Food Research International 151 (2022) 110818

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Food Research International

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Valorization of cereal by-product hemicelluloses: Fractionation and

purity considerations
Anis N. Arzami a, *, Thao M. Ho a, b, Kirsi S. Mikkonen a, b
a
Department of Food and Nutrition, P.O. Box 66, 00014, University of Helsinki, Finland
b
Helsinki Institute of Sustainability Science (HELSUS), P.O. Box 65, 00014, University of Helsinki, Finland

A R T I C L E I N F O A B S T R A C T

Keywords: The biomass from cereal side streams is rich in valuable components, such as hemicelluloses. Among the
Cereal side stream hemicelluloses, arabinoxylans and β-glucans are the most acknowledged for potential health benefits. Numerous
Cereal hemicellulose publications discuss the potential to use purified forms of these hemicelluloses for various applications. However,
Arabinoxylan
as the purification of hemicelluloses may not be economically feasible to upscale, sustainable and cost-effective
β-glucan
Industrial application
methods are needed to make their valorization more realistic for industrial applications. Co-components present
Cereal crop in hemicellulose-rich fractions may also provide added functionality, such as flavonoid content and antioxidant
capacity. This review provides an overview on the feasibility of sustainably upscaling hemicellulose extraction
processes, focusing on by-products from different cereal streams. We describe the hemicelluloses’ physico­
chemical properties and provide various possible applications of pure and impure fractions from small scale to
pilot and industrial scale. Furthermore, real case examples on the industrial utilization of cereal side streams are
enclosed. This review provides pathways for future research for developing the hemicellulose extraction methods
to obtain fractions with optimized purity, and offers suggestions to valorize them.

1. Introduction
Global food production is expected to rise by about 12% by 2025
(OECD & FAO, 2016), and the most important contribution to this in­
crease, according to the data from Food and Agriculture Organization
(FAO), comes from wheat (10%), rice (14%) and maize (13%). At the
moment, about 12.9% of total food waste is generated from agricultural
side streams (Baiano, 2014). The increase in cereal production over the
coming decades may lead to an excessive amount of cereal processing
waste (biomass). In most countries, cereal biomass will be utilized as
animal feed and biofuel. However, extensive research over the past
decades has revealed that these biomasses are rich in valuable compo­
nents such as dietary fibre (e.g. arabinoxylans and β-glucans) (Andre­
wartha et al., 1979; Bengtsson & Aman, 1990; Izydorczyk & Biliaderis,
2000; Knudsen & Lærke, 2010; Lambo et al., 2005).
These findings have increased the general public’s awareness about
the benefits of higher amounts of dietary fibre in their daily diets. The
food industry is trying to meet these demands by exploring new and
more economical methods to incorporate functional dietary fibre into
food products. In addition, the development of domestic food in­
gredients can be improved to guarantee food security and sufficiency
during difficult times (e.g. pandemics, natural disasters and wars). The
utilization of cereal biomass in other industries is also crucial to boost
the economy. Therefore, seeking alternative and cost-effective ways to
optimize the valorization of cereal processing by-products is on the
global agenda. This is in line with two of the 17 Global Sustainability
Goals of the United Nations which emphasize Zero hunger (Goal 2) and
Responsible consumption and production (Goal 12; UN, 2021) where
one of the key focuses is to strengthen natural resource management in
order to nurture the economy and societal growth.
The first documented use of the term dietary fibre occurred in 1953
when Hipsley (1953) defined it as cellulose, lignin and hemicelluloses.
Over the years, the definition of dietary fibre has been the centre of
numerous international debates. Recently, dietary fibre can be defined
as “polysaccharides, lignin and oligosaccharides that are not hydrolyzed by
human alimentary enzyme” (Lee & Prosky, 1995). There are two types of
dietary fibre; water-soluble (mostly non-starch polysaccharides) and
water-insoluble (cellulose, most hemicelluloses, non-starch poly­
saccharides and lignin).
Among the dietary fibres, hemicellulose which is the second most
abundant cereal biomass (20–35%) shows the most promise for high-
value applications. Compared to cellulose and lignin, hemicelluloses

* Corresponding author.
E-mail address: anis.arzami@helsinki.fi (A.N. Arzami).

https://doi.org/10.1016/j.foodres.2021.110818
Received 12 April 2021; Received in revised form 9 September 2021; Accepted 21 November 2021
Available online 30 November 2021
0963-9969/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A.N. Arzami et al.
are highly branched, naturally amorphous with a lower degree of
polymerization, making it easier to be utilized in polymeric materials,
food, energy and medicine (Luo et al., 2019). However, the value-added
applications of hemicelluloses are still underutilized, especially in in­
dustrial scale (Farhat et al., 2017; Luo et al., 2019; Qaseem et al., 2021).
The most known health beneficial hemicelluloses are arabinoxylans and
β-glucans. Both polysaccharides have been linked to gut health promo­
tion (Broekaert et al., 2011; Chen et al., 2019; Jayachandran et al.,
2018), reduce the risk of type II diabetes (Fadel et al., 2018; Liatis et al.,
2009) and cardiovascular diseases (CVD) (Pins & Kaur, 2006; Salden
et al., 2018).
In the last fifty years, special attention has been given to cereal by-
product hemicelluloses as evidenced by the increased amount of scien­
tific publications on the subject (Skendi et al., 2020). Their valorization
has been gaining attention due to their health promoting effects, various
possible industrial applications, impact on economy and support to­
wards sustainability. However, most of the available publications focus
on the extraction and application of pure fractions of hemicelluloses
from the cereal side streams. This is not a comparable or realistic case
when considering industries, as their cereal processing waste contain
impure fractions of hemicelluloses. The idea to purify the fractions for
possible high-end applications are currently too costly to upscale and
unsustainable.
For example, the physicochemical properties and extraction methods
to isolate hemicelluloses in wood, bamboo, cereal, fruit and vegetable
residues were described in detail in previous studies (Peng et al., 2012;
Peng & She, 2014; Tejada-Ortigoza et al., 2016). However, there is
limited information about whether the extraction methods were suitable
to be used in pilot scale. Another study by Farhat et al. (2017) focused on
the chemical modification of hemicelluloses especially for biomedical
applications. They also reviewed the pros and cons of hemicelluloses
extraction methods and the possibility to upscale. However, their study
Fig. 1. A sketch showing various cereal side streams from which health-beneficial hemicelluloses such as arabinoxylans and β-glucans can be fractionated and
purified for different industrial applications.
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Food Research International 151 (2022) 110818
focusses on wood hemicelluloses and other hemicellulose applications
were not discussed in detail.
The aim of this review is to provide an overview on the feasibility to
sustainably upscale hemicellulose extraction processes (Fig. 1). This
work first identifies the streams of cereal processing waste which pro­
vide adequate quantities of hemicelluloses. Then, the extraction and
purification techniques which are economically feasible to be upscaled,
and a brief description on the polymers’ physicochemical properties are
presented. Compared to existing related studies, the possible applica­
tions of the pure and impure fractions of these polymers are also dis­
cussed in this paper. Finally, this review summarizes real case examples
on how industries utilize cereal side streams.
2. Source and chemical structure of hemicelluloses from cereal
residues and by-products
It is important to identify the most abundant sources of hemi­
celluloses in cereal by-products, in order to obtain the most economical
and sustainable fractionation methods. The purity of each hemicellulose
fraction in the native cereal by-products should also be considered.
Cereals are staple food sources in human and animal diets. Many
different types of cereals are grown worldwide such as rice, wheat,
barley, oat and corn, and they share some structural similarities. During
processing of cereals, large amounts of residues (e.g., straw and corn
stover) and by-products (e.g., husk, bran, germ and endosperm) are
generated, with the majority being used for animal feeds, energy pro­
duction and fertilizers (Papageorgiou & Skendi, 2018). However, the
residues and by-products are major sources for the extraction of dietary
fibres, which are then utilized as supplementary ingredients in many
health-promoting products (Maphosa & Jideani, 2016; Dapčević-Had­
nađev et al., 2018). Cereal germs and endosperms are good sources for
hemicelluloses (Evers et al., 1999), however in the scope of this review,
A.N. Arzami et al. Food Research International 151 (2022) 110818

we will focus on hemicelluloses from cereal side streams such as bran,
straw and husk.
Hemicelluloses are heterogeneous polysaccharides including both
linear and branched molecules which are mainly built by pentose
(xylose and arabinose) and hexose units (glucose, galactose, mannose,
rhamnose, glucuronic and galactouronic acids). The main function of
hemicelluloses is to act as filling agents for the spaces between celluloses
and lignins, thus hemicelluloses in the cells are closely associated with
celluloses and lignins (Mudgil & Barak, 2013). Table 1 is a summary of
the amount of hemicelluloses compared to other lignocellulose materials
in different sources of cereal residuals and by-products. The summarized
data indicate that the content of lignocellulose materials markedly
varies according to the material types and sources. In most cereal re­
siduals and by-products, lignins are less abundant polymers than cellu­
loses and hemicelluloses. For the same cereal type, husk and straw
contain a higher amount of lignin than bran, with the exception of barley
bran which has the highest content of lignins (~21%, w/w) as compared
to barley husk (13.8–19.0%, w/w) and straw (6.3–9.0%, w/w) (Cruz
et al., 2000; Kim et al., 2008; Passoth & Sandgren, 2019). In all cereals,
the content of celluloses in straws and husks is much higher than that of
hemicelluloses. In contrast, the hemicellulose content in cereal brans is
more than double that of cellulose, making cereal brans an excellent
source for hemicellulose extraction and isolation. With the exclusion of
oat bran (~7.83%, w/w) (Olt et al., 2019), other cereal brans contain
>30% (w/w) hemicellulose. A high hemicellulose content is also found
in rye straw, barley husk, barley straw, corn cob and corn stover
(Table 1).
Based on current knowledge and structural variations, hemi­
celluloses can be categorized into four general classes: xyloglycans
(xylans), mannoglycans (mannans), mixed-linkage β-glucans and xylo­
glucans (Ebringerová et al., 2005). Nevertheless, the predominant and
research-attracting hemicellulose types in cereal residuals and by-
products are arabinoxylans (AX) and glucans (especially β-glucan), so
they are the main focus in this section.
2.1. Chemical structure of arabinoxylans and glucans
2.1.1. Arabinoxylans (AX)
AXs are constituted structurally by pentoses such as xylose and
arabinose. They are composed of a linear backbone chain of β(1,4)-
linked D-xylopyranosyl units (Xylp) to which most monomeric α-L-ara­
binofuranosyl units (Araf) are linked either at O-2 or O-3 positions
(monosubstitution) or at both O-2 and O-3 positions (disubstitution) of
the xylose units as side chain residues. In addition, Xylp can be
substituted with acetyl groups, D-glucopyranosyluronic acid (D-GlcA)
and its 4-O-methyl ether (4-O-Me-α-D-GlcA) (Bastos et al., 2018), and
forms ester linkages with ferulic acids which further form interactions
with β-glucan, lignin, cellulose, glucose or proteins (Zhang et al., 2014).
General chemical structure of AXs is illustrated in Fig. 2(a). However,
the structure of AXs varies between cereal tissue sources and species,
making definition of the universal structure of AXs impossible. For
example, non-lignified and low-lignified tissues are found in starchy
endosperms and brans, respectively while high-lignified tissues are
found in straws, husks and corn cobs. The most lignified tissues have the
highest diversity in the side chains of AXs, and thus AXs from cereal
brans (e.g., rice, corn and sorghum) have more complex side chains than
those from starchy cereals (e.g., wheat, rye and barley) (Izydorczyk &
Biliaderis, 2007). Moreover, it was found that the ratio of xylose and
arabinose (X/A) in AXs, which is an indicator to measure the branching
degree of AXs, varies according to cereal tissue sources such as wheat
endosperm (0.50–0.71), wheat bran (1.02–1.07), rye endosperm
(0.48–0.55) and corn bran (0.75–1.82) (Zhang et al., 2014). Depending
on the substitution degree in the molecule, AXs can be water soluble or
insoluble. AXs with high amounts of unsubstituted Xylp and high co­
valent linkages with lignin are water insoluble while those with high
content of Araf residues are easily solubilized in water (Bastos et al.,
2018).

Table 1 2.1.2. Glucans

Compositions (%, w/w) of lignocellulosic materials in cereal residues and by- Glucans are polysaccharides of D-glucopyranosyl units (Glcp), which
products. are different in anomeric configuration, position and distribution of
Sources Cellulose Hemicellulose Lignin References glycosidic bonds, molecular size, and type and degree of branching
Straw Wheat 32.6 22.6 16.8 Passoth and (Synytsya & Novak, 2014). Generally, glucans consist of a wide range of
Oat 31.0–35.0 20.0–26.0 10.0–15.0 Sandgren substances which are commonly found in nature including cellulose,
Barley 36.0–43.0 24.0–33.0 6.3–9.0 (2019) glycogen and starch. However, most of them do not interact with the
Rice 29.2–34.7 12.0–29.3 17.0–19.0
immune system. The immunomodulatory effect of glucans is attributed
Rye 37.9 36.9 17.6 Fang et al.
(2000)
to a chain of glucose residues linked by β-1,3-linkages, also known as
Sorghum 32.0–35.0 24.0–27.0 15.0–21.0 Passoth and β-glucans. β-glucans are rich in yeast, fungi, bacteria and cereal grains,
Sandgren and depending on the sources where β-glucans are extracted, the
(2019) chemical structure and bioactivities of β-glucans are different (Zhu et al.,
Bran Wheat 10.5–14.8 35.5–39.2 8.3–12.5 Spieß (2018)
2016). Unlike β-glucans derived from baker’s yeast which are composed
Wheat 10.15 30.35 5.46 Matavire
(2018) of β-1,3/1,6-glucans, cereal β-glucans are known as mixed-linkage (1,3/
Oat 3.4 11.22 Olt et al. (2019) 1,4)-β-glucans. In cereals, β-glucans are linear homopolysaccharides
Barley 23.0 32.7 21.4 Cruz et al. constructed by glucose molecules connected by β-(1,4) glycosidic and
(2000) β-(1,3) glycosidic linkages. In linear chain of β-glucans, β-(1,4) glyco­
Rice 15.8 31.3 11.6 Sunphorka
et al. (2012)
sidic linkages occurs in sequences of two or more, separated by a single
Rye 5.5 30.37 4.26 Matavire β-(1,3) glycosidic linkage. A general chemical structure of cereal
(2018) β-glucan is shown in Fig. 2b. The presence of β-(1,3) glycosidic linkages
Husk Wheat 36.0 18.0 16.0 Mirjalili et al. also gives the β-glucan molecule an irregular shape, flexibility and
(2011)
partial solubility in water due to their prevention of close packing of
Oat 48.4 16.1 16.2 Perruzza
(2010) molecules (Laroche & Michaud, 2007). β-glucans have many health
Barley 34.0 36.0 13.8–19.0 Kim et al. benefits and biological activities beyond their basic nutrition such as
(2008) lowering cholesterol, regulating blood glucose and enhancing the im­
Rice 28.7–35.6 12.0–29.3 15.4–20.0 Dagnino et al. mune system, thus they have been employed as nutraceutical products
(2013)
Rye 26.0 16.0 13.0 Fang et al.
and functional ingredients in many food applications (Ahmad et al.,
(2000) 2012).
Corn cob 33.7–41.2 31.9–36.0 6.1–15.9 Passoth and
Corn stover 35.0–39.6 16.8–35.0 7.0–18.4 Sandgren
(2019)

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Fig. 2. Basic chemical structure of (a): arabinoxylans - including a linear backbone chain of β(1,4)-linked D-xylopyranosyl residues (Xylp) to which most monomeric
α-L-arabinofuranose units (Araf) are linked, possibility of substitution by glucopyranosyluronic acid (GlcA) and formation of ester linkages with other molecules; and
the structure of arabinose and xylose were also given [adapted with permission from Zhang et al. (2014)], and (b) cereal β-glucan - indicating β(1,3)- and β(1,4)-
linkage [adapted with permission from Mejía et al. (2020)].

2.2. Arabinoxylans and glucans in cereal residues and by-products
Table 2 shows the amount of AXs and glucans in cereal residuals and
by-products, which is summarized from numerous research studies. The
summarized data indicate that these materials are great sources for the
extraction and/or isolation of AXs and glucans. However, most glucans
in cereal straws and husks are β-1,4-D-glucan chains which are the
construction units of celluloses, and do not have as much biological
functionality as β-glucans which are classified as hemicellulosic com­
ponents. This, together with low protein and starch content means that
cereal straws and husks are considered non-food biomass, and are
generally used for agricultural amendments, energy production, envi­
ronmental adsorbents and construction materials. Almost no β-glucan
isolation was reported for cereal husks and straws. Unlike cereal husks
and straws, cereal brans are excellent sources for β-glucan production,
especially oat and barley brans (Kerckhoffs et al., 2003; Zheng et al.,
2011). β-glucan content in wheat and rye brans are much lower with at
2% (w/w) (Phantuwong et al., 2017; Roye et al., 2020) while that in rice
and corn brans are extremely low with <0.2% (w/w) (Roye et al., 2020).
Cereal brans are also good sources of AXs, especially corn bran (Table 2).
Oat and rice brans have the lowest amount of AXs among cereal brans.
Barley is a unique material whose bran, husk and straw contain high
concentration of AXs. A relatively high amount of AXs can be found in
soybean husk and corn straw. Therefore, selection of cereal residues and
by-products for hemicellulose extraction and/or isolation is greatly
dependent on the targeted hemicellulose compounds. While some ma­
terials are excellent sources for isolation of either AXs or β-glucans,
others are suitable for production of both AXs and β-glucans. Also, a
combination of various selected cereal residues and by-products allows
the extraction of a more desirable mixture of hemicellulose compounds.
3. Extraction, purification and feasibility to upscale
In this section, fundamentals of general techniques for extraction and

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Table 2 celluloses, hemicelluloses and lignins are tightly cross-linked together

Amounts (%, dry weight) of arabinoxylans and glucans in cereal residues and by- mainly via ether bonds, ester bonds and hydrogen bonds to form a very
products. complex structure (Harmsen et al., 2010). This property, along with
Sources Arabinoxylans Glucans References limited water solubility makes extraction of hemicelluloses by using
(β-glucans)* only water relatively ineffective. Therefore, chemicals such as alkali and
Bran Barley 19.0–21.4a (6.15–7.58) Zheng et al. (2011) acid solutions, enzymes and mechanical-assisted treatments are
Oat 3.0a (5.4–8.5) Kerckhoffs et al. required to break the cross-linkages and modify the biomass structure,
(2003) facilitating the release of hemicelluloses from the complex matrix of cell
Rice 4.8–5.1a (0.04–0.21) Phantuwong et al.
walls. Currently, there are four main groups of extraction methods, as
(2017)
Wheat 18.0–24.0 b
(2.1) Roye et al. (2020) indicated in Fig. 3 (Zhang et al., 2014). Water extraction can be done at
Rye 12.0–18.0b (2.9) either low or high temperatures. At temperatures below 100 ◦ C, biomass
Corn 27.2–29.9a (0.1) is stirred or refluxed with water for a certain time period (approximately
Husk Barley 19.0–20.0b 37–40 Linde et al. (2006) 24 h), by which hemicelluloses solubilized into water are extracted. Low
Oat 3.5a 37.10 Romaní et al. (2016)
Rice 8.4–9.2a 34.2 Szulczyk (2007)
temperatures can preserve the native state of extracted hemicelluloses
Wheat NR 38.2 but is unable to break the cross-linkages between lignocellulose mate­
Soybean 13.1a NR rials, leading to low extraction yield and long extraction time (Zhang
Straw Barley 11.0–14.0b 33.6 Kim et al. (2008) et al., 2014). At high temperatures (>100 ◦ C) and pressures the
Oat NR 32.1 Perruzza (2010)
extraction process is more rapid and results in an increased extraction
Rice 11.0–18.3c 34.1 Dagnino et al. (2013)
Wheat NR 30.4 Momayez et al. yield. This technique is also known as hydrothermal treatment, hydro­
(2019) thermolysis, aqueous fractionation, solvolysis, aquasolv, or supercritical
Rye NR 33.12 Sun and Cheng (2005) water treatments depending on extraction temperature and pressure
Corn 27.0–30.0b 40.9 Szulczyk (2007) levels. For hydrothermal treatment at 160–200 ◦ C and 4–15 MPa (e.g.,
Corn cob 12.8d 41.6 Fan et al. (2014)
autohydrolysis), compressed hot water molecules penetrate into the
*Data in the brackets are the amount of β-glucans; aZhang et al. (2014), bBastos material matrix to hydrate and depolymerize hemicelluloses via
et al. (2018), cJaichakan et al. (2019), dEgüés et al. (2014); References for glucan hydronium-catalyzed reactions, and experience autoionization to form
content were in the last column; NR: Not reported. acidic hydronium ions which initiate the hemicellulose hydrolysis
(Bastos et al., 2018). Hydrothermal treatment can be executed as steam
purification of hemicelluloses from lignocellulosic biomass are firstly explosion in which high-pressure saturated water is injected into a
introduced. Details of these extraction and purification techniques have reactor filled with biomass, during which temperature can rise to
been reported elsewhere (Zhang et al., 2014; Bastos et al., 2018; Peng 160–240 ◦ C. After pressurizing for a short time period (seconds to mi­
et al., 2012; Skendi et al., 2020). Then, their applications to extract and nutes), the pressure is suddenly released, leading to explosive decom­
purify AXs and β-glucans from cereal residues and by-products are dis­ position of the materials causing disruption of complex matrix of cell
cussed. Hereon the term “biomass” is used to refer to to-be-extracted walls (Harmsen et al., 2010). Despite high extraction efficiency and
materials. environmentally-safe, hydrothermal treatments can cause the degrada­
tion and damage to the extracted hemicelluloses.
The most commonly-used chemicals for extraction of hemicelluloses
3.1. Fundamentals of extraction and purification processes for are alkali solutions such as NaOH, KOH, Ba(OH)2, Ca(OH)2 and NH4OH.
hemicelluloses from cereal residues and by-products Under alkali conditions, hydroxyl (OH− ) ions disrupt intermolecular
hydrogen bonds between celluloses and hemicelluloses and ester link­
3.1.1. Extraction processes ages, promoting hemicellulose solubilization. When Ba(OH)2 solution is
In cereal residues and by-products, lignocellulosic materials such as

Fig. 3. Extraction techniques for hemicelluloses from lignocellulosic materials.

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used as the extraction environment Ba2+ ions can form specific in­ Table 3
teractions with hemicelluloses, facilitating their extractability. In the Main pros and cons of the extraction techniques.
extraction of AXs, under alkaline conditions, uronic acid residues change Extraction Pros Cons
to negatively charge form, resulting in an increased repulsion force methods
between the different molecules and subsequently improved extract­ Water – Environmentally-friendly – Low extraction yield and long
ability (Zhang et al., 2014). Other chemicals that can be used to extract – Preservation of native treatment time, especially
hemicelluloses are inorganic acids (HCl and H2SO4) and organic acids structure of extracted extraction at low
(acetic and formic acid). Unlike alkalis, acids hydrolyze the glycosidic molecules (extraction at temperatures
temperatures below100◦ C) – Possibility of hydrolysis and/
linkages during treatment, resulting in degradation of hemicelluloses to – Low cost or degradation of extracted
smaller molecular weight compounds (oligo- and mono-saccharides), – Relatively high extraction components at high
and thus low extraction yield (Zhang et al., 2014). In addition, other yield at high temperatures extraction temperatures and
organic solvents such as H2O2 and NaClO2 are also employed for and pressures pressures
Chemicals – Highly efficient treatment – Not environmentally-friendly
hemicellulose extraction due to their ability to oxidize lignin and cleave
– High cost
cross-linked bonds, promoting the dissolution of lignins and hemi­ – Operational safety issues
celluloses (Harmsen et al., 2010). Limitations of chemical extraction – High hydrolysis degree of
includes high cost, safety and adverse environmental impacts (Bastos extracted components and
et al., 2018). high possibility of breaking
down functional groups
With extraction efficiency considered, enzyme extraction is the most Enzymes – Environmentally friendly – High cost
environmentally-safe hemicellulose extraction technique. Depending on most – Requirement of additional
target hemicelluloses, a specific enzyme is used to selectively depoly­ – Less effect on functional treatment steps to stop
merize water insoluble hemicelluloses, and thus render them both sol­ groups and controlled enzyme activities
degradation of extracted
uble and extractable (such as endo-β-(1,4)-xylanases can be used for AX
molecules
extraction). However, the complex structure of lignocellulosic materials – Relatively high efficiency
and presence of some enzyme inhibitors which possibly hinder the hy­ treatment (but lower than
drolysis of enzymes lead to low extraction yield as compared to chemical chemical approach)
techniques. A mixture of various enzymes is an alternative approach Mechanicals – Environmentally-friendly – Special instrument withstand
– Short treatment time high temperatures and
typically employed to improve extraction yield (Zhang et al., 2014).
– Highly efficient treatment pressures
Mechanical extraction techniques including ultrasound, microwave and – Uncontrolled hydrolysis
extrusion are often used as pre-treatment methods and in combination degree and/or degradation of
with water and chemical techniques to improve extraction efficiency of extracted molecules
hemicelluloses. The implosion of the cavitation bubbles by ultrasound
radiation causes microfractures on the surface of lignocellulosic mate­
purification steps involve the treating of biomass with hot aqueous
rials, enhancing the rate of diffusion and mass transfer during extraction
alcohol, isopropanol and petroleum ether to deactivate endogenous
process. Meanwhile, in microwave-assistant extraction, a rapid heating
enzymes which cause the degradation of target hemicelluloses (e.g.
of lignocellulosic materials via electromagnetic radiation allows
β-glucanase for β-glucan or xylases for xylan), and to eliminate lipids,
extraction time to be shortened while significantly lowering the amount
free sugars, amino acids, small proteins and some phenolic compounds.
of solvent required. For extrusion-assisted extraction method, a twin-
However, the endogenous enzymes are effectively destroyed under
screw extruder in which the extrusion and cooking steps happen
strong alkaline (e.g., 1 N NaOH) or acidic extraction conditions (Lazar­
simultaneously is typically used to induce many physical and chemical
idou et al., 2007).
transformations of lignocellulosic materials in a single step (Bastos et al.,
Once extracted, hemicelluloses are a mixture of various poly­
2018; Peng et al., 2012; Zhang et al., 2014). Table 3 provides a summary
saccharides with different structure and properties, thus they need to be
of the pros and cons of different extraction techniques for hemi­
further purified to get highly homogeneous hemicellulose fractions
celluloses. Each extraction technique has its own operating mechanism
(Peng et al., 2012). Typically, the residue starches are removed simul­
and characteristics, and affect the properties of extracted hemicelluloses
taneously or successively with extraction via the incubation of extracted
differently. Thus, to maximize the extraction yield of hemicelluloses,
hemicelluloses with amylolytic enzymes such as thermostable α-amylase
which is the main focus of current research studies, a combination of two
(e.g., Termamyl®). Meanwhile, the residue proteins are eliminated by
or more extraction techniques such as mechanical treatment with either
either using proteolytic enzymes (e.g., pancreatin) and adsorption ma­
water extraction or chemical extraction, or water extraction with en­
terials (e.g., celite), or adjusting pH to the protein isoelectric point (pH
zymes is preferred, and selection of extraction technique is dependent on
4.5) to precipitate proteins (with or without using flocculants) which are
desirable properties and types of extracted hemicelluloses and corre­
then separated by centrifugation (Lazaridou et al., 2007). In order to get
sponding their applications (Details in Section 5).
the hemicellulose fractions with desired purity of target hemicelluloses
(e.g., AXs and β-glucans), the extracted hemicelluloses still require
3.1.2. Purification processes
further purification. This is a very complex and tedious procedure as it
Along with lignocellulosic materials, other minor components such
includes multiple steps of fractionation and purification. Generally, this
as starches, proteins, lipids and minerals also co-exist in biomass in
can be done via either precipitation with organic solvents (e.g., ethanol,
either a free state or bound with lignocellulosic materials (Raven et al.,
methanol and acetone), ammonium sulfate, iodine complex formation
1999). They should be removed either before or after the extraction
and supercritical carbon dioxide; column chromatography; or mem­
stage to maximize the extraction yield and the purity of extracted
branes (Peng et al., 2012). The purification technique and its operating
hemicelluloses. Typically, the first pre-treatment step in hemicellulose
conditions determine the composition, yield and purity of hemi­
extraction involves the reduction of the size of biomass by chopping,
celluloses. A general procedure for extraction of various hemicellulose
milling or grinding to achieve as narrowest size distribution as possible.
molecules from cereal biomass is illustrated in Fig. 4. Depending on
This significantly increases the surface area to volume ratio, and thus
sources and characteristics of biomass, as well as desirable properties
facilitates the extraction process (Harmsen et al., 2010). The larger size
and applications of hemicelluloses, some steps can be omitted and
of biomass leads to the lower heat transfer, and consequently inadequate
optimal conditions for each step differ.
hydrolysis of interior materials due to low impregnation and solubili­
zation, causing low extraction yield (Carvalheiro et al., 2016). Other

6
A.N. Arzami et al.
Fig. 4. A flow chart of general extraction and purification procedure for hemicellulose materials from cereal residues and by-products. Descriptions in the dotted
rectangular boxes are further explanations for steps connected by dotted arrows.
3.2. Extraction and purification of arabinoxylans and β-glucans from
cereal residues and by-products
3.2.1. Arabinoxylans
AXs are found mostly in the outer layer and endosperm cell walls of
cereal grains, thus cereal brans are the most abundant sources for AX
isolation. However, straws and husks of several cereals such as rice,
barley and corn also contain a relatively high amount of AX (Table 2).
Therefore, AX extraction and purification attempts have extended
beyond cereal brans, and many studies on cereal straws and husks are
reported. In a review article published by Zhang et al. (2014), the effects
of different extraction and purification techniques on the yield and
properties of AXs from cereal by-products (e.g., bran, straw and hull of
wheat, oat, rice, rye, barley and corn) were well described. However,
most studies reported in Zhang’s review were about AX extraction
investigated at a laboratory scale. To avoid unnecessary repetition of
Zhang’s review and provide an insight into the possibility of scaling up
AX extraction and purification, the main focuses of this section are to
provide an update of recent studies and describe the possibility of AX
extraction and purification at larger scale.
A summary of recent laboratory and pilot scale studies about AX
extraction and purification from cereal residues and by-products is
shown in Table 4. Note, that the yield values were reported as the total
amount of extracted hemicelluloses to initial raw materials, thus they
appear relatively low. Similar to laboratory scale extraction, in the pilot
scale the use of chemicals such as NaOH and Na2CO3 to extract AXs from
rye and wheat brans resulted in a higher extraction yield and higher
purity of AX fractions than the use of either water (<100 ◦ C), endox­
ylanase enzyme, or combination of water and α-amylase enzyme
(Mansberger et al., 2014; Bender et al., 2017; Aguedo et al., 2014). In
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Food Research International 151 (2022) 110818
the bran residues discarded from the first extraction by either chemicals
or enzymes, there were still high amounts of bound AXs which could be
extracted by using other techniques which are different in extraction
mechanism to the first extraction approach. Bender et al. (2017) re­
ported that in a two-step extraction process in which soluble AXs were
firstly extracted by alkali solution, and the bound AXs in the residues
were subsequently extracted with xylanase enzymes (e.g., Pentopan
Mono, BG Viscoflow MG and Deltazym VR-XL), the extraction yield and
purity of extracted AX fractions increased from 3.85 and 43.92% (w/w)
in the first stage to 9.85 and 67.1% (w/w), respectively in the second
stage. A similar finding was also reported for the pilot scale extraction of
AX from wheat bran, further extraction of the solid residues, after
enzyme extraction, with either hydrothermal (180 ◦ C/3 min) or alkali
(0.44 M NaOH) could obtain an additional extraction yield of 15.6 or
19.3%, respectively. These studies indicated the importance of the
combination of several extraction techniques with different extraction
mechanisms to extract both free (soluble) and bound (insoluble) AXs. A
high effectiveness when combining several extraction techniques in the
enhancement of yield and purity was also reported for destarched wheat
bran extracted by hydrothermal (180 ◦ C/10 min) and heterogeneous
catalysts (RuCl3/Al-MCM-48) (Sánchez-Bastardo et al., 2017). Similarly,
it was reported that the use of enzymes in combination (e.g., xylanase
and cellulase) to extract AX from deoil, destarch and deprotein corn bran
enabled a very high extraction yield (40.73%) and purity (75.88%),
which were higher than those obtained by chemical extraction (Ma
et al., 2020).
Purification of the extracted AX fractions reduces the final yield and
increases the production cost, therefore depending on the final appli­
cations of extracted AX fractions, the extraction yield and purity may
need to be compromised. In small scale extraction, purification is
A.N. Arzami et al. Food Research International 151 (2022) 110818

Table 4
A summary of recent studies on arabinoxylan extraction and isolation from cereal residues and by-products.
Sources Pre-treatment Extraction Fractionation and Yield Extracted hemicellulose References
purification (%)a compositions*
Scale Method and conditions

Corn bran – Grinning (<0.8 Lab – Xylanase & cellulase – Centrifugation 40.73 AX (75.88) Ma et al. (2020)
mm) (1:30) – Membrane filtration
– Deoil (hexane) – Freeze drying
– Destarched
(termamyl &
fungamyl)
– Deproteins
(proteases)
Wheat – 80% ethanol Lab – Water (45 ◦ C) – Destarch (α-amylase) N.A – 50% (NH₄)₂SO₄: AX (41.5), Malunga et al. (2017)
bran – Deprotein (celite and β-Gl (12.5), Pr (16.9) &
clay) ferulic acid (16.78)
– 50 & 75% (NH₄)₂SO₄ – 75% (NH₄)₂SO₄: AX (66.6),
precipitation β-Gl (15.7), Pr (11.3) &
– Dialysis ferulic acid (4.34)
– Freeze drying
– Grinning (<0.8 Lab – 0.2 M NaOH (40 ◦ C/4h) – 4 M HCl, pH 4.0 7.68 Total carbohydrate (75.16), Liu et al. (2020)
mm) (remove proteins) uronic acid (3.46), Pr (6.3), St
– Cold ethanol (4.76) & As (0.34)
precipitation
– Dialysis
– Freeze drying
Above treatment + 2.29 Total carbohydrate (90.56),
sequential ethanol uronic acid (4.97), Pr (1.39),
precipitation (15, 20, St (0.13) & As (0.30)
40%)
– Grinning (<1.5 Lab – 0.25 M NaOH – 4 M HCl, pH 4.0 3.7–5.6 AX (68.28–72.08), Pr Wang et al. (2019)
mm) (remove proteins) (6.09–8.59) & As (6.19–12.08)
– Starch removing – Ethanol precipitation
(α-amylase & – Freeze drying
water wash)
– Defat (methanol Lab – Subcritical water – Dialysis 46.7 AX (29.5), β-Gl (68.8) & St Rudjito et al. (2019)
& chloroform) extraction – Membrane filtration (<1)
– Destarch – Freeze drying
(α-amylase, 95%
ethanol and water
washing)
Pilot 29.0–32.6 AX (68.1–73.3), β-Gl (16) & St
(<1)
Wheat – Straw: grinding Large – Twin-screw extruder – Alcoholic precipitation 4.7–6.2 Ara (4.8–6.4), Xyl (10.1–17.8), Jacquemin, Mogni,
straw (<6 mm) with NaOH Gal (0.8–1.1), Glcp Zeitoun, Guinot,
and – Bran: H2O (22.5–42.1), Man (0.3–0.4), Sablayrolles, Saulnier,
bran (40 ◦ C/15 min) Xyl/Ara (2.1–2.8), Pr and Pontalier (2015a)
mixture (12.9–18.8) & As (3.5–9.4)
– Ultrafiltration 4.9–5 Ara (4.4–6.6), Xyl (9.9–17.6),
– Alcoholic precipitation Gal (0.7–1.2), Glcp
(20.7–41.8), Man (0.3–0.4),
Xyl/Ara (2.2–2.7), Pr
(15.6–18.8) & As (3.6–5.5)
– Ultrafiltration 4.3–4.6 Ara (5.1–7.1), Xyl (11–18.8),
– Anion-exchange Gal (0.8–1.2), Glcp
chromatography (22.9–44.5), Man (0.3–0.4),
– Alcoholic precipitation Xyl/Ara (2.2–2.6), Pr (37.0) &
As (5.9)
– Straw: grinding – Alcoholic precipitation 8.2 Ara (6.3), Xyl (12.5), Gal (1.0),
(<6 mm) Glcp (11.7), Man (0.2), Xyl/
– Bran: BAN 480L Ara (2.0), Pr (37.0) & As (5.9)
enzyme + H2O
wash (40 ◦ C/15
min)
– Ultrafiltration 11.7 Ara (4.9), Xyl (10.4), Gal (0.9),
– Alcoholic precipitation Glcp (10.4), Man (0.0), Xyl/
Ara (2.1), Pr (39.3) & As (6.3)
– Ultrafiltration 7.6 Ara (5.7), Xyl (11.5), Gal (1.0),
– Anion-exchange Glcp (11.4), Man (0.2), Xyl/
chromatography Ara (2.0), Pr (38.2) & As (7.8)
– Alcoholic precipitation
Wheat – H2O wash (95 ◦ C/ Semi- – Endoxylanase enzyme – Ultrafiltration (10 kDa) 4.3 Ara (27.8), Xyl (41.1), Gal Aguedo et al. (2014)
bran 10 min) pilot (2.4), Glcp (6.1), Man (0.2) &
– Drying (100 ◦ C/ Ara/Xyl (0.68)
24 h)
– Membranes (100 kDa) 4.2 Ara (29.1), Xyl (40.1), Gal
(3.2), Glcp (5.3), Man (0.3) &
Ara/Xyl (0.73)
(continued on next page)

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Table 4 (continued )
Sources Pre-treatment Extraction Fractionation and Yield Extracted hemicellulose References
purification (%)a compositions*
Scale Method and conditions

– 0.44 M NaOH (pH 12.5,
80 ◦ C/15 h)
– Fungamyl Lab – Hydrothermal method
assisted by
heterogeneous catalysts
(RuCl3/Al-MCM-48)
Rye bran – Oven (90 ◦ C/30 Pilot – H2O (65 ◦ C)
min)
– 0.17 M Na2CO3
– 0.17 M Ca(OH)2
Lab – H2O & α-amylase
Pilot – H2O & α-amylase
– Subtilisin & bacillolysin
– 0.25 M NaOH, 20 ◦ C
– Corolase PP
– 0.17 M NaOH, 30 ◦ C
– Corolase PP & 7089
– Centrifugation (4400 20.8 Ara (27.8), Xyl (29.7), Gal
rpm/15 min) and ultra- (2.0), Glcp (2.9), Man (0.1) &
dia-filtration (100 kDa) Ara/Xyl (0.94)
– Centrifugation 29 N.A Sánchez-Bastardo
– Filtration et al. (2017)
– Thermamyl and AGM 2.92 AX (38.57), β-Gl (6.40), Pr Bender et al. (2017)
enzymes, and neutrase (10.99), St (2.22) & gluten
– Alcalase (99.25 ppm)
– Gluten hydrolysis
– Ultra/dia-filtration (8
kDa)
3.81 AX (41.8), β-Gl (7.59), Pr
(12.46), St (0.98) & gluten
(31.11 ppm)
3.85 AX (43.92), β-Gl (0.43), Pr
(14.04), St (0.08) & gluten
(6.08 ppm)
– 65% ethanol 1.3 AX (60.3), ArGa (4.2), GM Mansberger et al.
precipitation (0.9), Glcp (2.9) & Pr (6.2) (2014)
– Freeze dying
– Ultra/dia-filtration (8 1.2 AX (38.5), ArGa (2.6), GM
kDa) (9.4), Glcp (22.2) & Pr (16.7)
– Freeze dying
– Ultra/dia-filtration (8 0.9 AX (85.0), ArGa (3.0), GM
kDa) (2.0), Glcp (2.0) & Pr (7.0)
– 65% ethanol
precipitation
– Freeze dying
– Ultra/dia-filtration (8 1.9 AX (68.9), ArGa (3.0), M (1.3),
kDa) Glcp (12.7) & Pr (15.4)
– Freeze dying
2.5 AX (62.2), ArGa (3.0), GM
(1.6), Glcp (9.9) & Pr (25.4)

*The figure in the brackets are percentage of corresponding hemicellulose components; aYield as total hemicelluloses extracted from initial raw material; AX: ara­
binoxylan; β-Gl: β-glucan;Pr: Protein; As: Ash; St: Starch; Ara: Arabinose; Xyl: Xylose; Gal: galactose; Glcp: glucose in pyranosyl form; Man: mannose; ArGa: ara­
binogalactan; GM: glucomannan.

typically done by precipitation of extracted AX fraction with (NH₄)₂SO₄
and ethanol, and degree of purity was increased by increasing their
concentrations and washing time (Malunga et al., 2017; Liu et al., 2020;
Mansberger et al., 2014). However, these techniques are not effective to
apply at a larger scale. To obtain effective precipitation of AX, it requires
the use of at least three volumes of (NH₄)₂SO₄ or ethanol per volume of
extracted AX fraction, leading to high cost and generation of a huge
amount of waste. Currently, environmentally-friendly purification
methods, which are easily scaled up, are not sufficiently effective for AX
fraction purification. Jacquemin et al. (2015b) reported that the com­
bination of ultrafiltration and anion exchange chromatography for large
scale purification of AX fractions extracted from wheat bran and straw
mixture via a twin-screw extruder resulted in a much lower purity than
ethanol precipitation. Low effectiveness of environmentally-friendly
purification methods is possibly due to the high content of salts,
starches, proteins and lignins in the extracted AX fractions. Therefore, to
achieve high AX fraction purity, these components should be removed
during extraction. Wang et al. (2019) reported that removal of starch in
wheat bran by α-amylase prior to alkali extraction markedly enhanced
the purity of extracted AX fractions. Rudjito et al. (2019) reported that in
water supercritical extraction, destarching was a critical pretreatment
step in both laboratory and pilot scale AX extraction from wheat bran, to
obtain high AX fraction purity. Similarly, Jacquemin et al. (2015a)
stated that starch removal from wheat bran prior to extraction was very
important for large scale extraction of AX from the wheat bran and straw
mixture by twin-screw extruder. The presence of starch reduced the
extraction efficiency and caused fouling of the ultrafiltration membrane.
The studies on large scale AX production from cereal residues and by-
products indicated that environmentally-friendly extraction and
purification techniques still need further investigation and optimization
to attain high yield and high purity of AX fractions to extend the ap­
plications of extracted AX fractions as well as to replace chemical
approaches.
Based on the studies reported in Table 5 and those reported in
Zhang’s review, it can be concluded that extraction of hemicelluloses
from cereal residues and by-products using water at temperatures below
100 ◦ C is not economical to up-scale due to very low extraction yield and
long extraction time. Meanwhile, despite the highest extraction yield
among available extraction methods, chemical extraction with alkali
and acids is also not suitable and economical for industrial/large pro­
duction because of high chemical cost that are also severely hazardous to
instruments and the environment, which requires extreme operating
caution and high costs to deal with wasted chemicals. In addition,
chemical extraction causes extensive structural degradation of extracted
AX fractions which changes their functional properties and ultimately
applications. Current studies and future exploration on AX extraction
tend to employ environmentally-friendly techniques for extractions (e.
g., hydrothermal treatment, enzymes, twin-screw extrusion and super­
critical extraction) and purification (e.g., dialysis, membrane or anion
exchange) combined with diluted alkali and acids. These techniques are
feasible for large scale AX production (Bastos et al., 2018).
3.2.2. β-glucans
Many products made of β-glucan powders are available commer­
cially, and most of them originate from cereal grains, seaweeds, fungi
and yeasts. Although many excellent reviews have reported extraction
and/or purification of β-glucans from cereal grains, and their structure
and functional properties (Hu, Zhao, Zhao, & Zheng, 2015; Lazaridou

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Table 5
A summary of reported results about extraction of β-glucan from cereal residues and by-products.
Sources Pre-treatment Extraction Fractionation, Yield (%) Extracted hemicelluloses References
purification and characteristics*
Scale Method and conditions
drying

Barley – Grinding (<1 Lab 20% Na2CO3 (45 ◦ C/30 – 2 M HCl 52-55a β-Gl (71.9), Pen (2.9), As (3.9), Bhatty (1993)
bran mm) min) – 1% Termamyl Pr (0.5) & St (0.4)
– 50% ethanol
precipitation
– Freeze drying
H2O (45–90 ◦ C) 40a β-Gl (74.9), Pen (1.9), As (6.8),
Pr (0.6) & St (1.0)
a
4% NaOH (Troom/18 h) 81 β-Gl (59.7), Pen (10.9), As
(12.6), Pr (0.2) & St (0.4)
Oat bran 20% Na2CO3 (45 ◦ C/30 61a β-Gl (79.7), Pen (1.1), As (3.7),
min) Pr (0.5) & St (1.4)
Barley – Grinding Lab 2 N NaOH 77a β-Gl (76.0), Pen (10.7), As (1.2), Bhatty (1995)
bran (<0.5 mm) Pr (0.6), St (0.7) & ether extract
(1.0)
Pilot 0.25 N NaOH 73a β-Gl (49.8), Pen (12.6), As
(15.7), Pr (4.6), St (2.9) & ether
extract (3.8)
Oat bran Lab 2 N NaOH 87-95a β-Gl (79.1), Pen (7.7), As (1.7),
Pr (1.3), St (2.3) & ether extract
(1.2)
Rice – None Lab H2O (37 ◦ C/20 h) – α-amylase 0.03–0.08b Not determined Neethi and Anie
bran – 60% ethanol (2017)
precipitation
– Freeze drying
Oat bran – Grinding Lab H2O (47 ◦ C/3h) – Termamyl 28a β-Gl (54) Ibrahim and
(<0.8 mm) – Ethanol Selezneva (2017)
precipitation
– Freeze drying
H2O (47 ◦ C/3h) & – Ethanol 3.1a
ultrasound precipitation
– Freeze drying
H2O (100 ◦ C/3h) +/- 50b (without
amylase amylase) & 90b (with
amylase)
H2O (120 ◦ C/10 min) +/- 53b (without
amylase amylase) & 71b (with
amylase)
Combine H2O (100 ◦ C/3h) 76b
& amylase
Combine H2O (100 ◦ C/3h) 73b
& amylase, and pancreatin
– 80% ethanol Lab – 1 M NaOH (45 ◦ C/2h) – 80% ethanol 3.14–4.4a β-Gl (90) Immerstrand et al.
(25 ◦ C/2h) – Acid citric, pH 3.5 precipitation (2009)
– Hot air drying
Barley – Grinding Lab Hydrothermal (70 ◦ C/9 – 1% α-amylase 16.39a Not determined Du et al. (2014b)
bran (<0.42 mm) min, 10 MPa & 4 cycles) and – 0.5% protease
– 80% ethanol celite – Anhydrous ethanol
(85 ◦ C) precipitation
– Air drying 40 ◦ C
Ultrasound (50 ◦ C, 100 W & 0.3a
1 h)
Microwave (800 W, 40 Hz & 0.3a
2 min)
H2O reflux (100 ◦ C/2h) 2.2a

*The bracketed figures are percentage of corresponding hemicellulose components; Yield as total hemicelluloses extracted by initial raw material; bYield as total
a

hemicelluloses extracted by original hemicelluloses content in raw material; β-Gl: β-glucan; Pr: Protein; As: Ash; St: Starch; Pen: Pentosan.

et al., 2007; Mejía et al., 2020), little attention has been dedicated to
extraction and/or purification of β-glucans from cereal residues and by-
products. As indicated in Table 2, cereal brans are very rich in β-glucans,
particularly those of barley and oat. Thus, not surprisingly most studies
focus on β-glucan extraction from oat and barley brans. Theoretically,
the extraction and purification techniques described in Section 3.1 and
those applied for AXs (Section 3.2.1) can be applied to extract and purify
β-glucans from cereal brans. However, as compared to AXs, extraction
and purification of β-glucans from cereal residues and by-products are
less attractive to researchers and industries, and only one study about
β-glucan extraction from cereal side streams in large scale can be found
in the literature and none from recent decades. Bhatty (1995) reported
that in pilot extraction of β-glucan from barley bran using NaOH, despite
high extraction yield (~73%), the pilot extracted β-glucan fractions
contained only 50% β-glucans due to high viscosity of the extracts pre­
venting the post-extraction purification process from operating
properly.
Although wheat and rye brans contain a relatively high amount of
β-glucan, studies about β-glucan extraction and purification from them
are limited. Cereal brans also have a very high content of AXs, and thus it
is currently more economical and efficient to use them for production of
AXs and/or dietary fibre which contains both AXs and β-glucans, instead
of only β-glucans. A summary of the studies on β-glucan extraction from
cereal brans is shown in Table 5. As aforementioned, water at temper­
atures below 100 ◦ C extracts only water easily-solubilized hemicellulose
molecules, leading to low extraction yield. Refluxing of rice and barley

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A.N. Arzami et al.
brans with water (<100 ◦ C) was shown to extract a very small amount of
β-glucans (Neethi & Anie, 2017; Du, Zhu, & Xu, 2014). Although
extraction yield of β-glucans from cereal brans increased with increasing
water temperatures and pressures (Ibrahim & Selezneva, 2017), the
yield from water extraction was much lower than that obtained by using
chemicals (Bhatty, 1993, 1995). Unlike generally assumed that ultra­
sound increases the diffusion of molecules at the solid–liquid boundary
and thus improves extraction yield, it was reported that β-glucan
extraction yield from barley bran using ultrasound (50 ◦ C, 100 W and 1
h) and microwave (800 W, 40 Hz and 2 min) was markedly low (Du,
Zhu, & Xu, 2014); and that combination of ultrasound with water
reflushing noticeably lowered the extraction yield (Ibrahim & Selez­
neva, 2017). Similar to AXs, the combination of different extraction and
purification approaches together with pre-treament methods to remove
other components such as proteins, lipid and starch will help to increase
the extraction yield and purity of extracted β-glucan fraction from cereal
side streams. Combination of 1 M NaOH (45 ◦ C for 2 h) and citric acid
(pH 3.5) for β-glucan extraction from oat bran with pre-treatment of raw
materials with 80% ethanol (25 ◦ C for 2 h) to defat, lead to extracted
fractions containing 90% β-glucan (Immerstrand et al., 2009).
All extraction and purification techniques of hemicelluloses from
cereal side streams described above can be considered “wet approaches”
as they require a large amount of water and subsequent energy for
dehydration, leading to high production cost and waste. Another tech­
nique to extract hemicellulose-enriched fractions from cereal side
streams, known as “dry fractionation”, includes three main steps: milling,
electrostatic separation and sieving, has been reported (Sibakov et al.,
2014; Wang et al., 2015; Zhang et al., 2019). After milled, wheat bran
particles are conveyed by N2 gas into a charging tube. Collisions be­
tween the tube wall and wheat bran particles gives the particles different
charges, depending on their histological and triboelectric charging
characteristics. Typically, the particles from the aleurone layer and the
endosperm will have a positive charge while particles from the pericarp
(rich in AXs) will have a negative charge. As wheat bran particles are
moved into an electrostatic separator, they are separated by applying
electric field. The AX-rich fractions can be subsequently sieved to
improve the purity by removing proteins and starches. Defat of raw
materials prior to electrostatic separation is also required to enhance the
enrichment of hemicellulose fractions. This approach allowed to create
AX fractions containing up to 56% AX from wheat bran (Wang et al.,
2015; Zhang et al., 2019), and β-glucan fractions containing 25% and
48.4–56.2% β-glucan from non-defatted and defatted oat bran, respec­
tively (Sibakov et al., 2014). It was also reported the defatted and pin-
milled oat brans were successfully separated into five β-glucan frac­
tions containing from 4.3% to 24% β-glucan by air classification (Ste­
venson et al., 2008). The dry fractionation technique not only requires
little energy and preserves the native state and functionality of AX
components, but also enables to produce hemicellulose fractions with
different enrichments allowing for different applications of extracted
hemicellulose fractions to be formulated. Therefore, the dry fraction­
ation technique has high potential to scale up for the fractionation of
hemicellulose-rich fractions from cereal side streams.
4. Physicochemical properties of cereal by-product
hemicelluloses
The solubility and solution properties of AX and β-glucan are vital to
determine their end-use applications. The physicochemical properties of
these hemicelluloses were affected by the chemical nature of their
components and also different processing parameters to extract them
(Bunzel et al., 2001; Schneeman, 1998). The behavior of these hemi­
celluloses in solutions have been discussed thoroughly in many review
articles (Biliaderis & Izydorczyk, 2006; Izydorczyk & Dexter, 2008;
Lazaridou et al., 2007; Zhang et al., 2014). Furthermore, Zhang et al.
(2014) discussed in detail the structural modification of AX after
different extraction and purification methods. In this review, the
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properties of cereal by-product hemicelluloses (AX and β-glucan) will be
discussed briefly. This section will give insight on the influence of
fractionation methods on the physicochemical properties of cereal by-
product hemicelluloses and whether purification is needed to achieve
promising physicochemical characteristics.
4.1. Solubility
The water solubility of cereal by-product hemicelluloses is affected
by structural features such as molecular size, chain length, the presence
and distribution of side-chain groups and/or covalent linkages (Saulnier
et al., 2007). In general, AXs are partly soluble and can be obtained in
water-extractable (WEAX) and water un-extractable (WUAX) forms.
Depending on the cereal varieties and processing methods, the amount
of WEAX and WUAX may vary. However, in all cases, the amount of
WUAX in cereal by-products is much higher than WEAX (e.g., only 5.4%
of WEAX obtained from total wheat bran AX) (Marcotuli et al., 2016;
Zhang et al., 2014). As mentioned in Section 2.2.1 (a) in this review, the
presence of higher A/X substitutes along the xylan backbone can in­
crease the water solubility of AX. Removal of arabinose substituents
using α-L-arabinofuranosidase can cause aggregation of the resulting
products into insoluble complexes (Andrewartha et al., 1979). Although
WUAX has higher A/X substitution compared to WEAX, the existence of
a large number of covalently cross-linked diferulic bridges hinders the
solubility of WUAX (Bunzel et al., 2001; Saulnier et al., 2007).
The solubility of cereal by-products β-glucan is not only affected by
the molecular features, but also the overall architecture and composition
of the cell wall constituents (Izydorczyk & Dexter, 2008; Lazaridou
et al., 2007). A study by Gajdošová et al. (2007) showed that the content
of soluble β-glucans in oats and barley decreases from the endosperm to
the outer coat and also decreases with storage time. Higher ratios of
β-(1–4)/(1–3) glycosidic linkages and a higher ratio of cellotriosyl units
to cellotetraosyl units (DP3:DP4) decreased the solubility of cereal
β-glucans in water (Izydorczyk et al., 1998). Water soluble β-glucan have
an irregular overall shape caused by a large amount of β-(1–3) glycosidic
linkages arranged at irregular intervals. It is known that water can get in
between the straight chain of β-glucan polymers because of the kinks
produced by the β-(1–3) glycosidic linkages, thus, improving the poly­
mer’s solubility (Vasanthan & Temelli, 2008). The solubility and water
binding capacity of the insoluble part of cereal by-product hemi­
celluloses can be enhanced by using mechanical treatments (e.g. high-
speed homogenization, high-pressure homogenization, high intensity
sonication and extrusion cooking), varying temperature, chemical
treatments (acid or alkali) and enzymatic treatment. For example,
Petersson et al. (2013) reported, the soluble content of rye and wheat
bran increased after enzymatic treatments with different xylanases and
endoglucanases. In another study, Hu, Zhang, Adhikari, and Liu (2015)
discovered that the wheat bran swelling, solubility, cation exchange, oil-
holding and water-holding capacities increased significantly by using
high-pressure homogenization alone or in combination with sonication
treatments. Besides, Zhang et al. (2011) also reported an increase in oat
bran solubility and swelling capacity by using extrusion process.
4.2. Molar mass (MM)
The MM of cereal by-products AXs and β-glucans differs greatly
based on their genotypes, fractionation methods and experimental
methods used for molar mass determination (Biliaderis & Izydorczyk,
2006; Henrion et al., 2019; Zhang et al., 2014). Cereal by-product
hemicelluloses are heterogenous polysaccharides that do not have a
uniform molecular weight (Mw). Instead, they have an average molar
mass (Kivelä et al., 2010). In this section, some authors reported their
results as Mw, although the authors in this review find MM is a more
accurate descriptor of heterogenous hemicelluloses. Liu et al. (2020)
investigated the effect of mechanical, enzymatic and chemical treat­
ments on the molar mass degradation of wheat bran AX (MM = >600
A.N. Arzami et al.
kDa). According to the authors, all treatments decreased the molar mass
of the wheat bran AX (ultrasonication: MM = 600 kDa–100 kDa, xyla­
nase treatment: MM = 600 kDa–<100 kDa, and trifluoroacetic acid
treatment: MM = 300 kDa–<100 kDa). In another study, the Mw of AXs
in barley husks fractionated by four different methods (acid, alkali,
combination of acid and alkali, and enzyme) were 3.50 × 104–4.50 ×
104 g/mol (Höije et al., 2005). The Mw of other cereal AXs were as
follows: corn bran (Mw = 3.62 × 105 g/mol), sorghum bran (Mw = 3.42
× 105–3.63 × 105 g/mol), rice bran (Mw = 1.52 × 103–5.79 × 104 g/
mol) and rye bran (Mw = 2.32 × 105 g/mol) (Kale, Yadav, Hicks, &
Hanah, 2015; Sárossy et al., 2013; Yuwang et al., 2018). On the other
hand, the Mw of white wheat bran purified β-D-glucan (91.58%) treated
with alkali and ammonium sulphate [(NH4)2SO4] was 4.87 × 105 g/mol
with a high polydispersity index (I) of 1.65 (I = Mw/Mn) (Li, Cui, &
Kakuda, 2006). Different processing methods can decrease the molar
mass of cereal by-product hemicelluloses. Demuth et al. (2020) showed
that the Mw of wheat bran AX (4.03 × 105 g/mol) decreased with
extrusion (3.45 × 105 g/mol) and milling (1.34 × 105 g/mol) processes.
Van Craeyveld et al. (2009) also recorded similar observations when
optimization of ball milling processes reduces the molar mass of wheat
bran AX from 15 kDa to 5 kDa. Andersson et al. (2017) reported a slight
decrease in Mw of wheat bran and rye bran β-glucans after treatments
with several extrusion process parameters. The reduction in molar mass
increases the hemicelluloses solubility and affect its overall physico­
chemical properties which will be discussed further in Section 4.3.
4.3. Viscosity, gelation and rheological behavior
Water solubility, molar mass and polymer conformation are among
the determinants of viscosity, gelation and rheological behavior of
cereal by-product hemicelluloses (Kale, Yadav, Hicks, & Hanah, 2015).
Cereal by-product AXs and β-glucan are highly viscous in water (act as
random coils or semi-flexible coils in solutions) and able to form gels
under certain temperature and oxidative conditions (Cui & Wood, 2000;
Mäkelä et al., 2017; Niño-Medina et al., 2010; Tosh & Wood, 2003).
Roye et al. (2020) studied the viscosity of several endosperm depleted
cereal brans in their native form (mixtures of AX, β-glucan, protein,
cellulose, lipids and others). Based on their study, rye demonstrated
higher viscosity (7.33 mPa.s) compared to maize (1.36 mPa.s) and
wheat (1.33 mPa.s), probably due to the higher WEAX composition in
rye bran (1.4%). Viscosity of AXs is also related to shear rate. Rheo­
logically, AXs in solutions at low shear rate displayed Newtonian fluids
behavior (Izydorczyk & Biliaderis, 1992; Rieder et al., 2017). At high
shear, AXs solution showed shear thinning behaviour where the vis­
cosity decreased. Izydorczyk, Biliaderis, and Bushuk (1990) stated that
the gelation of wheat AXs under oxidative condition (addition of 0.11
PU/mL peroxidase and 0.2 ppm hydrogen peroxide) was attributed by
AX participation in the network. The elastic modulus (Ǵ ) increased
rapidly in the first phase of gelation followed by a slower rate of gelation
afterwards. On the other hand, the optimum temperature for acid-
hydrolyzed oat bran β-glucan to form gels is between 70 and 80 ◦ C
(Tosh & Wood, 2003). Mäkelä et al. (2017) found that both oxidized
(samples treated with 70 mM hydrogen peroxide and 1 mM ferrous
sulphate) and non-oxidized oat and barley β-glucan gelled at 37 ◦ C and
57 ◦ C respectively. In another study, Roye et al. (2020) showed that
endosperm depleted oat bran (in native form) has the highest viscosity
(976.81 mPa.s) compared to other cereal brans due to the excessive
amount of β-glucan (17%) in oat bran. The study by Roye et al. (2020)
proved that mild fractionation to remove remaining endosperm in oat
bran is sufficient to achieve thickening ability.
Extensive physical, chemical and enzymatic treatments can irre­
versibly reduce the viscosity and flow behaviour of cereal by-product
hemicelluloses in solution. According to Kivelä et al. (2010), the
molar mass of oat bran β-glucan after homogenization is directly pro­
portional with the viscosity of the hemicelluloses. This statement is
supported by Tosh et al. (2010) who found that a different molecular
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Food Research International 151 (2022) 110818
weight of oat bran β-glucan (Mw = 1.93 × 106 – 0.25 × 106 g/mol) was
produced by several extrusion parameters gave a linear relationship
with the viscosity trend (2900 – 131 mPa.s; at 30 1/s). Besides, extensive
homogenization also enhances oat bran β-glucan molecular degradation
and thus reducing its viscosity and molar mass; creating a more spherical
and denser shape of β-glucan (Kivelä et al., 2010). Furthermore, Liu
et al. (2020) found that the molecular degradation of wheat bran AX
from ultrasonication, xylanase and trifluoroacetic acid treatments,
decreased the viscosity of AX in solution.
5. Industrial applications of cereal by-product hemicelluloses
and the needs for purification to fit each type of application
As discussed in previous sections, based on the abundant availability
and physicochemical properties, cereal side streams which consist of
hemicellulose rich-residues have various potential industrial uses aside
from animal feed and fertilizer. During milling, cereal bran is often
removed due to rancidity issues and organoleptic properties (Patel,
2012). In another example, unprocessed oat husks which account for up
to ~ 28% of the total grain weight are low in protein and energy (but
high in dietary fibre), and uneconomical due to their low packing den­
sity (Abedi & Dalai, 2019; Korchagina et al., 2019). However, the
hemicellulose fractions in cereal side streams have attracted a lot of
interest in both academia and industry due to the economic value of
possible applications. Recently, companies are looking for alternative
ways to utilize oat hulls (Xinova, 2019). It is known that efficient
valorization of cereal by-products requires fractionations of their com­
ponents. The purer the fractions, the higher the value of the applications
(Snelders et al., 2014). In this review, we will look into the possible use
of cereal by product hemicelluloses in the laboratory and industry. The
discussion in this section will be arranged from low-value to high-value
applications. The real case industrial uses are summarized in Table 6.
This section will offer an insight in to the considerations required to
purify cereal by-products hemicelluloses in order to expand their
applications.
5.1. Biorefineries
The depletion of natural fossil fuels has increased the interest to
valorize lignocellulosic biomass including cereal side streams to power
biorefineries. The term “biorefinery” encompasses biofuels (e.g. bio­
methanol, bioethanol, biogas, biodiesel and biochar), energy and heat
(Balat, 2011; Berntsson et al., 2012). Production of cereal by product-
based bioethanol is cost-effective and provides a clean alternative, but
has not been industrialized (Balat, 2011). If scale up is possible, it is
estimated that the bioethanol from Asia’s corn stover, wheat and rice
straw can yield up to 291 GL/year followed by Europe’s wheat straw
(69.2 GL/year) (Kim & Dale, 2004). On the other hand, the production
of biogas is mostly from cellulose and hemicellulose fractions of biomass
(e.g. cereal straw) (Banik, 2004). Recently, Oatly, Sweden has built a
new plant for biogas energy renewal by utilizing their oat fiber residues
(Oatly, 2021). The most ideal method to efficiently valorize cereal
straws for biorefineries purposes is organosolv fractionation where the
cereal straws are treated with mixtures of water with organic solvents
such as acetone, methanol, ethanol or acids (Snelders et al., 2014).
Biochar from cereal crops is also gaining attention as it can replace the
existing active carbon and enhance soil structure by increasing soil
productivity (e.g. increase soil’s water holding capacity, improve nu­
trients retention and supports the growth of beneficial microorganisms)
(Khan & Umarah, 2012). Caban et al. (2019) confirmed that the surface
of cereal-based biochars are full of polar moieties which are beneficial to
remove polar pollutants. The method to create biochar is very simple
and straightforward and impure fractions of hemicellulose can be used.
The steps involved pre-treatment of the cereal grains and straws with tap
water and distilled water, followed by oven drying for 24 h. Finally, the
cereal grains and straws were burned at 650 ◦ C in a controlled furnace
A.N. Arzami et al. Food Research International 151 (2022) 110818

Table 6
A summary on how some companies re-purpose cereal side streams.
Product Applications Source Company References

Xylitol Food, cosmetic and pharmaceutical Oat hull Fazer Oy, Finland. Fazer (2019)
Renewable energy Biorefinery Oat residues and xylitol Fazer Oy, Finland. Enerstena (2020)
processing residues
Biogas Biorefinery Oat residue Oatly AB, Sweden. Oatly (2021)
Prototypes of oat-based food (not yet Food Oat residue Oatly AB, Sweden. Oatly (2021)
commercialized)
PromOat Oat Beta-glucan Food and beverage Wholegrain oats; oat bran Lantmännen AB, Lantmännen (2021)
Sweden.
TM
OatWell Original/Crispy Hearts/Snack Bites Food and beverage Oat bran OatWellTM, UK. OatWell (2021)
Cocoa/Snack Bites Coconut
Organic Oat Bran/Stabilized Rice Bran. Food- ingredients in baked goods and Rice bran; oat bran Now Foods, USA. NowFoods (2021)
thickener in smoothies
Cereal Pore Foamcrub Cosmetics- facial scrub Rice bran (70%) Some By Mi, South SomeByMi (2021)
Korea.
High quality oat feed Animal feed and biomass Oat hulls and straw Richardson Milling, RichardsonMilling
UK. (2021)
Barley straw pond treatment Other- treating algae bloom in pond Barley straw Feed For Less, USA. FeedForLess (2020)
Equestrian, poultry, pet, pig, cattle, sheep bedding Other- animal bedding Wheat straw Capper Trading Ltd., CapperTrading (2021)
UK.
Eco-Fibre Compostable Wheat Food Boxes Biodegradable packaging Wheat straw Nisbets, UK Nisbets (2021)
Life Extension NK Cell Activator Pharmaceutical Rice bran Life Extension, USA. LifeExtension (2021)

for an hour (Caban et al., 2019).
5.2. Animal feed
According to FAO (2020) the use of cereal grains for world animal
feed in 2019/2020 is 977 MT from 2711 MT of cereal production. Cereal
biomass can be directly used for animal feed without any fractionation
or purification. Depending on the type of animal, the consumption of a
high concentration of cereal by-products containing AX (e.g. in wheat
and barley) and β-glucans (e.g. in barley) may induce anti-nutritional
effects in the animal’s stomach (Annison et al., 1995). To avoid
malnutrition in animals, endo-β-1,4-xylanase is usually added in the
cereal by-products’ feed to increase nutrient digestability. Bautil et al.
(2019) summarized the hypotheses on the mechanisms involved with
the enzyme addition in feed. In any case, the consumption of dietary
fiber can benefit the animals. Moon et al. (2016) showed that incorpo­
ration of β-glucan (60 ppm) in broiler’s diet increased the chickens’
survival rate at a similar level as adding antibiotics. Oat hulls are
valuable feed for ruminants and rabbits, and can increase litter weight of
pregnant sows (Cameron et al., 1991; Liangzhan et al., 2017; Mroz et al.,
1986). Zhang et al. (2004) found that corn hull AX increases broiler
chicks’ weight and decreases Salmonella attachment at ileal tissue in the
chicken’s small intestine.
5.3. Biodegradable plastics and packaging
For the last 60 years, non-renewable plastics made from fossil hy­
drocarbons have been seen floating in the sea. According to Lebreton
and Andrady (2019) about 60–90 million tons of mismanaged global
plastic waste were generated in 2015. This figure could triple by 2060.
From this amount, about 91% of plastic waste was transported by rivers
to the ocean. This has created a major global problem since plastics take
1000 years to naturally decompose, thus, endangering the ecosystem
(Kale, Deshmukh, Dudhare, & Patil, 2015). In recent decades, there has
been a great interest to produce biodegradable plastics and packaging
from renewable sources such as cereal by-product hemicelluloses (Li &
Pan, 2018; Mikkonen & Tenkanen, 2012). Péroval et al. (2002) used
maize bran AX emulsified with hydrogenated palm oil to create edible
AX-based films. The authors found that this combination produces sur­
face hydrophobicity similar to LDPE (contact angle > 90◦ ), smallest fat
particle size (0.54 µm) and lowest water vapor permeability. Mikkonen
et al. (2009) plasticized oat spelt AX (osAX) with sorbitol and glycerol.
They demonstrated that the plasticized osAX films were efficient oxygen
barriers, after removal of water insoluble part, which comprised almost
30% of osAX. Another study by Höije et al. (2005) indicated that highly
purified AX from barley husks (purity: 83%) were able to form strong,
stiff and amorphous film without any addition of plasticizer. However, it
is known that purification of cereal hemicelluloses for packaging
application is currently too costly for most industries. Besides, hemi­
celluloses possess a more intricate structure, lower tensile strength and
higher oxygen transfer rate than celluloses (Wang, 2015). Therefore,
hemicellulose packaging is less commercially viable compared to starch
and cellulose packaging (Mikkonen & Tenkanen, 2012). Razzaq et al.
(2016) developed an economical method to purify barley β-glucans for
biobased films. The purification process was done by creating milled
barley suspension under alkaline medium with final pH of 9 to 10 fol­
lowed by centrifugation at 20 ◦ C. Based on their findings, alkaline
extracted barley β-glucans film has better thermal stability, tensile
strength, water stability and water vapor permeability compared to non-
alkaline extract film. A detailed review on the development of biobased
films from different sources of β-glucans including oat and barley was
discussed by Peltzer et al. (2018).
5.4. Nano-materials
Sarker et al. (2020) utilized chemically modified wheat bran AX (by
alkaline extraction followed by ethanol precipitation and centrifuga­
tion) to develop functional nano-materials for nucleic acid delivery in
plants. According to the authors, the cationic AX formed stable nano­
particles and were able to complex with CRISPR-Cas9 DNA. Ngu et al.
(2016) converted rice husk into fluorescent carbon nanoparticles (CNPs)
using a thermally-assisted carbonization technique under high acidic
condition using sulfuric acid. Their work found that the water solution of
the CNPs can emit very bright blue luminescence at 439 nm, and the
higher the concentration of Sn(II) ions in the CNPs, the lower the fluo­
rescence capacity. This finding may provide a solution to replace un­
sustainable quantum dots and fluorescent dyes.
5.5. Food and beverage
Impure fractions of cereal hemicelluloses for use in food and bever­
ages can be easily obtained by milling followed by air classification and
ethanol precipitation (Kivelä et al., 2009; Valoppi et al., 2021). On the
contrary, purer fractions of cereal hemicelluloses can be obtained
enzymatically (e.g. using starch degrading enzyme) or chemically (e.g.
alkaline extraction) (Herrera-Balandrano et al., 2020; Kvist & Lawther,

13
A.N. Arzami et al.
2011). Koegelenberg and Chimphango (2017) demonstrated the effect
of using different purities of wheat bran AXs fractions in bread. The
authors found that the addition of 0.8% crude (44% purity) and partially
purified (49% purity) fractions of wheat bran AX can substitute 2.5% of
flour without affecting the height, volume, weight and firmness of the
bread. Bread with highest AX purity (95%) gave softer bread crumb
compared to AX with lower purities. The moisture content of bread with
crude AX added was higher than partially purified AX. In another study,
0.15% and 0.30% of nixtamalized maize bran with feruloylated AX can
enhance the antioxidant capacity, phenolic content and physicochem­
ical properties of frankfurter sausages (Herrera-Balandrano et al., 2019).
Other than AX, previous research has shown that a mixture of inulin
(3.1%) and oat β-glucans (2.2%) significantly improved the cooking
yield, water holding capacity and textural properties of low-fat beef
burgers (Afshari et al., 2015). Additionally, a mixture of 1.5% barley
β-glucans and 1.5% microcrystalline cellulose produced beef emulsions
with appropriate textural properties (Vasquez Mejia et al., 2019). Kivelä
et al. (2009) used oat bran β-glucan (impure fraction: mixtures of
β-glucan, proteins and others) in model beverages with acidic condi­
tions. According to the authors, the viscosity and the Mw of β-glucan
extract decreased with the addition of ascorbic acid. This may cause
molecular instability of the model beverage during storage. In research
conducted by Gangopadhyay et al. (2019), wheat flour was replaced by
10% and 15% of impure barley bran (β-glucan content 0.39% and
0.64%, respectively) in crackers. The results showed higher total
phenolic content, antioxidant capacity and total flavonoid content in
15% barley bran cracker sample compared to other samples. Valoppi
et al. (2021) also showed that impure fractions of oat side streams
(consists of AX, β-glucan, protein, fat and cellulose mixtures) formed
stable emulsions and suspensions after a combination of homogeniza­
tion treatments. All these studies indicated that it is possible to use
impure fractions of hemicelluloses in food products to achieve desired
physicochemical properties. However, the utilization of these impure
fractions may not be sufficient to achieve desired health effects in con­
sumers. For example, The European Food Safety Agency (EFSA) and U.S.
Food and Drug Administration (FDA) recommends consumption of 3 g of
β-glucan per day to reduce blood serum cholesterol and the risk of CVD
(EFSA Panel on Dietetic Products, 2011; FDA, 1997, 2005). Fig. 5
summarises the nutritional content of commercially available oat bran
product OatWellTM Original which has been confirmed by EFSA to
promote health effects.
5.6. Pharmaceutical and cosmetics
The utilization of cereal AX and β-glucans in pharmaceutical and
biomedical applications have been discussed in detail by Mendez-Enci­
nas et al. (2018), Niño-Medina et al. (2010) and Zhu et al. (2016). Over
the years, cereal AX has demonstrated good anticancer, prebiotic,
Fig. 5. Nutritional content of OatWellTM Original oat bran powder.
Source: OatWell (2021).
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gelling capacity and antioxidant properties. Carvajal-Millan et al. (2006)
and Berlanga-Reyes et al. (2009) reported that wheat WEAX and maize
bran AX have great potential to entrap proteins and function as
controlled-release agents. Enzymatically modified purified wheat bran
arabinoglucuronoxylan (purity: 53%) and oat spelt arabinoxylan were
reported to successfully encapsulate (using in-situ encapsulation pro­
cess) while maintaining the functional properties of gallic acid (Chim­
phango & Matavire, 2019). There are numerous reports on β-glucans
beneficial properties, including; wound healing enhancer, anticancer,
protein delivery carriers, blood cholesterol reducer and anti-diabetes
(Choromanska et al., 2015; Delatte et al., 2001; Jenkins et al., 2002;
Lazaridou et al., 2015; Seo et al., 2019; Wolever et al., 2010). Majority of
the studies used purified cereal β-glucans. Several patents have been
filed on purification of cereal β-glucan to fit pharmaceutical applications
(Kvist & Lawther, 2011; Morgan, 2002; Redmond and Fielder, 2005,
2006). The most suitable and cost-effective method to purify β-glucan
from cereals for food, cosmetic and pharmaceutical uses is by using
enzymatic hydrolysis technique (Kvist & Lawther, 2011). This method
uses a combination of dry (milling) and wet (enzymatic hydrolysis)
fractionation techniques to produce medium and high molar mass
β-glucan (MM = > 800 and > 1300 kDa).
Based on our current investigation, we have not found any β-glucan
health supplements with cereal side streams origin. Most β-glucan sup­
plements for immune boosters were extracted from yeast (Saccharomyces
cerevisie), mushroom or algae. This is probably due to a lack of
economically feasible extraction methods to obtain large scale, high
purity cereal by-product β-glucans as discussed in Section 3.2.2. On the
other hand, there are a lot of commercially available AX immunomod­
ulator supplements where rice bran AX was used as one of the main
ingredients (e.g. BioBran Plus Tablets, Life Extension NK Cell Activator
and Peak Immune 4). Most of the AX in these supplements were
extracted enzymatically. In cosmetic applications, cereal AXs and
β-glucans have been reported to improve skin moisturizing properties,
reduce wrinkles and act as natural antioxidants (Du, Bian, & Xu, 2014;
Pillai et al., 2005; Przybylska-Balcerek & Stuper-Szablewska, 2019).
Surprisingly, research on utilization of cereal by-product hemicelluloses
in cosmetic applications are not as extensive as for other applications.
Based on the findings in this section, it is clear that improved purifica­
tion of cereal hemicellulose is needed to explore pharmaceutical and
cosmetics application.
6. Future perspective
The human population is expected to increase to 9 billion by 2050.
There is a dire need to secure food by increasing food production and
minimizing loss along the agri-food chain. Besides, with the need to limit
the effects of climate change and global warming, there is a desperate
call to replace non-renewable resources with green materials and
A.N. Arzami et al.
technologies. Over the years, scientists and industry players have come
together to explore the potential uses of cereal by-products. Further­
more, with the discovery of health-beneficial hemicelluloses such as AX
and β-glucan especially in cereal brans, there is a strong interest to
incorporate these hemicelluloses into special diet feed, food, cosmetics
and pharmaceutical applications. However, up to this point, there is no
excellent solution to fully utilize cereal by-products other than for feed
and biomass. This is due to the lack of more economical and sustainable
fractionation methods at a pilot and industrial scale. Additionally, as
discussed in this review, different processing methods may decrease the
molar mass of AX and β-glucan. Different molar mass may affect the
functionality of these hemicelluloses and their health potential proper­
ties. For example, low molar mass β-glucan is efficient as an anticancer
agent and high molar mass β-glucan can reduce cholesterol and act as a
glycemic control agent (Choromanska et al., 2015; Schmidt, 2020).
Future studies need to focus on a combination of methods to fractionate
pure AX and β-glucan sustainably and economically while carefully
monitoring the changes in its physicochemical properties.
If fractionation of pure cereal by-product hemicelluloses is not sus­
tainably and economically feasible to upscale and takes a long time to
research, an alternative scope should be considered; the utilization of
impure fractions should be put in focus. This idea can enhance circular
economy while saving a lot of industrial costs. In reality, cereal side
streams are composed of a mixture of hemicelluloses, lignins and cel­
luloses. Aside from AX and β-glucan, cereal side streams especially in
brans, are also rich in proteins, vitamins, saponins and minerals (Patel,
2012). As discussed in the previous sections of this review, impure
fractions of cereal by-products AX and β-glucan can be used as food
ingredients and in biorefineries. Future studies should expand on the
applications of impure fractions of these hemicelluloses in various areas.
Valoppi et al. (2021) has showed that full utilization of cereal side
streams without further fractionation is possible when native insoluble
oat bran fraction (consists of equal fractions of AX, β-glucan and protein,
with few percentages of fat and cellulose mixtures) and native soluble
oat bran fraction (mixtures of 78% β-glucan, 5% AX and 11% proteins)
can be used together to form stable emulsions and suspensions over
time. This opens up the potential to utilize the native fractions of oat side
streams in various applications such as packaging, food, beverage,
pharmaceuticals and cosmetics. Besides, researchers also have report­
edly found phenolic acids in the native form of cereal brans (Gong et al.,
2012; Verma et al., 2009). These phenolic compounds particularly
ferulic acid and diferulic acid are responsible for the antihypertensive,
anti-inflammatory and antioxidant properties in vivo and in vitro (Bau­
tista-Expósito et al., 2020; Palani Swamy & Govindaswamy, 2015).
Another idea is to use the whole cereal grain including its husk, bran
and straw as suggested by Lie-Piang et al. (2021). According to the au­
thors, besides optimizing the number of resources and supporting cir­
cular economy, this idea was proven to reduce cancer-causing risk in
humans, future global warming, water consumption and solve fossil
resources problems. Studies on impure fractions of legumes such as
lupin and pea using mild fractionation have been proven to produce
promising thickening and emulsifying properties (Berghout et al., 2014;
Kornet et al., 2020; Sridharan et al., 2020). There is an opportunity to
explore similar studies on cereal grains in the future. This indicates that
sustainable materials are not solely based on purity, but also superior
physicochemical characteristics (Lie-Piang et al., 2021).
7. Conclusions
Cereal brans of oat, wheat and barley are abundant sources of
hemicelluloses, especially arabinoxylans and β-glucans. Extractions of
the arabinoxylans and β-glucans from corn, rice and rye side streams are
limited although these streams provide an ample amount of hemi­
celluloses. There are many ways to extract cereal by product hemi­
celluloses such as using water, enzyme, chemical and mechanical
treatments. The purification of these hemicelluloses can be performed
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either before or after extraction. Among the techniques, the most sus­
tainable methods were using enzymes, hydrothermal treatment, twin-
screw extrusion and supercritical extraction along with purification (e.
g. membrane or anion exchange, dialysis) under very weak alkali or
acidic conditions. However, in terms of having both sustainable and
cost-effective methods to extract large scale and high purity arabinox­
ylans and β-glucan for industrial purpose, further research in this area is
needed. Knowledge on the physicochemical properties of cereal by-
product hemicelluloses are crucial to determine their applications. The
solubility, molecular mass, viscosity, gelation and rheological behaviour
of these hemicelluloses were affected by the different genotypes (e.g. the
chemical nature of its component, composition of the cell wall constit­
uents and overall architecture), fractionation methods and the experi­
mental techniques chosen to determine the properties. Impure fractions
of cereal by-product hemicelluloses can be used for feed, food in­
gredients and biorefineries. However, high-end applications such as
pharmaceutical and health-promoting food requires pure fractions of
hemicelluloses.
This study has found that in recent years, some industries are
trending towards the sustainable use of cereal side streams as many
products have been made available for public use. Although many ef­
forts have been made to maximize the valorization of cereal by-product
hemicelluloses in the last twenty years, it is still important to have a pure
fraction of hemicelluloses to increase the value of the potential final
product. A clear framework of knowledge and technology transfer be­
tween academics and industries is the most crucial step to successfully
maximize the valorization effort in both developing and developed
countries. This will result in an enhanced global circular bioeconomy
and help solve the global food waste problem.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors acknowledge Mr. Troy Faithfull for proofreading the
manuscript.
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