 1218 (2011) 4918–4927.

I. Pagano, L. Campone, R. Celano et al. Journal of Chromatography A 1651 (2021) 462295

[72] M.J. Ko, C.I. Cheigh, S.W. Cho, M.S. Chung, Subcritical water extraction of [98] K. Ghafoor, Y.H. Choi, J.Y. Jeon, I.H. Jo, Optimization of ultrasound-assisted ex-
flavonol quercetin from onion skin, J. Food Eng. 102 (2011) 327–333. traction of phenolic compounds, antioxidants, and anthocyanins from grape
[73] P.P. Singh, M.D.A. Saldaña, Subcritical water extraction of phenolic compounds (Vitis vinifera) seeds, J. Agric. Food Chem. 57 (2009) 4988–4994.
from potato peel, Food Res. Int. 44 (2011) 2452–2458. [99] Y.Q. Ma, J.C. Chen, D.H. Liu, X.Q. Ye, Simultaneous extraction of phenolic com-
[74] D.T. Santos, P.C. Veggi, M.A.A. Meireles, Optimization and economic evaluation pounds of citrus peel extracts: effect of ultrasound, Ultrason. Sonochem. 16
of pressurized liquid extraction of phenolic compounds from jabuticaba skins, (2009) 57–62.
J. Food Eng. 108 (2012) 444–452. [100] M.K. Khan, M. Abert-Vian, A.S. Fabiano-Tixier, O. Dangles, F. Chemat, Ultra-
[75] C.I. Cheigh, E.Y. Chung, M.S. Chung, Enhanced extraction of flavanones hes- sound-assisted extraction of polyphenols (flavanone glycosides) from orange
peridin and narirutin from Citrus unshiu peel using subcritical water, J. Food (Citrus sinensis L.) peel, Food Chem. 119 (2010) 851–858.
Eng. 110 (2012) 472–477. [101] J. Londoño-Londoño, V.R. de Lima, O. Lara, A. Gil, T.B.C. Pasa, G.J. Arango,
[76] L. He, X. Zhang, H. Xu, C. Xu, F. Yuan, Ž. Knez, Z. Novak, Y. Gao, Subcritical J.R.R. Pineda, Clean recovery of antioxidant flavonoids from citrus peel: op-
water extraction of phenolic compounds from pomegranate (Punica grana- timizing an aqueous ultrasound-assisted extraction method, Food Chem. 119
tum L.) seed residues and investigation into their antioxidant activities with (2010) 81–87.
HPLC–ABTS+ assay, Food Bioprod. Process. 90 (2012) 215–223. [102] R. Tabaraki, A. Nateghi, Optimization of ultrasonic-assisted extraction of natu-
[77] L.C. Cardoso, C.M. Serrano, E.T. Quintero, C.P. López, R.M. Antezana, ral antioxidants from rice bran using response surface methodology, Ultrason.
E.J. Martínez de la Ossa, High pressure extraction of antioxidants from Sonochem. 18 (2011) 1279–1286.
Solanum stenotomun peel, Molecules 18 (2013) 3137–3151. [103] G. Zhang, L. He, M. Hu, Optimized ultrasonic-assisted extraction of flavonoids
[78] S. Tunchaiyaphum, M.N. Eshtiaghi, N. Yoswathana, Extraction of bioactive from Prunella vulgaris L. and evaluation of antioxidant activities in vitro, In-
compounds from mango peels using green technology, Int. J. Chem. Eng. Appl. nov. Food Sci. Emerg. Technol. 12 (2011) 18–25.
4 (2013) 194. [104] E.Y. Jin, S. Lim, S. oh Kim, Y.S. Park, J.K. Jang, M.S. Chung, H. Park, K.S. Shim,
[79] M.P. Garcia-Mendoza, J.T. Paula, L.C. Paviani, F.A. Cabral, H.A. Martinez-Cor- Y.J. Choi, Optimization of various extraction methods for quercetin from onion
rea, Extracts from mango peel by-product obtained by supercritical CO2 and skin using response surface methodology, Food Sci. Biotechnol. 20 (2011)
pressurized solvent processes, LWT Food Sci. Technol. 62 (2015) 131–137. 1727–1733.
[80] H. Xu, W. Wang, X. Liu, F. Yuan, Y. Gao, Antioxidative phenolics obtained from [105] C. Carrera, A. Ruiz-Rodríguez, M. Palma, C.G. Barroso, Ultrasound assisted ex-
spent coffee grounds (Coffea arabica L.) by subcritical water extraction, Ind. traction of phenolic compounds from grapes, Anal. Chim. Acta 732 (2012)
Crops Prod. 76 (2015) 946–954. 100–104.
[81] N. Kryževičiūtė, P. Kraujalis, P.R. Venskutonis, Optimization of high pressure [106] M.B. Hossain, N.P. Brunton, A. Patras, B. Tiwari, C.P. O’Donnell, A.B. Martin–
extraction processes for the separation of raspberry pomace into lipophilic Diana, C. Barry-Ryan, Optimization of ultrasound assisted extraction of an-
and hydrophilic fractions, J. Supercrit. Fluids 108 (2016) 61–68. tioxidant compounds from marjoram (Origanum majorana L.) using response
[82] B. Pedras, M. Salema-Oom, I. Sá-Nogueira, P. Simões, A. Paiva, S. Barreiros, surface methodology, Ultrason. Sonochem. 19 (2012) 582–590.
Valorization of white wine grape pomace through application of subcritical [107] D. Pingret, A.S. Fabiano-Tixier, C. Le Bourvellec, C.M.G.C. Renard, F. Chemat,
water: analysis of extraction, hydrolysis, and biological activity of the extracts Lab and pilot-scale ultrasound-assisted water extraction of polyphenols from
obtained, J. Supercrit. Fluids 128 (2017) 138–144. apple pomace, J. Food Eng. 111 (2012) 73–81.
[83] M.S. Mariotti-Celis, M. Martínez-Cifuentes, N. Huamán-Castilla, F. Pedreschi, [108] L.G. d’Alessandro, K. Kriaa, I. Nikov, K. Dimitrov, Ultrasound assisted extrac-
N. Iglesias-Rebolledo, J.R. Pérez-Correa, Impact of an integrated process of tion of polyphenols from black chokeberry, Sep. Purif. Technol. 93 (2012)
hot pressurised liquid extraction–macroporous resin purification over the 42–47.
polyphenols, hydroxymethylfurfural and reducing sugars content of Vitis [109] Z. Pan, W. Qu, H. Ma, G.G. Atungulu, T.H. McHugh, Continuous and pulsed ul-
vinifera ‘Carménère’pomace extracts, Int. J. Food Sci. Technol. 53 (2018) trasound-assisted extractions of antioxidants from pomegranate peel, Ultra-
1072–1078. son. Sonochem. 19 (2012) 365–372.
[84] S. Mazzutti, L.G.G. Rodrigues, N. Mezzomo, V. Venturi, S.R.S. Ferreira, Inte- [110] G. Pan, G. Yu, C. Zhu, J. Qiao, Optimization of ultrasound-assisted extrac-
grated green-based processes using supercritical CO2 and pressurized ethanol tion (UAE) of flavonoids compounds (FC) from hawthorn seed (HS), Ultrason.
applied to recover antioxidant compouds from cocoa (Theobroma cacao) bean Sonochem. 19 (2012) 486–490.
hulls, J. Supercrit. Fluids 135 (2018) 52–59. [111] S. Şahin, R. Şamlı, Optimization of olive leaf extract obtained by ul-
[85] I. Pagano, A.L. Piccinelli, R. Celano, L. Campone, P. Gazzerro, M. Russo, L. Ras- trasound-assisted extraction with response surface methodology, Ultrason.
trelli, Pressurized hot water extraction of bioactive compounds from artichoke Sonochem. 20 (2013) 595–602.
by-products, Electrophoresis 39(15) (2018) 1899–1907. [112] C. Da Porto, E. Porretto, D. Decorti, Comparison of ultrasound-assisted extrac-
[86] D.T.V. Pereira, A.G. Tarone, C.B.B. Cazarin, G.F. Barbero, J. Martínez, Pressurized tion with conventional extraction methods of oil and polyphenols from grape
liquid extraction of bioactive compounds from grape marc, J. Food Eng. 240 (Vitis vinifera L.) seeds, Ultrason. Sonochem. 20 (2013) 1076–1080.
(2019) 105–113. [113] M. Jang, L. Asnin, S.H. Nile, Y.S. Keum, H.Y. Kim, S.W. Park, Ultrasound-assisted
[87] L. Loarce, R. Oliver-Simancas, L. Marchante, M.C. Díaz-Maroto, M.E. Alañón, extraction of quercetin from onion solid wastes, Int. J. Food Sci. Technol. 48
Implementation of subcritical water extraction with natural deep eutectic (2013) 246–252.
solvents for sustainable extraction of phenolic compounds from winemaking [114] Z. Izadifar, Ultrasound pretreatment of wheat dried distiller’s grain (DDG) for
by-products, Food Res. Int. 137 (2020) 109728. extraction of phenolic compounds, Ultrason. Sonochem. 20 (2013) 1359–1369.
[88] P. García, C. Fredes, I. Cea, J. Lozano-Sánchez, F.J. Leyva-Jiménez, P. Robert, [115] V. Briones-Labarca, M. Plaza-Morales, C. Giovagnoli-Vicuna, F. Jamett, High
C. Vergara, P. Jimenez, Recovery of bioactive compounds from Pomegranate hydrostatic pressure and ultrasound extractions of antioxidant compounds,
(Punica granatum L.) peel using pressurized liquid extraction, Foods 10 (2021) sulforaphane and fatty acids from Chilean papaya (Vasconcellea pubescens)
203. seeds: effects of extraction conditions and methods, LWT Food Sci. Technol.
[89] P. Gullón, B. Gullón, A. Romaní, G. Rocchetti, J.M. Lorenzo, Smart advanced 60 (2015) 525–534.
solvents for bioactive compounds recovery from agri-food by-products: a re- [116] M. Peanparkdee, R. Yamauchi, S. Iwamoto, Characterization of antioxidants
view, Trends Food Sci. Technol. 101 (2020) 182–197. extracted from Thai riceberry bran using ultrasonic-assisted and conventional
[90] F. Chemat, N. Rombaut, A.G. Sicaire, A. Meullemiestre, A.S. Fabiano-Tixier, solvent extraction methods, Food Bioprocess Technol. 11 (2018) 713–722.
M. Abert-Vian, Ultrasound assisted extraction of food and natural products. [117] C.D. Goldsmith, Q.V. Vuong, C.E. Stathopoulos, P.D. Roach, C.J. Scarlett, Ultra-
Mechanisms, techniques, combinations, protocols and applications. a review, sound increases the aqueous extraction of phenolic compounds with high an-
Ultrason. Sonochem. 34 (2017) 540–560. tioxidant activity from olive pomace, LWT 89 (2018) 284–290.
[91] T. Belwal, S.M. Ezzat, L. Rastrelli, I.D. Bhatt, M. Daglia, A. Baldi, H.P. Devkota, [118] Y. Riciputi, E. Diaz-de-Cerio, H. Akyol, E. Capanoglu, L. Cerretani, M.F. Caboni,
I.E. Orhan, J.K. Patra, G. Das, A critical analysis of extraction techniques used V. Verardo, Establishment of ultrasound-assisted extraction of phenolic com-
for botanicals: trends, priorities, industrial uses and optimization strategies, pounds from industrial potato by-products using response surface methodol-
TrAC Trends Anal. Chem. 100 (2018) 82–102. ogy, Food Chem. 269 (2018) 258–263.
[92] B.K. Tiwari, Ultrasound: a clean, green extraction technology, TrAC Trends [119] M. Irakli, P. Chatzopoulou, L. Ekateriniadou, Optimization of ultrasound-as-
Anal. Chem. 71 (2015) 100–109. sisted extraction of phenolic compounds: oleuropein, phenolic acids, pheno-
[93] L. Campone, R. Celano, A.L. Piccinelli, I. Pagano, N. Cicero, R. Di Sanzo, S. Cara- lic alcohols and flavonoids from olive leaves and evaluation of its antioxidant
betta, M. Russo, L. Rastrelli, Ultrasound assisted dispersive liquid-liquid mi- activities, Ind. Crops Prod. 124 (2018) 382–388.
croextraction for fast and accurate analysis of chloramphenicol in honey, Food [120] M. de los Ángeles Fernández, M. Espino, F.J.V Gomez, M.F. Silva, Novel ap-
Res. Int. 115 (2019) 572–579. proaches mediated by tailor-made green solvents for the extraction of pheno-
[94] M. Mitchell, J.E. Brandenburg, Process for fractionation and extraction of lic compounds from agro-food industrial by-products, Food Chem. 239 (2018)
herbal plant material to isolate extractives for pharmaceuticals and nutraceu- 671–678.
ticals, (2015). U.S. Patent Application No. 14/454,998. [121] K.M. Jeong, S.Y. Han, E.M. Kim, Y. Jin, J. Lee, Deep eutectic solvent-based val-
[95] M. Mitchell, Method for isolating lignin from a biomass and products pro- orization of spent coffee grounds, Food Chem. 255 (2018) 357–364.
vided therefrom, (2015). U.S. Patent Application No. 14/619,451. [122] N.A. Al-Dhabi, K. Ponmurugan, P.M. Jeganathan, Development and validation
[96] M. Mitchell, Method for isolating cellulose from a biomass and products pro- of ultrasound-assisted solid-liquid extraction of phenolic compounds from
vided therefrom, (2015). U.S. Patent Application No. 14/619,406. waste spent coffee grounds, Ultrason. Sonochem. 34 (2017) 206–213.
[97] M. Mitchell, Isolation method for water insoluble components of a biomass [123] M.M. Meregalli, B.M.S. Puton, F.D. Camera, A.U. Amaral, J. Zeni, R.L. Cansian,
and products provided therefrom, (2015). U.S. Patent Application No. M.L. Mignoni, G.T. Backes, Conventional and ultrasound-assisted methods for
14/454,972. extraction of bioactive compounds from red araçá peel (Psidium cattleianum
Sabine), Arab. J. Chem. 13 (2020) 5800–5809.


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