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Article history: By-products of plant origin represent an abundant source of bioactive compounds. However, to exploit these
Received 17 April 2011 resources commercially relevant strategies for their extraction must be developed. This review focuses on the
Accepted 27 September 2011 extraction of bioactive compounds from food by-products of plant origin by a number of novel methods, in-
cluding pressurised liquid extraction and supercritical CO2 extraction. In general supercritical CO2 extraction
Keywords:
is most effective for apolar compounds such as carotenoids, while pressurised liquid extraction can be used to
By-products
Carotenoids
extract more polar compounds such as polyphenols. Both techniques are sustainable and green techniques. In
Polyphenols addition, pre-treatment of plant by-products by novel non-thermal processing techniques in order to en-
Pomace hance extraction will be highlighted. In general the selection of an appropriate extraction strategy is depen-
Pressurised liquid extraction dent on the type of compound to be extracted as well as the potential up scaling of the technique.
Supercritical CO2 extraction © 2011 Elsevier Ltd. All rights reserved.
Pulsed electric fields
0963-9969/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodres.2011.09.027
506 H. Wijngaard et al. / Food Research International 46 (2012) 505–513
Table 1
Efficiency of and conditions used to extract bioactive compounds from by-products of plant origin using supercritical fluid extraction.
Tomato paste waste Carotenoids 30 MPa, 5% ethanol Lycopene (54%) Baysal, Ersus, and Starmans (2000)
β-Carotene (50%)
Tomato paste waste Carotenoids 80 °C, 30 MPa, 5% ethanol, solvent Lycopene (88%) Sabio et al. (2003)
flow rate (0.792 kg/h) β-Carotene (80%)
Tomato seeds Carotenoids 34.5 MPa, 88 °C Lycopene Rozzi, Singh, Vierling, and Watkins
(2002)
Tomato skins and seeds Carotenoids 30 MPa, 60 °C, solvent flow-rate trans-Lycopene Nobre, Palavra, Pessoa, and Mendes
of 0.59 g/min, particle size of 0.36 mm (2009)
and feed moisture content of 4.6
Tomato seeds and skins Carotenoids 46 MPa, 80 °C Lycopene (90%) Vági et al. (2007)
Tomato skins Carotenoids 62 °C, 45 MPa (450 bar), and 14% trans-Lycopene Kassama, Shi, and Mittal (2008)
ethanol (33%)
Tomato skins Carotenoids 40 MPa, 100 °C, and 2.5 mL of CO2/min Lycopene Topal, Sasaki, Goto, and Hayakawa
(94%) (2006)
Tomato skins Carotenoids 35 MPa, 75 °C, ethanol (10%) and Lycopene Shi, Yi, et al. (2009)
olive oil (10%) (73%)
Apricot by-products Carotenoids 40 MPa, 50 °C, 2,2-dimethoxypropane, β-Carotene (60%) Sanal, Güvenç, Salgin, Mehmetoglu
moisture content 10% and Çalimli (2004)
Apricot by-products Carotenoids 31 MPa, 59 °C, 27% ethanol β-Carotene (60%) Sanal et al. (2005)
Carrot press cake Carotenoids 34.5 MPa, 55 °C, 10% ethanol β-Carotene (99.5%) Vega, Balaban, Sims, O'Keefe, and
Cornell (1996)
Apple and peach pomaces Polyphenols 30% ethanol and 40 min Total phenols (25%) Adil et al. (2007)
Citrus peel Polyphenols 9.5 MPa, 60 °C, 15% ethanol Naringin Giannuzzo, Boggetti, Nazareno, and
(14.4 mg/100 g DW) Mishima (2003)
Grape by-products Polyphenols 40 MPa, 35 °C, using 5% v/v ethanol Resveratrol Casas et al. (2010)
(seed, stem, skin and pomace) (19.2 mg/100 g DW)
Grape skin Polyphenols 40 °C, 11 MPa, 7.5% ethanol, Resveratrol Pascual-Martí et al. (2001)
extraction time 15 min (100%)
Grape skins Polyphenols 45–46 °C temperature, 1.56–1.6 MPa 12.3%, total phenols (2.156 mg Ghafoor, Park and Choi (2010)
pressure and 6–7% ethanol GAE/100 mL), antioxidants
(1.628 mg/mL) and total anthocyanins
(1.176 mg/mL).
Orange pomace Polyphenols 30 MPa, 40 °C, 2% co-solvent Phenolic compounds Benelli, Riehl, Smânia, Smânia and
(36 ± 2 mg GAE/g) Ferreira (2010)
Tea seed cake Polyphenols 20 MPa, 80 °C, and 60% aqueous Two kaempferol glycosides Li et al. (2010)
ethanol, extraction time 150 min (11.4 ± 0.4 mg/g)
Guava (Psidium guajava L.) seeds Polyphenols 10 MPa at 60 °C, ethanol (10%) Total phenolic content (153 mg Castro-Vargas, et al. (2010)
GAE/100 g DW)
Pistachio (Pistachia vera) hull Polyphenols 45 °C, 355 bar, 15 min, 15% methanol Total phenolic content (7810 mg Goli, Barzegar and Sahari (2005)
GAE/100 g DW)
Olive leaves Polyphenols 33 MPa, 100 °C (CO2 density 0.70 g/mL), Total phenolic content (45%) Le Floch, Tena, Rios, and Valcárcel
flow rate 2 mL/min, 140 min, 10% (1998)
methanol
Liquid grape seed extract Anthocyanins 30–40 °C; 10–13 MPa, pH Total anthocyanins Bleve et al. (2008)
2–4; 25–30% ethyl alcohol; (85%)
flow rate 25–50 mL/min
Distilled white grape pomace Monomeric 50 °C, 90 min, 8% ethanol, Gallic acid, catechin and epicatechin Pinelo et al. (2007)
polyphenols solvent-to-solid ratio 1:1
White grape seeds Monomeric 55 °C, 20 min, 20% methanol Gallic acid, catechin and epicatechin Palma and Taylor (1999)
polyphenols
Grape seeds Polyphenols 30 MPa, 15% methanol Low molecular weight polyphenols Murga, Ruiz, Beltran, and Cabezas
(N 90%) (2000)
molecules, and hence increasing the interactions between the target therefore surprising that the addition of a polar aprotic solvent such as
compound and CO2 molecules (Topal, Sasaki, Goto, & Hayakawa, ethanol (dielectric constant 33) enhances the extraction of carotenoids.
2006). Therefore, solubility increases with pressure, especially at pres- However it is clear that in all cases the use of modifier increases extrac-
sures from 10 to 20 MPa as there is a sharp increase in the density of tion yields over and above pure CO2. The reason for this in not entirely
SC-CO2 in this range (Shi, Khatri, et al., 2009). At pressures above clear, however some authors have postulated that the addition of a mod-
20 MPa only small increases in solvent density occur and since most au- ifier enhances extraction by distorting the analyte–matrix bonds, allow-
thors investigate pressures from 20 to 40 MPa pressure has less of an in- ing the supercritical fluid better access to the analyte (Shi, Yi, et al.,
fluence on extraction efficiency than temperature in this range. 2009). Ethanol is of course an attractive solvent for SC-CO2 extractions
After temperature and pressure, modifier percentage appears to be because of its food friendly nature. The use of vegetable and other oils
the most critical factor affecting carotenoid yields in SC-CO2 extractions. as modifiers has many advantages over ethanol since they are food
Ethanol is the most widely used modifier solvent in SC-CO2 and most au- friendly and deliver all the benefits of the use of modifiers in general
thors recommend relatively low amounts (10–15%) of ethanol be added but are also cheap and more hydrophobic thus enhancing extraction
to enhance SC-CO2 extraction of carotenoids. In general carotenoids are yields. This has been clearly illustrated in the study of Shi, Yi, et al.
polyene hydrocarbon chains which sometimes undergo ring closure at (2009) where the use of olive oil as modifier gave better recoveries of ly-
one or both ends meaning they are largely hydrophobic in nature. It is copene than ethanol or water from tomato skins at 75 °C.
508 H. Wijngaard et al. / Food Research International 46 (2012) 505–513
There are conflicting reports on the effect of source material mois- extraction is measured not by the levels of specific compounds but as
ture content on the recovery of carotenoids from by-products. For ex- total phenolic content. Unlike carotenoids polyphenols are moderately
ample Nobre et al. (2009) reported that the extraction yield of trans- polar compounds and when extracted by SC-CO2 a modifier usually eth-
lycopene rose when the moisture content of the sample increased anol is added to create a more polar environment. Addition of ethanol
from 4.6% to 22.8%, possibly due to the modifications in the skin struc- increases the critical temperature of SC-CO2 and if temperatures and
ture mentioned before, implying less available compounds in tomato pressure are not increased to compensate, the mixture remains at or
waste with lower moisture content. However, for higher moisture near its critical point instead of the supercritical point. For extraction
contents the yield decreased, in this case, probably due to the water of polyphenols the addition of a moderately polar modifier is critical
preventing contact between CO2 and tomato particles. In contrast, with most authors reporting zero yields when no ethanol is added
Sanal et al. (2004) reported that extraction yields of β-carotene (Casas et al., 2010; Palma & Taylor, 1999). Similar to carotenoids ethanol
from apricot pomace increased markedly when the moisture content is usually added at relatively low levels (10–20%) although extraction
was decreased from 30 to 10%. The reason for the conflicting reports is using up to 60% ethanol has been reported (Li et al., 2010). In addition
unclear. However it should be noted that all carotenoids are susceptible to the benefits listed above for addition of a modifier for carotenoid ex-
to degradation in the presence of light and heat. Therefore a drying traction, the addition of a polar modifier for polyphenol extraction will
method such as freeze drying is preferable as this will preserve caroten- also increase the solubility of the target compounds in the supercritical
oids in the starting by-product material (Sanal et al., 2004). solvent. As a result very high yields for modifier assisted SC-CO2 extrac-
It is clear that a variety of extraction conditions can influence extrac- tion of polyphenols from by-products have been reported. For example
tion efficiencies of carotenoids from plant by-products. This can make it Casas et al. (2010) reported that resveratrol, a well known bioactive
difficult to pinpoint optimal conditions using conventional statistical ap- phenolic compound in grape by-products (seed, stem, skin and pom-
proaches. However, many authors have utilised response surface meth- ace) was efficiently extracted using SC-CO2 at high pressure (400 bar)
odology (RSM) to minimise the number of experiments required to and low temperature (35 °C) using 5% v/v ethanol as a co-solvent. In
identify optimal extraction. For example Sanal et al. (2004. 2005) used fact using these conditions, the extraction yields were 14.67 and 21.33
RSM to increase extraction yields of β-carotene from apricot pomace times higher than those of a conventional extraction method. Contrary
by 10% over a previous experiment which utilised a conventional statis- to most studies, Goli, Barzegar and Sahari (2005) reported a significant
tical approach. In summary SC-CO2 represents a promising technique for lower extraction yield of phenolic compounds in SC-CO2 extraction
recovery of carotenoids from plant by-products which uses smaller (45 °C, 355 bar, 15 min) from pistachio (Pistachia vera) hull even after
amounts of solvent than conventional approaches and therefore could using 15% methanol as modifier in comparison to solid/liquid water ex-
be used to valorise carotenoid rich plant based by-products. A number traction. The presence of highly polar compounds in pistachio might
of promising sources of carotenoids in plant by-products have been iden- have been the determinant factor in this study.
tified and optimal extraction conditions are broadly in agreement. A wide variety of extraction temperatures have been reported as op-
timal for polyphenol extraction (Table 1, 35–100 °C) from by-products
3.2. Polyphenols of plant origin. However in general most authors report that tempera-
tures between 40 and 60 °C are best. This is slightly lower than the op-
The world market for polyphenols is significant. For example, timal conditions for carotenoid extraction and would appear to imply
Leatherhead Food Research (2009) estimates the current market is that polyphenols are less heat stable than carotenoids. Similar to carot-
worth approximately $200 million. The majority of polyphenols enoids extraction pressures between 20 and 30 MPa are optimal for ex-
extracted for sale as nutraceuticals or for use in functional foods come traction of polyphenols. As outlined above the enhanced solubility of
from either grapes, apples, olives or green tea and this is reflected in polyphenols at higher pressures is related to an increase in solvent den-
the studies that have been performed on optimising SC-CO2 for their ex- sity at higher pressures.
traction. Table 1 lists optimal conditions for the extraction of polyphe- The type of pomace from which polyphenols are recovered can in-
nols from various by-products using SC-CO2. A variety of potentially fluence extraction yields. For example for apple and peach pomaces
valuable polyphenolic compounds have been targeted in SC-CO2 extrac- Adil, Çetin, Yener and Bayindirli (2007) reported that yields were
tion studies including resveratrol (Fig. 2d), naringin (Fig. 3d) and quite low with about 25% of phenols in comparison to 100% using an
kaempferol glycosides, however in many cases the efficiency of ethanolic solid liquid extraction (SLE) (Adil et al., 2007). In contrast
COOH
HO COOH COOH
HO OH HO HO
OH OCH3
OH HOOC OH
O
HO
OH
HO O
OH
OH
OH
Resveratrol (d) Chlorogenic acid (e)
Fig. 2. Structures of the major phenolic acids and their derivatives extracted from food by-products.
H. Wijngaard et al. / Food Research International 46 (2012) 505–513 509
OH
R1 HO O
OH
OH
OH
OH
HO O OH
R2 HO O
OH
O-glu
OH
OH
OH
HO OH
HO OH
H3C O
O OCH3
O
HO O O
HO
OH
OH O
Hesperidin (c)
OH OH
O
HO O O
HO
O
H3C O
HO
OH OH O
OH Naringin (d)
Fig. 3. Structures of flavonoids and their derivatives commonly found in food by-products.
Giannuzzo, Boggetti, Nazareno and Mishima (2003) reported that when 4. Pressurised liquid extraction (PLE)
naringin was recovered from fresh citrus peel a higher yield was
obtained when SC-CO2 was used than with SLE and a similar level to During PLE, pressure is applied, allowing the use of temperatures
that obtained by Soxhlet extraction. Polyphenols are structurally di- above the boiling point of solvents (Mendiola, Herrero, Cifuentes, &
verse class of plant metabolites which usually go through various mo- Ibanez, 2007). Extracting at elevated temperatures can be advanta-
lecular modifications predominantly by hydroxylation, glycosylation geous due to changes in mass transfer and surface equilibria. Higher
and polymerisation. For example Pinelo et al. (2007) reported that mo- extraction temperatures will increase the mass transfer rate and ex-
nomeric polyphenol levels, such as catechins and phenolic acids were traction rates, because higher temperatures generally imply: i) an in-
increased, while polymeric polyphenols were not that well extracted crease in capacity of solvents to solubilise solutes, ii) an increase in
in SC-CO2. Murga, Ruiz, Beltran and Cabezas (2000) also reported that diffusion rates, iii) better disruption of solute–matrix bonds, iv) a de-
low molecular weight polyphenols were best extracted by SC-CO2 at crease in viscosity of the solvent and v) decrease in surface tension
15% of added methanol. Even at these conditions high molecular weight (Ramos, Kristenson, & Brinkman, 2002; Richter et al., 1996). The ap-
tannins were not extracted. Using methanol makes the application unu- plied high pressure, usually ranging from 4 to 20 MPa, ensures the
sable for food ingredient production. As noted earlier CO2 is a non-polar solvent maintains in the liquid state at the applied temperature
solvent and some authors have utilised SC-CO2 as a pre-treatment to re- (Ramos et al., 2002). This is the main reason for the use of pressure,
move non-polar components prior to extraction of polyphenols from although pressure has also been reported to help driving the solvent
plant by-products. For example Vatai, Skerget and Knez (2009) devel- into the pores of the matrix and enhance analyte solubility (Mustafa
oped a 2 step process for extraction of phenolic compounds from & Turner, 2011; Ramos et al., 2002). The extra pressure effects seem
grape pomace involving pre-treatment with SC-CO2 to remove non- negligible though (Mustafa & Turner, 2011) and therefore researchers
polar compounds followed by solvent extraction of the residue. This usually apply one constant pressure in PLE experiments.
technique gave better recoveries of phenolic compounds than single PLE is also known as pressurised solvent extraction, subcritical sol-
step solvent extraction. In summary, it is possible to extract certain vent extraction or accelerated solvent extraction. When 100% water is
polyphenols from by-products, but the use of modifier seems unavoid- used as a solvent, PLE is generally called superheated water extraction,
able. Therefore for the recovery of polyphenols other techniques, such subcritical water extraction, pressurised low polarity water extraction
as PLE, may be more interesting. or pressurised hot water extraction (Pronyk & Mazza, 2009).
510 H. Wijngaard et al. / Food Research International 46 (2012) 505–513
PLE has mainly been used to optimise analytical extractions minimum pressure of 1.5 MPa is required, while extraction at 300 °C re-
(Alonso-Salces et al., 2001; Luthria, 2008), although a few commercial quires a minimum pressure of 8.5 MPa (Smith, 2002). The thermo-
applications exist in the field of extraction of flavourings from natural dynamical properties of water change dramatically when the tempera-
products as an alternative to steam distillation (Cravotto & Cintas, ture is increased, especially the dielectric constant. Dielectric constants
2007). PLE generally requires less time and a lower consumption of that are similar to organic solvents such as methanol can be achieved at
organic solvents than conventional techniques (Mendiola et al., 200 °C (Mendiola et al., 2007).
2007). This is the reason why PLE may have commercial interest as al- Hydroethanolic mixtures are the other liquid often used in PLE of
ternative extraction method to obtain bioactive compounds from by- bioactives (Table 2). By using solvent mixtures, advantages of both
products. King and Grabiel (2007) for example patented the potential can be utilised. For example one solvent can improve the solubility of
of the use of PLE in order to extract polyphenols from fruit and vege- the solute (ethanol), while the other solvent can assist in desorption
table by-products. of the solute from the matrix (water) (Mustafa & Turner, 2011). The
In order to recover bioactive compounds from food by-products, use of ethanol reduces the boiling point and affects the polarity of the
food grade solvents such as aqueous ethanol or water can be used. At- solvent. The ethanol concentration has therefore a large effect on the
tempts to recover bioactive compounds from by-products have been extraction yield of polyphenols (Wijngaard & Brunton, 2009).
published, focusing mainly on polyphenolic compounds as is discussed The temperature also affects extraction yield. As explained in the in-
below. troduction paragraph on PLE, mass transfer rates and extraction rates can
be enhanced by using an elevated temperature. Table 2 shows that opti-
4.1. Polyphenols mal PLE temperatures ranged between 100 and 180 °C, with one excep-
tion at 40 °C. A required high temperature for efficient extraction was
As mentioned before, the world market for polyphenols is signifi- confirmed by Monrad, Howard, King, Srinivas and Mauromoustakos
cant, which generates interest in non-conventional extraction tech- (2010a), who reported that a temperature higher than 80 °C at a pres-
niques. PLE is one of the techniques that can be used in order to sure of 6.8 MPa was required to enable an efficient procyanidin extrac-
extract polyphenols from by-products and has thus been studied by tion from red grape pomace when using PLE. García-Marino,
various researchers. An overview is shown in Table 2. The main pa- Rivas-Gonzalo, Ibáñez and García-Moreno (2006) found that the sum
rameters that are important in PLE, are temperature, pressure, flow of individual polyphenols of winery by-products also increased at elevat-
rate and extraction time (Cravotto & Cintas, 2007). It should be ed temperatures. In addition, the solubility of phenolic acids such as gal-
noted that optimal conditions depend on applied reference methods lic, chlorogenic, caffeic, ferulic and coumaric acids (Fig. 2) increased with
and analytical procedures. Therefore yields higher than 100% have enhanced temperatures, but at temperatures higher than 180 °C, the
been reported, since apparently, the conventional standard extraction phenolic acids were degraded (Singh & Saldaña, 2011). This showed
procedures were not extracting all of the polyphenols present. Keep- that increased temperatures can also have disadvantages and this should
ing this in mind, general trends of the influence of various processing be taken into consideration when optimising the process. It is especially
parameters on extraction efficiency can be noted. of importance for thermo-labile bioactive compounds, such as anthocya-
Firstly the extracting efficiency depends on the type of compound nins, which can be degraded at relatively low temperatures. Monrad
to be extracted. As shown in Table 2, optimal conditions for anthocy- et al. (2010b) reported degradation of anthocyanins in hydroethanolic
anins (Fig. 3a), procyanidins (Fig. 3b) and flavonols differ. This is to be solutions at temperatures higher than 120 °C, while Ju and Howard
expected as with any compound, the solubility of polyphenols de- (2003) mentioned degradation of anthocyanins at temperatures higher
pends on various parameters, such as polarity, size and the character- than 100 °C. They did not use the same solvents (Table 2), which may ex-
istics of the extraction medium. The characteristics of the solvent can plain the difference in results. In any case, at atmospheric pressure con-
be changed by adjusting the concentration of solvents used, for exam- ditions, anthocyanins were already degraded at temperatures higher
ple the temperature. The solvent used is also of great importance to than 50 °C (Ju & Howard, 2005), which shows one of the advantages of
extraction yield. As shown in Table 2 aqueous ethanol and water are using PLE.
the major liquids used in PLE of polyphenols from by-products. By Another consequence of using high temperatures (around 140–
using water only, rules and regulations for using organic solvents as 150 °C) is that certain compounds, such as Maillard reaction products
means of extraction can be avoided. In addition, using 100% water is and 5-(hydroxymethyl)furfural (HMF) can be produced de novo when
eliminating the cost of ethanol itself and the process cost of evaporat- using PLE (Monrad et al., 2010b; Wijngaard & Brunton, 2009). These
ing off organic solvents. compounds may not be desired. This should be taken into account
The temperature range that can be used for SWE ranges from the when designing an optimal process.
boiling point (100 °C) of water to its critical point (374 °C). The critical Flow rate is another parameter that can be adjusted. Although
pressure of water is 218 bar. The pressure required to maintain water in most researchers do not optimise flow rate, the important role it
the condensed form depends on the temperature applied: for 200 °C a may play when extracting polyphenols was emphasised by Srinivas,
Table 2
Efficiency of and conditions used to extract polyphenols from by-products of plant origin using pressurised liquid extraction.
Red grape pomace Procyanidins 6.8 MPa, 140 °C, 50% ethanol Total procyanidins (115%) Monrad et al. (2010a)
Red grape pomace Anthocyanins 6.8 MPa, 100 °C, 50% ethanol Total anthocyanins (112%) Monrad et al. (2010b)
Red grape pomace Anthocyanins 10 MPa, 100 °C, 5 min, 0.1% HCl in water Total anthocyanins (100%) Ju and Howard (2003)
Apple pomace Polyphenols 10.3 MPa, 102 °C, 5 min, 60% ethanol Total flavonols (130%) Wijngaard and Brunton (2009)
Dried grape skin Polyphenols 110 °C, 40 s, 100% water Total anthocyanins (100%) Ju and Howard (2005)
110 °C, 40 s, sulfured watera
Winery by-products Polyphenols 6–7 MPa, 150 °C, 100% water Procyanidins + catechins (38%) García-Marino et al. (2006)
Onion waste Flavonols 5 MPa, 120 °C, 15 min, 100% water + enzyme hydrolysis Quercetin (106%) Turner et al. (2006)
Potato peel Phenolic acids 6 MPa, 180 °C, 60 min, 100% water Phenolic acids (177%) Singh and Saldaña (2011)
Pomegranate peel Polyphenols 10.2 MPa, 40 °C, 5 min, 100% water Total phenolic content (100%) Çam and HisIl (2010)
Onion skin Flavonols 9–13.1 MPa, 160 °C, 15 min, 100% water Quercetin (92%) Ko et al. (2011)
a
Sulfured water contained 1400 μg/mL Na2S2O3.
H. Wijngaard et al. / Food Research International 46 (2012) 505–513 511
King, Howard and Monrad (2011). They discovered that optimisation Extremely high temperatures of 5000 °C and pressures of 1000 bar have
of the flow rate is of major importance in order to effectively dissolve been measured. The process is affected by mechanical forces surround-
a solute such as quercetin in SWE. ing the bubble when a solid matrix is present (Luque-García & Luque de
In addition sulphured water (water with an added 1400 μg/mL Castro, 2003). Due to the cavitation process plant cell walls can be pen-
Na2S2O3), can enhance extraction of certain polyphenols, such as an- etrated, which provides an easier cell access. In addition, ultrasound can
thocyanins (Table 2). The mechanism is poorly understood, but it is result in swelling of the plant material, which in turn can enhance ex-
thought that the solubility is increased due to improved diffusion traction (Vinatoru, 2001).
through cell walls (Gao & Mazza, 1996), and/or the dielectric constant Various studies have tested ultrasound and its effect on the extrac-
of the solvent reduced. The reaction products of anthocyanins with tion of polyphenols. Ultrasound has been shown to enhance the ex-
sulphites are more soluble in aqueous solvents than their parent an- traction of bioactive compounds such as polyphenols from different
thocyanins (Jackson, 2008) resulting in higher extraction yields. plant by-products in several studies (Khan, Abert-Vian, Fabiano-Tixier,
Sequential procedures can also be used to enhance extraction yields. Dangles, & Chemat, 2010; Vilkhu, Mawson, Simons, & Bates, 2008;
For example SWE at 100 °C, followed by an extraction at 150 °C was Virot, Tomao, Le Bourvellec, Renard, & Chemat, 2010). Orange peels
found to be optimal to extract flavonols and gallic acid (Fig. 2a) (García- were treated with ultrasound to extract the flavanones hesperidin
Marino, et al., 2006). In summary, mainly temperature and type of solute (Fig. 3c) and naringin (Fig. 3d). Temperature, ethanol:water ratio and
and extraction medium were reported to be of high importance when sonication power were optimised using RSM. A temperature of 40 °C,
extracting polyphenols from by-products. a 4:1 (v/v) ethanol:water ratio and a sonication power of 150 W were
determined as optimal. These conditions resulted in an enhanced ex-
5. Novel non-thermal and microwave assisted extraction traction of 38% for naringin and 41% for hesperidin when compared to
non-sonicated samples (Khan et al., 2010).
In addition to pressurised liquid extraction techniques discussed When ultrasound was applied to apple pomace, a by-product of the
above, other techniques exist that may assist in the extraction of bio- apple cider industry, catechins were 20% better extracted than when a
active compounds, such as pulsed electric fields (PEF), ultrasound conventional extraction was used. In addition, a scale up test was per-
waves and microwaves. These techniques could for example be ap- formed with an ultrasonic bath of a volume of 30 L. (Virot, Tomao, Le
plied as a preliminary step in the extraction of bioactive compounds. Bourvellec, Renard, & Chemat, 2010). Ultrasound has also been success-
In PEF, material located between two electrodes is exposed to a fully applied to enhance the extraction of carotenoids from different by-
strong electrical field. If the stress caused by the electrical field on the products of plant origin. Sun, Liu, Chen, Ye and Yu (2011) investigated
membrane is large enough pore formation occurs. The pore formation the effect of variety of factors (particle size, solvent type, solid:solvent
can be reversible or irreversible, and depends on the conditions of PEF ratio, temperature, extraction time, acoustic intensity, height of liquid
treatment, such as electric field strength, pulse duration and the num- and duty cycle of ultrasound exposure) on the ultrasound assisted ex-
ber of pulses. Pore formation enhances cell permeability (Angersbach, traction yield of all-trans-β-carotene from citrus peel. All tested UAE
Heinz, & Knorr, 2000). PEF has been extensively investigated as a non- conditions yielded higher all-trans-β-carotene than that of conven-
thermal preservation technique. On the other hand, the use of PEF in tional solid/liquid extraction, with a maximum of ca. 11 μg all-
the recovery of bioactive compounds from by-products is not well stud- trans-β-carotene/g DW at an extraction time of 120 min. The height
ied up to now. The technique has been mainly used to extract polyphe- of the liquid present in the sample beaker showed an inverse rela-
nols from grape by-products. In red grape by-product the level of tionship with extraction yield in UAE. The authors reported that
anthocyanins was 60% increased when PEF was applied as a pre- this may be explained by the fact that the cavitation intensity de-
treatment of 1 min at 25 °C in combination with a conventional thermal creases with increasing height due to the attenuation of the waves
extraction at 70 °C for 1 h (Corrales et al., 2008). When white grape caused by absorption and scattering.
skins were treated with PEF at a temperature of 20 °C, 10% more poly- Microwaves are electromagnetic waves, which are usually operat-
phenols than non-treated samples were extracted (Boussetta et al., ed at a frequency of 2.45 GHz. Microwaves can access biological ma-
2009). PEF seems a potential technique to use as pre-treatment in the trices and interact with polar molecules, such as water, and
extraction of polyphenols from by-products, although industrial scale generate heat. The temperature will rise, which generally leads to en-
equipment is still under development and the technique does not hanced extraction efficiency (Wang & Weller, 2006). An overview of
apply to solid products (Han, 2007). results of MAE of polyphenols from by-products is shown in Table 3.
Ultrasound assisted extraction (UAE) can also be used in the food in- By using MAE the extraction time can be reduced in comparison to
dustry to perform extractions. The technique uses high frequency sound conventional extraction methods (Ballard, Mallikarjunan, Zhou, &
waves (higher than 20 kHz). When the ultrasound waves are strong O'Keefe, 2010; Liazid, Guerrero, Cantos, Palma, & Barroso, 2011;
enough, bubbles are formed in the liquid. Eventually the formed bub- Pérez-Serradilla & Luque de Castro, 2011). MAE extraction efficiency
bles cannot absorb the energy any longer and will collapse: “cavitation” principally depends on microwave energy, treatment time and tem-
takes place. This collapse causes a change in temperature and pressure perature used. It should be noted that in general temperature in-
within the bubble and hence energy for chemical reactions is generated. crease enhances extraction rates of solutes due to the same reasons
Table 3
Efficiency of and conditions used to extract polyphenols from by-products of plant origin using microwave assisted extraction.
Longan peel Polyphenols 95% ethanol, 80 °C, 500 W, 30 min, 2.45 GHz Total phenolic content (115%) Pan et al. (2008)
Grape seed Polyphenols 66 °C, 200 s, 30 W Total phenolic content (13.5%) Hong et al. (2001)
Satsuma peels Flavonoids 70% ethanol, 140 °C, 7 min, 1000 W, 2.45 GHz Narirutin (93%) Inoue et al. (2010)
Hesperidin (91%)
Peanut skins Polyphenols 30% ethanol, 30 s, 855 W Total phenolic content (122%) Ballard et al. (2010)
Grape skins Anthocyanins 40% methanol, 100 °C, 5 min, 500 W Total anthocyanins (118%) Liazid et al. (2011)
Wine lees Polyphenols 75% ethanol, 200 W, 17 min Total phenolic content Pérez-Serradilla and
Luque de Castro (2011)
Mandarin pomace Phenolic acids Dry, 125 W, 5 min, 2.45 GHz Total phenolic acids (99%) Hayat, Zhang, Chen, et al. (2010),
Hayat, Zhang, Farooq, et al. (2010)
512 H. Wijngaard et al. / Food Research International 46 (2012) 505–513
as mentioned with PLE. But as with PLE very high extraction temper- of Agriculture, Fisheries and Food for the funding of this literature
atures can generate unwanted compounds. For example, Tsubaki, research.
Sakamoto and Azuma (2010) reported that the proportion of poly-
phenol in the extract of tea residue increased from 25.3% to 74.4%
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