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saccharides:
manufacture and
applications
M.J. Va zquez, J.L. Alonso,
H. Dom
a Qu
mica, Universidade
de Vigo (Campus Ourense), Edicio Polite cnico, As
Lagoas, 32004 Ourense, Spain (tel: +34-9-8838-7047;
fax: +34-988-387001; e-mail: jcparajo@uvigo.es)
Xylooligosaccharides (sugar oligomers made up of xylose
units) are useful for a variety of purposes. This article
reviews the production of xylooligosaccharides from lig-
nocellulosic materials (by chemical or enzymatic methods)
and the purication of the end products, as well as their
application as food ingredients, with special attention to
the benecial eects caused on health by these types of
compounds. # 2001 Elsevier Science Ltd. All rights
reserved.
Production of xylooligosaccharides from ligno-
cellulosic materials
Xylooligosaccharides (XOs) are sugar oligomers
made up of xylose units, which appear naturally in
bamboo shoots, fruits, vegetables, milk and honey.
Their production at an industrial scale is carried out
from lignocellulosic materials (LCMs). XOs can be used
for several of purposes (see Fig. 1). Among them, this
review is focused on food-related applications.
The LCM for XO production come from variety of
feedstocks (from forestry, agriculture, industry or urban
solid wastes) that show similarities in composition.
Besides non-structural components (such as extractives
or ash), LCMs are made up of three polymers: lignin
(with phenolic nature), cellulose (a linear polymer made
up of b-glucose units linked 1!4) and hemicelluloses
(branched heteropolysaccharides made up of a variety
of monosaccharides, including xylose, arabinose, man-
nose, glucose and rhamnose). Compositional data of
representative raw materials have been summarized by
Garrote et al. [1].
Depending on the nature of the lignocellulosic mate-
rial, polymers of xylose (xylan), arabinose (arabinan) or
mannose (mannan) may account for a substantial part
of hemicellulose, which can be substituted via ether or
ester bonds (for example with a-d-glucopyranosyl uro-
nic acid or its 4-O-methyl derivative, acetyl groups and
acids [2,3], see Fig. 2). Typical raw materials for XO
production are hardwoods, corn cobs, straws, bagasses,
hulls, malt cakes and bran.
The concept for manufacturing XOs from a suitable
LCM is simple: starting from a xylan-rich feedstock,
some of the heterocyclic ether bonds of the xylan back-
bone have to be hydrolyzed to give compounds of lower
polymerization degree. Three dierent approachs have
been used for XO production from these feedstocks:
a. Enzyme treatments of native, xylan-containing
LCM
b. Chemical fractionation of a suitable LCM to iso-
late (or to solubilize) xylan, with further enzymatic
hydrolysis of this polymer to XOs; and
c. Hydrolytic degradation of xylan to XOs by steam,
water or dilute solutions of mineral acids.
All these possibilities are considered in the following
paragraphs.
The direct xylooligosaccharide production from
xylan-containing LCMs must be carried out from a
susceptible feedstock. For this purpose, XO manu-
facture from the membranes of citrus fruit pulp by
enzymatic methods has been reported by Takao and
Yoshio [4].
The production of XO by combined chemical-enzy-
matic methods is shown in Fig. 3a: xylan (or soluble
xylan fragments) can be obtained from LCMs by treat-
ments with alkalis (for example, with solutions of
NaOH, KOH, Ca(OH)
2
, ammonia or a mixture of these
compounds). The processing of xylan-containing LCM
in alkaline media is favoured by the pH stability of this
polymer, and the solubilized fraction can be recovered
from liquors by further processing. In some cases, the
raw material has been pretreated with oxidizing agents,
0924-2244/00/$ - see front matter Copyright # 2001 Elsevier Science Ltd. All rights reserved.
PI I : S0924- 2244( 01) 00031- 0
Trends in Food Science & Technology 11 (2000) 387393
*Corresponding author.
Review
salts or alcohols to remove lignin or pectic sustances. In
case the xylan has been solubilized in caustic liquors,
precipitation with organic compounds (including acids,
alcohols or ketones) allows the recovery of dissolved
hemicelluloses and hemicellulose-degradation products.
Once the xylan has been isolated or degraded to a solu-
ble form, further DP reduction can be accomplished by
hydrolysis with xylanases [57]. For enzymatic produc-
tion of XOs, enzyme complexes with low exo-xylanase
and/or b-xylosidase activity are desired, in order to
avoid the production of xylose. The enzymes can be
directly added to the reaction media [8], immobilized [9],
or produced in situ by microorganisms [10]. With this
approach, low-DP xylooligosaccharides can be pro-
duced. For food-related applications, the preferred DP
range is 24 [11].
Alternatively, XO can be produced from LCMs in a
single step by reaction with steam or water through
hydronium-catalysed degradation of xylan, according to
the procedure known as autohydrolysis, hydro-
thermolysis or water prehydrolysis (see Fig. 3b). In the
rst stages of the reaction, the catalytic species come
from water autoionization, but side reactions (for
example, cleavage of acetyl groups to give acetic acid)
contribute to the generation of hydronium ions in fur-
ther reaction stages. The hydrolytic degradation of
hemicelluloses is facilitated when an acid is externally
added (acid prehydrolysis), but in this case the oligo-
saccharides behave as reaction intermediates and the
main reaction products are monosaccharides. Besides
the degradation of xylan, several side-processes occur in
such kinds of treatment, including extractive removal,
solubilization of acid-soluble lignin and neutralization
of ash. All of them contribute to the presence of com-
paratively high concentrations of undesired, non-sac-
charide compounds in liquors from hydrothermal
processing. Because of this, the purication of XOs is of
major importance. In order to simplify the purication
of XOs, the feedstock can be pretreated before the water
treatment (see Fig. 3b). For example, solvent extraction
of the LCMs before the water treatment allows the
removal of the extractives contained in the feedstock.
Usually, mild operational conditions are preferred in
order to achieve high extent of xylan solubilization (to
give xylooligosaccharides with DP typically 20) while
sugar-degradation reactions are avoided. If the nal
distribution of molecular weights is unfavourable for
the desired application (for example, for food-related
purposes), further DP reduction can be achieved by
enzymatic treatments [9,12,13].
Purication of crude XO solutions
The purication of crude XO solutions is a complex
problem, particularly when they come from hydro-
thermal processing. A variety of strategies have been
proposed for rening the crude liquors, in order to
remove undesired compounds and/or to select XOs
within a given DP range. Depending on the degree of
purity desired, a sequence of several physicochemical
treatments may be necessary.
Vacuum evaporation can be the rst stage in the pro-
cessing of crude oligosaccharide solutions. Besides the
expected increase in concentration, evaporation allows
the removal of acetic acid and avours or their pre-
cursors, which can be responsible for o-avours [14].
In some cases, the presence of avours in the nal solu-
tions is favourable for further utilization [15,16].
Starting from dry fractions of hemicellulose extracts,
organic acids (such as formic, acetic or propionic) have
been proposed to purify the xylan-degradation pro-
ducts. In this kind of treatment, the water concentration
should be limited in order that the impurities become
soluble while avoiding appreciable solubilization of the
hemicellulose [17]. Other organic solvents (such as alco-
hols and acetone) have been proposed for the recovery
of hemicellulose-degradation products [18].
Fig. 1. Applications of xylooligosaccharides (XOs).
388 M.J. Vazquez et al. / Trends in Food Science & Technology 11 (2000) 387393
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M.J. Vazquez et al. / Trends in Food Science & Technology 11 (2000) 387393 389
The separation of XOs within a given DP range has
been carried out by membrane techniques, in order to
remove both XOs within the undesired DP range and
non-saccharide compounds [13,1921].
Adsorption (using adsorbents such as activated char-
coal, acid clay, bentonite, diatomaceous earth, alumi-
nium hydroxide or oxide, titanium, silica and porous
synthetic materials) has been used for purication of
XO-containing liquors. Figure 4 shows a process based
on the utilization of activated charcoal followed by elu-
tion with ethanol proposed by Peller n et al. [8]. In the
rst stage, xylooligosaccharides are retained by char-
coal, and the DP range of the fractions coming from
ethanol elution depends on the alcohol concentration,
allowing a fractionation of the XOs on the basis of their
molecular weight.
Ion-exchange resins are useful for desalination, but
show limited ability for retaining coloured compounds
[22]. Studies dealing with cation-exchange resins, anion-
exchange resins and mixed beds have been reported
[19,23]. Alternatively, the simultaneous removal of
colouring compounds and salts from XO solutions can
be accomplished by chromatographic separation [12].
Technological properties of XOs and their eects
on health
XOs are used as food ingredients owing to their tech-
nological properties and healthy eects.
For food applications, xylobiose (DP=2) is con-
sidered to be a xylooligosaccharide, even if for other
purposes the concept oligo is associated with higher
DP. The sweetnees of xylobiose is equivalent to 30%
Fig. 3. (a) General idea of XO manufacture by chemical-enzymatic methods. (b) Procedure for XO manufacture by hydronium-catalyzed
process.
390 M.J. Vazquez et al. / Trends in Food Science & Technology 11 (2000) 387393
that of sucrose, and the sweetness of other xylooligo-
saccharides is moderate and possess no o-taste.
Xylooligosaccharides are stable over a wide range of pH
(2.58.0, an advantage compared with other non-diges-
tible oligosaccharides such as fructooligosaccharides
(FOs), particularly in the acidic range, even at the rela-
tively low pH value of the gastric juice) and tempera-
tures (up to 100