Food Chemistry 152 (2014) 46–55

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Review

Bound phenolics in foods, a review

Beatriz A. Acosta-Estrada, Janet A. Gutiérrez-Uribe ⇑, Sergio O. Serna-Saldívar
Centro de Biotecnología-FEMSA, School of Biotechnology and Foods, Tecnológico de Monterrey-Campus Monterrey, Av. Eugenio Garza Sada 2501, Monterrey, N.L. C.P. 64849, Mexico

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

Article history: Among phytochemicals, phenolic compounds have been extensively researched due to their diverse
Received 18 June 2013 health benefits. Phenolic compounds occur mostly as soluble conjugates and insoluble forms, covalently
Received in revised form 4 November 2013 bound to sugar moieties or cell wall structural components. Absorption mechanisms for bound phenolic
Accepted 18 November 2013
compounds in the gastrointestinal tract greatly depend on the liberation of sugar moieties. Food
Available online 27 November 2013
processes such as fermentation, malting, thermoplastic extrusion or enzymatic, alkaline and acid hydro-
lyses occasionally assisted with microwave or ultrasound have potential to release phenolics associated
Keywords:
to cell walls. Different kinds of wet chemistry methodologies to release and detect bound phenolic have
Bound phenolics
Malting
been developed. These include harsh heat treatments, chemical modifications or biocatalysis. New
Thermoplastic extrusion protocols for processing and determining phenolics in food matrices must be devised in order to release
Ultrasound assisted hydrolysis bound phenolics and for quality control in the growing functional food industry.
Chemical hydrolysis Ó 2013 Elsevier Ltd. All rights reserved.
Fermentation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2. Bound phenolics in food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.1. Phenolic covalent bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.2. Bioavailability of bound phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3. Releasing of bound phenolics through food processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.4. Bound phenolics from fibre in functional foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.5. Phenolic as functional ingredients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.6. Potential approaches to extract bound phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.6.1. Alkaline and acid hydrolyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.6.2. Enzymatic hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.6.3. Microwave assisted hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.6.4. Ultrasound-assisted hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.6.5. Other assisted hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.6.6. Detection methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

1. Introduction phytochemicals. Among these, phenolic compounds have been

extensively studied due to their diverse health benefits as antioxi-
Most of the beneficial properties of fruits, vegetables and whole dants, and for preventing chronic inflammation, cardiovascular
grains have been attributed to bioactive non-nutritional chemical diseases, cancer and diabetes.
compounds commonly named phytochemicals. Whole foods have Simple phenolic acids and flavonoids are the most common
been estimated to have between 5,000 and 25,000 individual phenolic compounds and they generally occur as soluble
conjugated (glycosides) and insoluble forms (Nardini & Ghiselli,
⇑ Corresponding author. Tel.: +52 81 83284322; fax: +52 81 83284262.
2004). In nature, phenolic acids occur mostly in the insoluble or
E-mail address: jagu@itesm.mx (J.A. Gutiérrez-Uribe).
bound forms whereas flavonoids present as glycosides with a

0308-8146/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2013.11.093
 B.A. Acosta-Estrada et al. / Food Chemistry 152 (2014) 46–55
single or multiple sugar moieties linked through an OH group
(O-glycosides) or through carbon–carbon bonds (C-glycosides).
In the early 1980s, an accurate procedure for the estimation of
free, soluble conjugated and insoluble bound phenolics was devel-
oped and proved in different foods (Krygier, Sosulski, & Hogge,
1982; Sosulski, Krygier, & Hogge, 1982). In numerous in vitro anti-
oxidant assays carried out, the insoluble bound phenolics have
demonstrated a significantly higher antioxidant capacity compared
to free and soluble conjugated phenolics (Chandrasekara & Shahidi,
2010; Liyana-Pathirana & Shahidi, 2006).
This paper will review (1) research conducted on bound phen-
olics in different food matrices and deal with the effects of different
physical, chemical and biocatalysis food processes aimed towards
increasing their bioavailability and functional properties, and (2)
extraction processes to obtain phenolic compounds as functional
ingredients.
2. Bound phenolics in food
Fruits and vegetables have most of their phytochemicals in the
free or soluble conjugate forms. Bound phenolics comprise an aver-
age of 24% of the total phenolics present in these food matrices
(Adom & Liu, 2002; Sun, Chu, Wu, & Liu, 2002). Examples of the
bound phenolic contents of fruits are shown in Table 1. Medlar ripe
fruit and oil palm fruit have 20.7% and 33.2% insoluble bound phe-
nolic contents, respectively (Gruz, Ayaz, Torun, & Strnad, 2011;
Neo, Ariffin, Tan, & Tan, 2010). Similar results are observed while
studying the phenolic profiles of vegetables. Onions have approxi-
mately 10% of bound phenolics while potato and pumpkin hull-less
seed (commonly consumed as a snack) have 39.9% and 21.1%,
respectively (Chu, Sun, Wu, & Liu, 2002; Peričin, Krimer, Trivić, &
Radulović, 2009), as depicted in Table 1.
On the contrary, most of the phenolic compounds associated to
whole cereal grains are in the insoluble bound forms (Table 1).
About 85, 75, and 62 of the total phenolics present in corn, wheat,
and rice, respectively, are in the insoluble bound forms (Adom &
Liu, 2002). Brown rice contains around 88% of bound phenolics
(Zhou, Robards, Helliwell, & Blanchard, 2004) and, according to
variety, barley (black, blue or yellow) might contain between
54.6% and 88.9% bound phenolics (Abdel-Aal, Choo, Dhillon, &
Rabalski, 2012).
2.1. Phenolic covalent bonds
Phenolics in the insoluble forms are covalently bound to cell
wall structural components such as cellulose, hemicellulose (e.g.
arabinoxylans), lignin, pectin and rod-shaped structural proteins
(Wong, 2006) as graphically described in Fig. 1. These phytochemi-
cals play important functions in the cell wall as providing both
physical and chemical barriers, protection against pathogen inva-
sion and astringency that deters attack by insects and animals,
antibacterial, antifungal and antioxidant functions (Liu, 2007;
Sancho, Bartolomé, Gómez-Cordovés, Williamson, & Faulds,
2001). Phenolic acids, such as hydroxycinnamic and hydroxyben-
zoic acids, form ether linkages with lignin through their hydroxyl
groups in the aromatic ring and ester linkages with structural
carbohydrates and proteins through their carboxylic group
(Bhanja, Kumari, & Banerjee, 2009; Liu, 2007; Liyana-Pathirana &
Shahidi, 2006).
2.2. Bioavailability of bound phenolics
Bound forms of phenolic compounds can be released and ab-
sorbed. For example, after coffee consumption, plasma levels of
caffeic acid increased due to the release and absorption of caffeic
47
acid from chlorogenic acid in bound complexes (Nardini, Cirillo,
Natella, & Scaccini, 2002).
There are different proved absorption pathways for bound phe-
nolic compounds in the gastrointestinal tract where microorgan-
isms, enzymes and even glucose transporters are involved
(Fig. 2). Partial release of bound phenolics takes place within the
gastrointestinal lumen in order to be rendered absorbable and
metabolized to exert their health benefits.
Kroon, Faulds, Ryden, Robertson, and Williamson (1997) pro-
posed that in humans over 95% of the total release of feruloyl
groups from wheat fibre took place during fermentation in the
colon due to enzymatic release (esterase and xylanase activities)
of the existing microflora. Only small amounts of ferulic acid were
released by gastric and small intestinal treatments (2.6%).
Insoluble bound phytochemicals survive stomach and intestinal
digestion and reach the colon since cell wall fibrous materials are
difficult to digest (Adom & Liu, 2002). Flavonols are also exten-
sively degraded by the colon microflora containing Clostridium
spp., and Eubacterium spp., to produce simpler phenolic compounds
(Selma, Espín, & Tomás-Barberán, 2009). Liu (2007) proposed that
the health benefits of bound whole grain phytochemicals are more
effective in the colon. This may partly explain the mechanism of
grain consumption in the prevention of colon cancer and other
digestive cancers, which is supported by epidemiological studies
(Adom & Liu, 2002).
Esterases are not limited to microbial origin. Andreasen, Kroon,
and Williamson (2001) proposed that hydrolysis by intestinal
esterases is very likely the major route for release and in vivo
absorption of hydroxycinnamic acid. In the small intestine, the
activity is located mainly in the mucosa epithelial cells. This study
provides the first evidence of human cinnamoyl esterases (Andrea-
sen et al., 2001), whereas in the large intestine most of the ester-
ases are of microbial origin. There are other mechanisms of
release and absorption of phenolic compounds in the small intes-
tine. Lactase phloridzine hydrolase (LPH) is a b-glycosidase found
on the brush border of mammalians small intestine cells capable
of hydrolyzing a range of flavonol and isoflavone glycosides (Day
et al., 2000). Aglycones formed can then be absorbed through the
epithelium. Some phenolics can also be transported through the
brush border as glycosides by sugar transporters. Glycosides could
be transported into enterocytes by the sodium-dependent glucose
transporter SGLT1 (Manach, Scalbert, Morand, Rémésy, & Jiménez,
2004). In the epithelial cells, cytosolic b-glucosidase hydrolyzes
these glycosides and aglycones are formed after absorption (Selma
et al., 2009).
The consumption of free or bound phenolic compounds
depends on the desired health impact. Dietary intake of bound
forms will have a chemopreventive activity against colon cancer.
Moreover, dietary intake of free and soluble conjugated forms will
be more rapidly absorbed in the stomach and small intestine and
distributed throughout the body with other health benefits such
as inhibition activities against oxidation of LDL cholesterol and
liposomes (Chandrasekara & Shahidi, 2011a). Therefore the release
of bound phenolics prior to intake will be necessary if other health
benefits beside prevention of colon cancer are preferred.
2.3. Releasing of bound phenolics through food processing
There are several food processes that enhance the liberation of
bound phenolics. These include fermentation and malting, as well
as thermomechanical processes such as extrusion cooking and
alkaline hydrolysis.
Fermentation increases total free phenolic content and antioxi-
dant activity. For instance, increased amounts of phenolic
compounds, DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS+
[2,20 -azinobis (3-ethylbenzothiazoline-6-sulphonic acid)] radical
48 B.A. Acosta-Estrada et al. / Food Chemistry 152 (2014) 46–55

Table 1
Insoluble bound phenolic content in food.

Source Insoluble bound phenolics in total phenolics References

(%)
Fruits
Apple (Malus domestica) 6.50 Sun et al. (2002)
Banana (Musa acuminate) 33.10 Sun et al. (2002)
Cranberry pomace (Vaccinium macrocarpon) 76.27 White et al. (2010)
Grapefruit (Citrus x paradisi) 23.60 Sun et al. (2002)
Huyou peel (Citrus paradisi Changshanhuyou) 16.65 Xu, Ye, Chen, and Liu (2007)
Medlar ripe fruit (Mespilus germanica L.) 20.69 Gruz et al. (2011)
Oil palm fruit (Elaeis guineensis) 33.19 Neo et al. (2010)
Orange (Citrus sinensis) 24.30 Sun et al. (2002)
Vegetables
Carrot (Daucus carota) 37.6 Chu et al. (2002)
Chinese cabbages <2 Harbaum, Hubbermann, Zhu, and Schwarz (2008)
 Pak choi (Brassica campestris L. ssp. chinensis var.
communis)
 Chinese leaf mustard (Brassica juncea Coss)
Hot pepper varieties (Capsicum annuum L.) 40.59–58.71 Hervert-Hernández, Sáyago-Ayerdi, and Goñi (2010)
 Arbol
 Chipotle
 Guajillo
 Morita
Kale leafs (Brassica oleraceae L. var. acephala DC.) 5.32 Ayaz et al. (2008)
Onion (Allium cepa) 9.70 Chu et al. (2002)
 Var. pearl 22.61 Albishi et al. (2013a)
Potato (Solanum tuberosum) 39.9 Chu et al. (2002)
Pumpkin hull-less seed (Cucurbita pepo) 21.07 Peričin et al. (2009)
Red pepper (Capsicum annuum L.) 9.80 Chu et al. (2002)
Edible flowers Kaisoon, Siriamornpun, Weerapreeyakul, &
Meeso(2011)
 Nelumbo nucifera 70.73
 Cosmos sulphureus 51.42
 Telosma minor 26.82
Cereals
Barley (Hordeum vulgare L.) 70.08 Dvoráková et al. (2008)
Barley malt 51.92
Barley varieties 54.62–88.87 Abdel-Aal et al. (2012)
 Black
 Blue
 Yellow
Maize (Zea mays) 85.00 Adom and Liu (2002)
Blue maize nejayote 91.05 Gutiérrez-Uribe et al. (2010)
Red maize tortillas 98.88 Mora-Rochin et al. (2010)
Oat (Avena sativa) 75 Adom and Liu (2002)
88.04 Irakli, Samanidou, Biliaderis, and Papadoyannis (2012)
Rice (Oryza sativa) 62 Adom and Liu (2002)
Brown rice 88 Zhou et al. (2004)
Red Sorghum (Sorghum L.) 85.48 Dykes and Rooney (2006)
Triticale ( Triticosecale) 82.02 Irakli et al. (2012)
Wheat (Triticum spp.) 75 Adom and Liu (2002)
Hard wheat 62.18 Liyana-Pathirana and Shahidi (2006)
White wheat bran 83.18 Kim et al. (2006)
Kodo millet (Paspalum scrobiculatum) 71.59 Chandrasekara and Shahidi (2010)
Other food products
Beer 76.94–99.19 Nardini and Ghiselli (2004)
Maverick pinto bean (Phaseolus vulgaris) 96.85–98.24 Ross et al. (2009)
Cowpea (Vigna unguiculata) 29.57 Gutiérrez-Uribe, Romo-Lopez, and Serna-Saldívar
(2011)
Mustard (Brassica juncea) <2 Naczk, Wanasundara, and Shahidi (1992)
Cashew nut (Anacardium occidentale L.) <2 Chandrasekara and Shahidi (2011b)

scavenging properties were observed in wheat after incubation -

with Aspergillus oryzae during 4 days (Bhanja et al., 2009). Similarly
buckwheat, wheat germ, barley and rye treated with Lactobacillus
rhamnosus and Saccharomyces cerevisiae increased their total phe-
nolic content by 17.2–39.4% when fermented with L. rhamnosus
and 4.9–22.7% with S. cerevisiae. As a result, an increase of the anti-
oxidant activity, measured by the FRAP assay, after fermentation
with both microorganisms was observed (Ðordević, Šiler-Marinković,
& Dimitrijević-Branković, 2010). Fermentation is preferred instead of
the utilization of commercial enzymes to enhance the nutraceutical
value of foods because it is relatively cheap.
A microorganism that synthesizes enzymes capable of breaking
ester links and consequently releases bound phenolics (Table 2)
was isolated by Sanchez-Gonzalez et al. (2011). This alkali resistant
 B.A. Acosta-Estrada et al. / Food Chemistry 152 (2014) 46–55
Fig. 1. Representations of primary cell wall structure of plant material and cross-linking between structural components and phenolic compounds. (A) Cellulose.
(B) Hemicellulose. (C) Structural proteins. (D) Pectin. (E) Phenolic acids. (F) Lignin.
Fig. 2. Absorption pathways of bound phenolic compounds in the gastrointestinal
tract. (A) Hydrolysis of bound soluble conjugated forms by mucosa cells cinnamoyl
esterases. (B) Soluble conjugated forms transport into enterocytes by the sodium-
dependent glucose transporter SGLT1. (C) Lactase phloridzine hydrolase (LPH) (b-
glycosidase) of the brush border hydrolysis soluble conjugated phenolic com-
pounds. (D) Epithelial cells cytosolic b-glucosidase hydrolyzes glycosides, and
aglycones are formed after absorption. (E) Esterase and xylanase activities of colon
microorganism (e.g. Clostridium spp., Eubacterium spp., and Bifidobacterium
adolescentis).
microorganism (Bacillus flexus NJY2), isolated from the wastewater
of alkaline-cooking of maize, has ferulic acid ester hydrolytic activ-
ity. This microorganism was capable of hydrolyzing ferulic acid es-
ters associated to the nixtamalized maize bran and released 1–5 g
of ferulic acid per kg of substrate.
Sprouting or malting, practiced for several centuries, is also
known to improve the nutritional and nutraceutical value of cere-
als (Subba Rao & Muralikrishna, 2002) and is another way to im-
prove the bioavailability of bound phenolics. It is defined as the
49
controlled germination of seeds in order to activate the respiration
system and produce different types of intrinsic enzymes (amylo-
lytic, proteolytic and cell wall degrading). Dvoráková et al. (2008)
found a significant decrease of bound phenolics with the corre-
sponding increase of free phenolic and antioxidant capacity due
to the germination of barley. Ferulic and sinapic acids increased
50% and nearly 10 times, respectively. Increase in phenolic com-
pounds during germination had also been observed in other matri-
ces beside cereals. Albishi, John, Al-Khalifa, and Shahidi (2013a)
observed an increase in the free forms of polyphenols in red onions
during germination due to the dismantling of the cell walls during
the sprouting process. Furthermore, the drying process or kilning
improved the phytochemical profile of barley malt (Maillard & Ber-
set, 1995). A similar positive effect of malting of brown rice was
observed by Tian, Nakamura, and Kayahara (2004).
Processing cereals with thermoplastic extrusion releases bound
phenolics due to breaking of conjugated moieties (Rochín-Medina
et al., 2012). A significant increase (31.25%) in the amount of free
flavonoids of extruded dehulled black beans (Phaseolus vulgaris
L.) has been observed (Chuck-Hernandez, Gutiérrez-Uribe, &
Serna-Saldívar, 2011). In extruded whole maize (Zea mays) and
chickpea (Cicer arietinum) flours, antioxidant activity of free
phenolic extracts increased while bound phenolics decreased in
comparison with the unprocessed samples (Rochín-Medina et al.,
2012). Likewise, extrusion cooking of white and yellow maize
increased free ferulic acid and decreased soluble conjugated and
bound ferulic acid forms of raw kernel (Mora-Rochin et al., 2010).
Traditional methods of food production such as alkaline treat-
ments are known to release bound phenolics. Lime-cooking of
maize kernels to produce tortillas changed the ratio between free
and bound phenolics in masa compared with raw maize. The aver-
age content of free phenolics in masa increased at least 20% of the
concentration originally present in raw kernels. Bound ferulic acid
present in masa was approximately 1/3 of that present in whole
kernels whereas free ferulic acid was concentrated at least 10
times in masa compared to raw kernels (Gutiérrez-Uribe,
Rojas-García, García-Lara, & Serna-Saldivar, 2010). Chemical
peeling (NaOH or KOH) is used to remove skin of fruits and
vegetables. Most fruits have significant amounts of total phenolics
50 B.A. Acosta-Estrada et al. / Food Chemistry 152 (2014) 46–55
Table 2
Microorganism and their effect in fermentation strategies to release bound phenolics in different plant matrices.
Plant matrix Microorganism Effect
Rice bran Rhizopus oryzae Increase 3.5 times (from 480 to 2200 lg/g bran) of ferulic acid at 24 h of solid
fermentation.
Cabbage Lactobacillus Significant release of bound phenolic compounds such as kaempferol.
leaves plantarum
Lactobacillus
collinoides
Palm oil mill Aspergillus niger DPPH scavenging activity IC50 on fermented samples found in 0.45 mg/ml instead of
waste 1.13 mg/ml on unfermented samples.
Apple Phanerocheate Polyphenol content of extract increase from 4.6 to 16.12 mg GAE/g dry weight.
pomace chrysosporium
associated to the skin. For instance, the skin of peaches (Prunus
persica) contains 35.4% of the total phenolic content associated to
the whole edible fruit (Asami, Hong, Barrett, & Mitchell, 2003).
Further research is needed in order to study effects of alkaline
peeling in the phenolic profile of fruits and skin byproducts.
2.4. Bound phenolics from fibre in functional foods
Fibres and bran are frequently supplemented to cereal-milled
fractions and dairy fermented products. Dried apple peel has been
successfully added to muffins with the aim of obtaining significant
improvements in terms of antioxidant activity and total phenolic
content (Rupasinghe, Wang, Huber, & Pitts, 2007). In the develop-
ment of soft dough biscuits, mango peel powder was also tested.
The replacement of 20% of wheat flour with mango powder in-
creased the total phenolic content 8.33 times compared to the con-
trol. However, only the biscuits prepared with less than 10% mango
powder were organoleptically accepted by panelists (Ajila,
Leelavathi, & Prasada-Rao, 2008). The effect of 4% addition of
triticale bran in yogurts with Lactobacillus acidophilus and
Bifidobacterium lactis used as probiotics was studied. Extracts
exhibited stronger antioxidant activity and triticale bran served
as prebiotic and antioxidant source (Agil & Hosseinian, 2012). In
drinking yoghurts, the addition of pectins before fermentation
yielded yoghurts with a greater TEPC and more polar polyphenolics
(Sun-Waterhouse, Zhou, & Wadhwa, 2012).
2.5. Phenolic as functional ingredients
Natural phenolic compounds have been suggested as ideal sub-
stitutes for preservatives in food formulations due to their antiox-
idant and antimicrobial properties (Fazary & Ju, 2007; Oliveira,
Cipolatti, Furlong, & Soares, 2012; Ou & Kwok, 2004). For example,
the FDA classifies ferulic acid as an antioxidant in the list of food
additives (Fazary & Ju, 2007). Since high percentages of fibres con-
taining phenolic compounds cannot be added, extracts containing
these compounds can be supplemented instead. Bhanger et al.
(2008) incorporated methanolic extracts of rice bran rich in pheno-
lic compounds in cookies and observed that these compounds ex-
erted antioxidant properties and therefore decreased lipid
oxidation. Thus, phenolic compounds can be alternatively used as
functional ingredients to improve the antioxidant capacity of pro-
cessed foods and to provide the health benefits associated with
these phytochemicals.
There are other applications besides the food industry for phe-
nolic compounds. Applications range from cosmetics (Sancho et al.,
2001), nutraceuticals and pharmaceuticals. Ferulic acid is also used
as precursor of the flavouring agent vanillic acid.
There is a need to develop new extraction methodologies for
phenolic compounds so that they can effectively be used as func-
tional ingredients. Agro-industrial byproducts are good sources of
References
Oliveira et al. (2012)
Knockaert, Camp, Struijs, Wille,
and Raes (2012)
Jamal, Idris, and Alam (2011)
Ajila, Brar, Verma, Tyagi, and
Valéro (2011)
lignocellulosic materials, which are rich in bound phenolics that
can be extracted and released. For instance, brewer’s spent grain
is a byproduct rich in ferulic and p-coumaric acids (Mussatto,
Dragone, & Roberto, 2007). Lettuce and chicory byproducts are
examples of cheap sources also rich in antioxidant phenolics
that can be extracted to functionalize foodstuffs (Llorach,
Tomás-Barberán, & Ferreres, 2004). Processing of onions and
potato produces large amounts of discards, mainly skins. These
byproducts can serve as natural sources of anti-inflammatory sub-
stances; the extracted polyphenols had shown to inhibit COX-2
activity (Albishi, John, Al-Khalifa, & Shahidi, 2013b). Potato and
onion skins contained 1.2–14.42 times and 6 times (pearl variety)
more bound phenolic compounds, respectively, than the edible
part (Albishi, John, Al-Khalifa, & Shahidi, 2013c; Albishi et al.,
2013a). On the other hand, the wastewater of the alkaline-cooking
of maize to produce tortillas, is also a good source of phytochemi-
cals such as ferulic acid (Gutiérrez-Uribe et al., 2010).
In the process of releasing phenolic compounds from lignocellu-
losic material, sugar moieties will also be released. These carbohy-
drates can be effectively fermented into ethanol. New and cheap
methods to separate fermentable sugars and phenolics compounds
have to be investigated for future use.
2.6. Potential approaches to extract bound phenolics
Different methodologies to release bound phenolic have been
developed. After the application of any of these treatments, the
naturally occurring and released phenolics are commonly ex-
tracted with organic solvents including two phase extraction sol-
vent systems. Commonly used extraction solvents are alcohols
(methanol and ethanol), acetone, diethyl ether, and ethyl acetate
(Del Pozo-Insfran, Serna-Saldivar, Hernández-Brenes, & Talcott,
2006; Gutiérrez-Uribe et al., 2010). However, extremely polar
phenolic acids, such as benzoic and cinnamic acids, could not be
effectively extracted with pure organic solvents so mixtures of
alcohol–water or acetone–water are recommended (Stalikas,
2007). In addition, acidified or chilled solvents are frequently used
(Rochín-Medina et al., 2012; Singh-Gujral, Sharma, Kumar, & Singh,
2012). Two phase extraction solvent systems consist of MeOH-
ammonia or 95% MeOH-ammonia and hexane (Naczk & Shahidi,
1989).
2.6.1. Alkaline and acid hydrolyses
Alkaline and acidic hydrolyses are the most common means of
releasing phenolic compounds (Stalikas, 2007). The main variables
of these chemical hydrolyses are concentration of acid/base, hydro-
lysis time and temperature. Acid treatment breaks glycosidic
bonds and solubilizes sugars, but generally leaves ester bonds
intact (Fazary & Ju, 2007). Acidic hydrolysis at elevated tempera-
tures results in the loss of some phenolics (Krygier et al., 1982;
Verma, Hucl, & Chibbar, 2009). In Opuntia ficus indica prickly fruit,
 B.A. Acosta-Estrada et al. / Food Chemistry 152 (2014) 46–55
acidic hydrolysis caused degradation of flavonols (Moussa-Ayoub,
El-Samahy, Kroh, & Rohn, 2011).
Phenolic compounds are better released with alkaline hydroly-
sis than in acid hydrolysis conditions (Kim, Tsao, Yang, & Cui, 2006)
and reduces their loss. For example, an alkali hydrolysis will cause
the loss of 4.8% of corn ferulic acid in contrast with 78% lost after
acid hydrolysis (Krygier et al., 1982). Alkaline hydrolysis breaks
the ester bond linking phenolic acids to the cell wall and thus is
an effective way to release phenolic compounds from polysaccha-
rides. Alkaline treatments are commonly used to extract bound
phenolic acids and other related compounds from cereal grains
(Fazary & Ju, 2007; Kim et al., 2006; Verma et al., 2009). Generally,
alkaline hydrolysis is performed at room temperature (Mussatto
et al., 2007) and left to proceed for 15 min up to overnight
(Stalikas, 2007). Treatment with different concentrations (1–4 M)
of sodium hydroxide for varying lengths of time has proven to be
effective in releasing these bound phenolics (White, Howard, &
Prior, 2010). Alkaline hydrolysis totally releases the bound pheno-
lics in short time at high alkali concentration and temperature
(Oufnac et al., 2007).
The addition of ascorbic acid (AA) and ethylenediaminetetra-
acetic acid (EDTA) to prevent the loss of phenolic acids during alka-
line hydrolysis has been investigated (Nardini, Cirillo, Natella, &
Mencarelli et al., 2002; Nardini, Cirillo, Natella, & Scaccini, 2002;
Peričin et al., 2009; Ross, Beta, & Arntfield, 2009). The addition of
10 mM EDTA and 1% of AA completely prevents the degradation
of phenolic acids susceptible to oxidative degradation. Del
Pozo-Insfran et al. (2006) investigated the acidification of masa
samples processed into corn tortillas with fumaric acid and
significantly reduced the loss of total phenolics, anthocyanins
and antioxidant capacity.
2.6.2. Enzymatic hydrolysis
A more specific and effective method to release bound phenolic
compounds is enzymatic hydrolysis. Carbohydrate-hydrolyzing
enzymes such as pectinases, cellulases, amylases, hemicellulases
and glucanases had been effectively used to release polyphenols
(Landbo & Meyer, 2001; Zheng, Hwang, & Chung, 2009). These en-
zymes play a role in disintegrating the plant cell wall matrix and
consequently facilitating the polyphenol extraction (Stalikas,
2007; Zheng et al., 2009).
Commercial enzyme preparations with pectinase and esterase
activities have been used to solubilize most phenolic acids present
in sugar beet pulp yielding free and esterified ferulic acids (Fazary
& Ju, 2007). Likewise, the release of ferulic acid from barley has
been accomplished using enzymatic extracts with esterase and
xylanase activities (Sancho et al., 2001). Polyphenol extraction
from unripe apples by carbohydrate-hydrolyzing enzymes contain-
ing arabinases, cellulases, b-glucanases, hemicellulases and xylan-
ases increased the contents of p-coumaric, ferulic and caffeic acids
8, 4, and 32 times, respectively (Zheng et al., 2009). Similarly, the
enzymatic release of phenolic compounds from black currant pom-
ace using commercial protease and pectinase produced higher
amounts of phenols but lower extraction yields of anthocyanins
(Landbo & Meyer, 2001). Landbo and Meyer (2001) attributed the
lower amounts of anthocyanins in extracts to the presence of
b-glucosidase, b-galactosidase, or a-L-arabinosidase activities in
multicomponent enzyme preparations, which liberated the sugar
moieties of anthocyanins producing unstable aglycones.
2.6.3. Microwave assisted hydrolysis
Microwave assisted extraction (MAE) enables heating of the sol-
vent mixture by directly interacting with the free water molecules
present in the system, which results in the rupture of the plant tis-
sue and release of the constituents into the solvent (Jokić et al.,
2012). MAE commonly increases phenolic yields and lowers
51
extraction costs due to the reduction of treatment time and solvent
consumption (Beejmohun et al., 2007; Gallo, Ferracane, Graziani,
Ritieni, & Fogliano, 2010). Additionally, the technique combines
high temperature and high pressure for optimal release of phenolic
acids with the simultaneous breakdown of the cell walls
(Chiremba, Rooney, & Beta, 2012) such as partial degradation of
hemicelluloses and lignin (Tsubaki, Ozaki, & Azuma, 2010).
There are many investigations that focus on the optimization of
the microwave-assisted extraction process for phenolic com-
pounds. Most frequently optimized variables considered are
extraction time, temperature, solvent type and ratio (solid/liquid)
and irradiation power. These studies focus on a variety of matrices
such as broccoli and mushroom (Jokić et al., 2012; Zhang, Lv, Pan, &
Fan, 2012).
Other investigations propose the combination of microwave
with alkaline hydrolysis. Examples of microwave-assisted hydroly-
sis to enhance and release bound phenolics are summarized in
Table 3. For instance, the extraction of sorghum and maize bran
and flour bound phenolic acids was performed with MAE (45 s,
and1400 W) in 2 M NaOH with the aim of releasing ferulic and
coumaric acids at 190 °C. This temperature is sufficient to break
ether bonds which are labile at 170 °C (Chiremba et al., 2012). Sim-
ilarly, alkaline hydrolysis extraction of lignans and phenolic acids
by MAE was compared with the traditional treatment. Lower
extraction times and better yields were observed since alkaline
hydrolysis of ferulic acid was accomplished in 6 h compared to
MAEs 15 min. Furthermore, the dual treatment yielded 2.09 times
more (2.1–4.4 mg/g) ferulic acid in the extract (Beejmohun et al.,
2007).
2.6.4. Ultrasound-assisted hydrolysis
Ultrasound-assisted hydrolysis has been developed to leach and
hydrolyze phenolic compounds faster than traditional methods
since the surface contact area between the solid and liquid phases
is increased by particle disruption (Herrera & Luque de Castro,
2004). In strawberries, phenolic compounds such as naringin,
rutin, naringenin, ellagic acid, quercetin and kaempferol are
effectively extracted by ultrasound in 3 cycles of 30 s compared
to 2–20 h of traditional methods (maceration/stirring) (Herrera &
Luque de Castro, 2004). Ultrasound has also been used to release
conjugated phenolics from free extracts of plant materials (Peričin
et al., 2009).
Ultrasound hydrolysis can also be paired with other hydrolysis
methods. The application of ultrasonication significantly acceler-
ated the hydrolysis rate of cranberry conjugated phenolics from
16 h required by a conventional hydrolysis technique to less than
1.5 h (Wang & Zuo, 2011). Combination of ultrasound with super-
critical fluids may be an effective and environmentally friendly
way to release and extract bound phenolic compounds. A compar-
ison of the effectiveness of extraction of rutin associated to buck-
wheat processed by ultrasound indicated that this process
yielded 1.5% dw rutin in contrast to only 0.1% obtained with the
common process (Fabjan et al., 2003).
2.6.5. Other assisted hydrolysis
Far-infrared radiation (FIR) can effectively release bound phen-
olics from plant matrices (Wanyo, Siriamornpun, & Meeso, 2009)
and activate low-molecular-weight natural antioxidants (Lee
et al., 2003). FIR rays are electromagnetic waves longer than
4 lm but shorter than microwaves (k > 0.1 cm) that transfer heat
to the centre of materials and are capable of breaking covalent
bonds of phenolic compounds such as flavonoids and tannins
(Lee et al., 2003). FIR is also an effective and economical dehydra-
tion method with significantly lower drying times (Senevirathne
et al., 2010). Rice and peanuts hulls where treated with FIR and
52 B.A. Acosta-Estrada et al. / Food Chemistry 152 (2014) 46–55

Table 3
Microwave-assisted hydrolysis applied to different plant matrices to release bound phenolic compounds.

Source MAE parameters Observations References

Temperature Time Energy
[°C] level
[W]
Mushroom 110 5 min 500 Higher phenolic compounds extraction yields using MAE compared to heat reflux and Zhang et al.
(3 cycles) maceration. (2012)
 Agaricus blazei
murrill
Spices 50 18 min 200 Average yield of extraction 4 times higher than sonication aided extraction. Gallo et al.
(2010)
 Cinnamomum
zeylanicum
 Coriandrum sativum
 Cuminum cyminum
 Crocus sativus
Mandarin pomace NS 5, 10, 250 Free phenolic acids increased whereas the bound fractions decreased. Hayat et al.
and and (2010)
15 min 500
 Citrus reticulata
 Prunus mume 110, 140, 2 min 1000 Syringaldehyde was the most abundant phenolic compound (49.8%) followed by Tsubaki
Stone 170 syringic et al. (2010)
and 200 acid (7.7%), both compounds originated from syringyl units of hydrolyzed lignin.
Wheat bran 60, 80, 100 20 min 500 MAE using methanol significantly increased the total phenolic compound content Oufnac
and 120 to et al.
1.92–2.02 times of traditional solvent extraction (solvent reflux with heat). (2007)
 Triticum spp
Bran and flour 190 45 s 1400 MAE extraction performed in 2 M NaOH significant release ferulic acid and coumaric Chiremba
acid. et al. (2012)
 Sorghum bicolor
Zea mays
Flaxseed NS 15 min 50, 100 MAE using 0.1 M NaOH was accomplished in 15 min instead of 6 h. Furthermore, the Beejmohun
and dual et al. (2007)
150 treatment yielded 2.09 times more (2.1–4.4 mg/g) ferulic acid in the extract.
 Linum usita-
tissimum
L., Linaceae

NS = Not specified.

total phenol contents increased 1.58 and 1.94 times, respectively
(Lee et al., 2003, 2006).
Pulsed electric field (PEF) is another kind of assisted hydrolysis.
The application of high voltage pulsed electric fields (PEF) to plant
tissues increases porosity of plant cells (Kannan, 2011). Red cab-
bage has been treated with PEF with a significant increase of
anthocyanins content in extracts (Kannan, 2011). Another example
of the effectiveness of PEF is in the extraction of polyphenols from
grape pomace and peel (Khalil, 2011).
Pressurized liquid-assisted hydrolysis modifies the properties of
water by heating above 100 °C and keeping the pressure suffi-
ciently high to maintain water in a liquid state and thus improves
the extraction capability (Buranov & Mazza, 2009). Extraction of
ferulic acid and vanillin from flax shives, wheat bran and corn bran
were carried out using two extraction methods: non-pressurized
alkaline hydrolysis (0.5 M NaOH) and pressurized solvents (0.5 M
NaOH, water, ethanol and ammonia) with significantly higher
amounts of phenolic compounds in pressurized solvents (Buranov
& Mazza, 2009).
Increase in phenolics in electron-beam irradiation-assisted
hydrolysis is attributed to the release of bound phenolics from
their cellular matrix (Teets, Minardi, Sundararaman, Hughey, &
Were, 2009). Teets et al. (2009) evaluated the effect of electron
beam irradiation doses from 0 to 30 kGy on extraction yield and
phenolic compounds in almond skin phenolic extracts. Electron
beam irradiation improved extraction yield by as much as 23%
and irradiated samples extracted with acidified methanol also
exhibited an increase in free phenolic compounds (Teets et al.,
2009).
2.6.6. Detection methods
Detection methods of phenolic compounds have widely been
discussed in the scientific literature. Quantification and identifica-
tion of natural products can be performed by different methods.
The Folin–Ciocalteu assay is used for the determination of total
phenols but it does not detect all phenolic groups found in the ex-
tracts and shows interference with ascorbic acid and reducing sug-
ars (Stalikas, 2007). In the last twenty years, HPLC has been the
analytical technique that has dominated the separation and char-
acterization of phenolic compounds (Stalikas, 2007). The preferred
column choice is almost exclusively reverse phase C18 (Adom &
Liu, 2002; Gutiérrez-Uribe et al., 2010; Mora-Rochin et al., 2010)
coupled with either an ultraviolet/visible (UV/VIS), photodiode ar-
ray (PDA) or UV-fluorescence detectors. Other methods used for
the detection of phenolics include fluorescence detection and mass
spectroscopy (MS). This last instrumental analytical technique is
used for elucidating the chemical mass of molecules. Diferulates
and disinapates have also been detected and structurally identified
by gas chromatography (GC)–MS and two-dimensional NMR (Qiu,
Liu, & Beta, 2010).
Wet chemistry measurement of phenolic acid and flavonoid
contents requires the extraction of compounds and destruction of
sample making it time-consuming and expensive. A method based
on physical structure is infrared (IR) spectroscopy. IR spectroscopy
 B.A. Acosta-Estrada et al. / Food Chemistry 152 (2014) 46–55
(near and mid) is powerful, fast, accurate and a non-destructive
analytical tool (Zhang, Shen, Chen, Xiao, & Bao, 2008) making it
an excellent option to determine bound phenolic compounds pro-
viding an alternative to traditional wet chemistry analysis. Infrared
spectroscopy has been used to measure phenolic compounds in a
wide range of food commodities, for example cereals (brown rice),
and fruits (blueberries) (Sinelli, Spinardi, Di Egidio, Mignani, &
Casiraghi, 2008; Zhang et al., 2008). IR has been underused as
detection method for phenolic compounds present in various types
of solvents. For example, it has been use for detection in methanol
extracts of onions and shallots (Lu et al., 2011). On the contrary,
detection of phenolic compounds with no sample preparation
has been made in wine using Fourier transform IR spectroscopy
(Versari, Parpinello, Scazzina, & Del-Rio, 2010).
It is necessary to develop and establish protocols that allow the
use of IR in the determination of bound phenolics for the screening
of raw materials for functional foods as well as for quality control
of finished goods in the food and nutraceutical industries.
3. Conclusions
Phenolic compounds are distributed throughout the plant king-
dom and it is not surprising to find them in foods like snacks
(pumpkin hull-less seed) and beer. Most phenolic compounds in
cereal-based matrices are in the insoluble bound forms. Fruits
and vegetables are rich in soluble conjugates. A large number of
variables can change the phenolics of a certain food. The use of
heat, enzymes, alkali cooking, fermenting microorganisms and
malting or controlled germination have a profound effect on these
phytochemicals. A method to process plant-based food must be
developed with the aim of rendering these insoluble bound forms
into more bioactive moieties to obtain their health benefits with-
out changing the organoleptic properties of the processed food.
Additionally released phenolic compounds within food matrix will
serve as food preservative. Furthermore, in order to utilize bound
phenolic compounds in the food, pharmaceutical or cosmetic
industries, methods to release and extract the phenolic compounds
from agroindustrial byproducts without using organic solvents
must be devised. Moreover, fast, accurate and non-destructive
detection approaches such as IR spectroscopy need to be developed
as methods of quality control in the production of functional ingre-
dients or applied to raw materials and finished products for the
pharmaceutical, cosmetic or functional food industries.
Acknowledgements
The senior author would like to express her sincere thanks to
the Research Chair Fund CAT-151 from Tecnológico de Monterrey
and CONACYT for their financial support for graduate studies and
project 168708 (Ciencia Básica).
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