14
Stability and Degradation of Polysaccharides
Valdir Soldi
Federal University of Santa Catarina, Florianópolis, SC, Brazil
I. INTRODUCTION
The interest in degradation of polysaccharides is strongly
associated with a variety of applications in the food, paper,
pharmaceutical, cosmetic, textile, and oil industries. More
specifically, polysaccharides have been used in drug deliv-
ery, medical devices, oil exploration, water-based paints,
emulsions, dispersions, wastewater treatment, etc. Besides
the dependence on their chemical structure, these functions
are also dependent on a controlled molecular size. For
example, the potential biomedical and food applications
for lower molecular weight chitosan encouraged the de-
velopment of viable processes for controlling the degrada-
tion of this polysaccharide [1,2]. Through decreasing the
molecular weight of chitosan (and other polysaccharides),
it is possible to control properties like viscosity, solubility,
and biological activity. In a similar manner, the water-
soluble polysaccharide, guar, needs to be depolymerized
for use in applications such as food and oil production
[3,4]. The primary degradation products from the thermal
degradation of polysaccharides are also of great interest.
For example, monomeric anhydrosugars have been
obtained from the pyrolysis of polysaccharides. By this
process, levoglucosan was obtained from cellulose [5,6]
and starch [7], and 2-acetamido-1,6-anhydro-2-deoxy-h-D-
glucopyranose from chitin [5,6]. Most of the applications
for cellulose depend on enzymatic modification or other
structural changes. This behavior is in general associated
with a total absence of solubility either in water or in
aqueous alkaline solutions due to the existence of intra-
and intermolecular hydrogen bonds in solid-phase cellu-
lose. To solve this problem, it is necessary to activate
cellulose by swelling and degradation processes (mechan-
ical or thermal treatment). In another example, cellulose is
easily dissolved in aqueous solution (9% NaOH) after
modification with cellulase (enzyme) and treatment with
sodium hydroxide [8].
The degradation of polysaccharides has been analyzed
by chemical, enzymatic, thermal, mechanical (ultrasonic),
and radiative processes, which are generally dependent on
the structure, conformation, and applicability of the poly-
saccharides, reactive agents, etc. For example, chemical
degradation reactions depend on the nature of initiation
(thermal, high energy, UV radiation, etc.) and reactive
agents such as oxygen and hydrogen ions. Depending on
the structure, conformation, and reactive agents, different
chemical bonds of the polymer can be attacked. In dextran,
for example, the bonds near the ends of a polymer chain are
more reactive than those at the center [9]. In cellulose, the
cleavage of the glycosidic bond is catalyzed either by H3O+
(acid hydrolysis) or by enzyme (cellulase) [10]. At the same
time, the acid hydrolysis in chitosan breaks preferentially
the ether linkages in the macromolecule increasing the
polymer reactivity [11]. For chitosan, nitrous acid attacks
the amine groups but not the N-acetyl moieties, and
subsequently cleaves the h-glycosidic linkages [12]. Xan-
than is able to retain a high molecular weight (106 g mol
1)
when submitted to depolymerizing conditions such as acids
or free radicals [13,14]. This is because the double-helical
structure of xanthan is stabilized by noncovalent bonds
between adjacent chains. In contrast to other polysaccha-
rides, in xanthan, the cellulosic regions are the primary sites
that suffer the attack by cellulases (enzymatic degradation)
[15,16].
The application of ultrasonic degradation in the lab-
oratory and the food industry (not discussed in detail in this
chapter) has received more attention in recent decades
mainly to depolymerize macromolecules, prepare emul-
sions, and disrupt biological cells. For polysaccharides,
the preliminary studies were related to cellulose derivatives
[17], starches [18,19], dextrans [20], chitosans [21], and
xanthans [22]. The main effect observed in these macro-
molecules was a reduction in solution viscosity or gel
strength due to a decrease in molecular weight [20,21,23].
395
396 Soldi

Recently, Lii et al. [24] studied the degradation kinetics of

agarose and carrageenans by ultrasound, observing that
for solutions with 0.5 wt.% polysaccharide, the degrada-
tion rate decreases linearly with the reduced viscosity. This
result indicated that the ultrasonic degradation of agarose
and carrageenans follows a first-order kinetics, and is
dependent on molecular size (decrease in viscosity). The
degradation mechanism has been attributed to cavitation
(mechanical effect); that is, the formation and collapse of
microscopic vapor bubbles generated by the strong sound
waves [25].
The aim of this chapter is to analyze the stability and
degradation of polysaccharides considering three main
general topics: (1) chemical (acid and alkaline) degrada-
tion in aqueous solution, (2) processes of biodegradation,
and (3) thermal stability (thermal degradation) of poly-
saccharides. The first topic was chosen because alkaline
degradation was the first process studied concerning the
stability of mono- and polysaccharides. Although most
work related to chemical degradation deals with cellulose
and cellulose derivatives, it is important to point out the
effects of temperature, concentration, and mechanism of
degradation (reaction products). In biodegradation, dif-
ferent aspects are considered such as the hydrolysis pro-
cess, effect on the molecular weight distribution, and effect
of pH. The thermal stability was analyzed in terms of the
kinetic parameters of degradation, viscosity (intrinsic vis-
cosity), temperature, depolymerization, and mechanism of
degradation. To better understand the mechanism of Figure 1 Reduced viscosity (gred) vs. concentration (A) and
degradation, a section with the main products associated log intrinsic viscosity (log [g]) vs. log molecular weight (log
with the degradation of polysaccharides was included in MW) (B). In A, 5 represents undegraded N-succinyl-chitosan
this chapter. and o, 4 represent two degraded samples of N-succinyl-
chitosan. (From Ref. 26.)

II. CHEMICAL DEGRADATION

In this section, different polysaccharides were analyzed in
terms of acid and alkaline degradation processes. For
example, the depolymerization of N-succinyl-chitosan so-
dium salt was studied in an aqueous solution of hydro-
chloric acid by Kato et al. [26] in terms of the molecular
weight and viscosity behavior. The acid treatment was
performed by stirring a solution of N-succinyl-chitosan in
7.5 M aq HCl at room temperature or 3.3 M aq HCl at
40jC. In the depolymerization process, two degraded
products were characterized in terms of the molecular
weight by the authors, using size-exclusion chromatogra-
phy-multiangle light scattering (SEC-MALS). Studies uti-
lizing 1H NMR and elemental analysis indicated that the
degraded products retained the fundamental structure of
the N-succinyl-chitosan. The molecular weights (Mw) for
the two degraded products were 70,000 and 28,000 g cm3,
very low values in comparison to the N-succinyl-chitosan
for which Mw = 310,000 g cm3. The viscosity behavior
[reduced viscosity (gred)] was analyzed as a function of the
concentration in salt solution at 37jC (Fig. 1A). As can be
observed, the viscosity of N-succinyl-chitosan, despite its
higher values, increased with the concentration. However,
for the depolymerized products, the viscosity values were
lower and a slight reduction was observed; that is, practi-
cally independent of the concentration. At the same time,
the intrinsic viscosity, obtained from the intercept of the
straight lines of Fig. 1A, increased linearly with the molec-
ular weight (Fig. 1B). The behavior in terms of viscosity
and molecular weight, associated with the analysis of the
composition of the degraded products indicated that the
chain scission of the N-succinyl-chitosan probably oc-
curred through the breakdown of the ether linkages in
the macromolecule, as was observed for chitosan [11].
Basedow et al. [9] studied the depolymerization reac-
tion of dextran at 80jC in 0.12 N sulfuric acid. During the
reaction, the molecular weight distribution was determined
by the gel permeation chromatography (GPC) method.
Different samples with initial concentrations of dextran in
the range of 0.25–2% were used. Considering the results, a
first-order reaction with respect to dextran concentration
was suggested by the authors. The average molecular
weight (Mw) changed from 117,000 to 3650 Da in the
reaction time range of 0–450 min and the rate constant
(k) was 6.30  10
6 sec
1.
Changes in the molecular weight were also analyzed by
the size exclusion chromatography-refractive index meth-
od (SEC-RI) considering the acid hydrolysis of (n-, L-, E-)
Stability and Degradation of Polysaccharides
carrageenans, dextran sulfate, and heparin [27]. The desul-
fation and depolymerization processes were studied at pH
2 (0.008 M LiCl + 0.012 M HCl buffer) at 35jC and 55jC.
After hydrolysis, the results showed that for carrageenans
and heparin, the sulfation was unaffected by the hydrolysis
conditions. However, for dextran sulfate, the desulfation
increased linearly with the hydrolysis time especially at
55jC. The difference in terms of the observed behavior was
attributed to the conformation flexibility of the polymer
chain. The average molecular mass (hMmi) measured as a
function of hydrolysis time is shown in Fig. 2. A significant
decrease in hMmi was observed for the carrageenans and
dextran sulfate (Fig. 2a–d) in comparison with the theo-
retical values determined assuming that desulfation was the
only mechanism for molecular mass loss. However, a very
slight effect was observed by the authors for heparin (Fig.
2e). The comparative analysis with the theoretical values
for dextran sulfate (Fig. 2d) indicated that besides the
sulfate loss, a chain scission occurred, significantly decreas-
ing the average molecular mass. From Fig. 2 and using Eq.
(1) [28,29] and the Arrhenius equation [Eq. (2)], the authors
determined the kinetic parameters (activation energy) for
the carrageenans and dextran sulfate. In Eq. (1), hMm(t)i
and hMm(0)i are the molecular mass at time t and time zero,
respectively
1 1 kt
D E¼D Eþ ð1Þ
ðtÞ
Mm
ð0Þ
Mm m tial-decay constant (the viscosity decreased with the hy-
ln k ¼ ln A
Ea =RT ð2Þ
where k is the first-order rate constant and m is the
molecular weight of the repeating unit. In the Arrhenius
equation [(Eq. (2)], Ea is the apparent activation energy, R
Figure 2 Average molecular mass as a function of hydrolysis time at (.) 35jC and (o)55jC, for (a) n-carrageenan, (b) L-
carrageenan, (c) E-carrageenan, (d) dextran sulfate, and (e) heparin. Theoretical molecular mass as a function of hydrolysis time
based on the desulfation effect is plotted as (–) at 35jC and (- - -) at 55jC. (From Ref. 27.)
397
is the gas constant, A is the pre-exponential factor, and T is
the temperature. The activation energy can be obtained
through the slope of the ln k vs. 1/RT plot. The activation
energy values were in the range of 100–120 kJ mol
1 except
for L-carrageenan, which was 162 kJ mol
1. The higher
stability for L-carrageenan was attributed to the steric effect
caused by the sulfate group in the polymer structure. Under
the above hydrolysis conditions, only the dextran sulfate
was sensitive to the process of desulfation. However, a
depolymerization process was characterized by the authors
for the carrageenans and dextran sulfate.
The cleavage of the glycosidic bond of cellulose is
catalyzed by H3O+ (acid hydrolysis), producing glucose as
the main reaction product (yield > 95%) and, in general,
the mechanism of degradation included the formation of
cationic intermediates that are responsible for the rate
constant. The degradation of cellulose fibers was analyzed
by Phillip [10] in HCl (100jC) and 1 N H2SO4 (80jC). In
both mediums, a significant decrease in the degree of
polymerization was observed. The mechanism of degrada-
tion includes a selective attack on the more unstable
glycosidic bonds (less-ordered regions) by the H3O+ ions.
As described by the author, the acid hydrolysis affects also
the fibrillar structure of the cellulose fibers.
In the degradation of xanthan in dilute acid (pH 1–4)
at 80jC and at high (500 mM) and low (10 mM) ionic
strengths, the viscosity was described by a single exponen-
drolysis time). At the same time, the stability increased with
the ionic strength [30].
The thermochemical degradation of starch and cellu-
lose to organic acids was studied by Krochta et al. [31–33] in
alkaline solution. Experimentally, the reactions were per-
formed at different temperatures (range of 180–240jC) and
398
products (organic acids) were determined by high-perform-
ance liquid (HPLC) and gas (GC) chromatography. For
both polysaccharides, the degradation was described as a
second-order kinetics by Eq. (3)
Ca
ln ¼ lnM þ Cp0 ðM
NÞka t ð3Þ
Cp
where Ca and Cp are the alkali and polysaccharide con-
centrations, respectively; M is the ratio between the initial
concentrations (Ca/Cp); N is the relation ((Ca0)/(Ca) / (Cp0)/
(Cp)); ka is the rate constant, and t is the reaction time. The
rate constant (ka) determined by Eq. (3) increased from
0.0026 L mol
1 min
1 (180jC) to 0.3733 L mol
1 min
1
(240jC) for starch and from 0.0034 L mol
1 min
1
(180jC) to 0.6000 L mol
1 min
1 (240jC) for cellulose.
A significant and similar effect due to the temperature, was
observed for both systems. The activation energy deter-
mined using the Arrhenius equation [Eq. (2)] was 165.10 kJ
mol
1 for the degradation of starch and cellulose. A
similar value (162 kJ mol
1) was determined by Karlsson
and Singh [27] for the degradation of L-carrageenan under
acidic conditions.
The stability of starch, cellulose, and rice straw in
various NaOH solutions was compared by Krochta et al.
[33]. The conversion of starch to water-soluble products
(degradation) in 4% NaOH occurred just by heating to
240jC. For cellulose and rice straw, the degradation
occurred in 40 min at 280jC, suggesting a higher stability
in comparison to the starch. Less time was required for the
degradation when 6% NaOH was used. By HPLC, the au-
thors identified seven organic acids resulting from the
alkaline degradation of 10% (w/w) starch, cellulose, rice
straw, and glucose in 6% (w/w) NaOH at 280jC for 10 min.
For both systems, the yields of lactic and formic acids were
more significant. For example, the starch degradation
mainly produced 19.8% lactic acid, 13.0% formic acid,
and 5.7% glycolic acid. Other organic acids such as acetic
acid, 2-hydroxybutyric acid, 2-hydroxyisobutyric acid, and
2-hydroxyvaleric acid were formed with ca. 2% content.
Similar percentages were determined for cellulose;
however, the percentages determined for the glucose were
totally different. For example, for glucose the amount of
lactic acid produced was 36.1%, for formic acid 5.4%, and
for 2-hydroxybutyric and 2-hydroxyisobutyric acids ca.
1%. In general, for both systems, the amount of organic
acids produced corresponds to the NaOH equivalents.
Recently, Knill and Kennedy [34] discussed the cellulose
degradation under alkaline conditions in terms of the
mechanism and physical aspects, which affect the degrada-
tion reaction and products. The predominant mechanism
suggested by the authors under alkaline conditions and at
temperatures <170jC, based on the literature [35–37], is
the formation of D-glucoisosaccharinic acids, as in the
alkaline degradation of 4-O-methyl-D-glucose.
The different processes of polysaccharides depolymer-
ization by acid hydrolysis discussed above, were in general,
described in terms of effects on the viscosity and the average
molecular weight. The extent of the effect depends on the
Soldi
experimental conditions, polysaccharide structure, confor-
mation, and other characteristics. The predominant mech-
anism for the chain scission was the breakdown of the
glycosidic bonds in the macromolecule, a well-known mech-
anism, which occurs in a wide range of polysaccharides.
III. BIODEGRADATION PROCESSES
Biodegradation was defined as an event that take place in
the natural environment and in living organisms [38,39].
Biodegradation, as well as other processes of degradation,
is dependent on the chemical structure of the polymers (or
biopolymers) because it is fundamental how easily they can
be attacked by microorganisms. The hydrolysis process is
also dependent on the local order of the macromolecule.
Unordered macromolecules are more susceptible to hydrol-
ysis (acid hydrolysis). Complex macromolecules, such as
lignin, which is a natural polymer, are less degradable than
synthetic polymers like aliphatic polyesters, confirming
that the molecular composition and architecture determine
the accessibility of a polymer to degradation by micro-
organisms. As described by Ratajska and Boryniec [40], the
mechanism of biodegradation by microorganisms primar-
ily occurs through an attack on the surface of the biode-
gradable fragments. By removing the fragments, the
porosity of the material increases, allowing the permeation
of water with the microorganisms that may cause mechan-
ical stress facilitating the process of degradation by the
enzymes produced.
The processes of biodegradation described in the
literature are, in general, associated with the hydrolysis
caused by added enzymes or those produced by the micro-
organisms, and can be followed by changes in molecular
weight, viscosity, and morphology. For example, in Fig.
3A,B, the molecular weight distribution for the biodegra-
dation process of pure viscose (cellulosic) fibers and mix-
ture with 30% of cellulose carbamate, respectively, are
shown under conditions of controlled temperature and
humidity of the air and soil [40]. For both systems, a
significant decrease in the molecular weight was observed
after the enzymatic degradation. The biodegradation pro-
cess was also analyzed by the authors in terms of the degree
of polymerization (DP) observing that for pure viscose, it
decreased from 268 (untreated) to 53 after 6 months in
contact with the microorganisms. For the viscose with 5%
(figure not shown) and 30% of cellulose carbamate, the
ranges of DP variation under the same conditions were
278–48 and 159–55, respectively.
The treatment of pectin extracted by autoclave from
sugar beet pulp (ABP), with enzymes to modify their
physicochemical properties, was studied by Ooterweld et
al. [41]. The experimental procedure included the dissolu-
tion of the samples in 0.04 sodium acetate buffer containing
0.01% of NaN3 (pH 5.0) to a final concentration of 5 mg/
mL. The enzymes arabinofuranosidase B (AF), endo-
arabinanase plus arabinofuranosidase (EA + AF), rham-
nogalacturonase plus rhamnogalacturonan acetyl esterase
(Rgase + RGAE), polygalactorunase plus pectin methyl
Stability and Degradation of Polysaccharides 399

radation was observed by the authors when polygalactor-

unase plus pectin methyl esterase (PG + PE) was used,
suggesting that changes in the physicochemical properties
depend on the chemical structure of the ABP. These
conclusions seem consistent if we consider that the struc-
ture of ABP consists mainly of homogalacturonans and the
enzyme used was polygalactorunase.
The effect on the molecular weight and structure of N-
acetylated chitosan by hemicellulase was studied by Qin et
al. [42]. For a sample with a degree of deacetylation of 73.2,
the Mw decreased from 659,000 to 4200 kDa when the
chitosan was submitted to degradation by hemicellulase for
4 hr at 50jC and pH 5.5. The effect observed in the Mw was
accompanied by an increase in the water solubility and
decrease in the thermal stability. For the authors, the
results suggested that the enzymatic hydrolysis was endo-
action and mainly occurred in a random fashion.

Figure 3 Molecular weight distribution of (A) 100% viscose

fibers and (B) viscose fibers containing 30% of cellulose
carbamate: (a) untreated, (b) treated for 3 months, (c) treated
for 6 months. (From Ref. 40.)

esterase (PG + PE), were added to a final concentration of

1 Ag protein/mL. Incubations were carried out at 20jC for
42 hr. The digests were analyzed in terms of the molecular
weight (Mw) at several stages of the incubation by high-
performance size-exclusion chromatography (HPSEC).
During the enzyme treatment, other parameters such as
the intrinsic viscosity ([g]w) and radius of gyration (Rgw) of
the polysaccharides were monitored. The behavior ob-
served for the above parameters is shown in Fig. 4A–C.
The Mw decreased from 271 to 112 kDa when ABP was
treated with RGase + RGAE. This effect was associated
with the hydrolysis of the rhamnogalacturonan backbone
present in the ABP. For the same enzymes, no significant
changes were observed in the intrinsic viscosity ([g]w) and
radius of gyration (Rgw). By adding EA + AF to ABP, the
Mw decreased to 207 kDa but a small change occurred in
the ([g]w) and (Rgw). However, by adding PG + PE, the
intrinsic viscosity ([g]w) and radius of gyration (Rgw) Figure 4 Effect of enzymatic modification of sugar beet
showed a significant decrease (Fig. 4B,C) and the Mw pulp, ABP, on (A) Mw, (B) [g]w, and (C) Rgw: () EA + AF;
decreased to 5 kDa. A greater effect on the enzyme deg- (z) Rgase + RGAE; (.) PG + PE. (From Ref. 41.)
400
The biodegradation of the ethyl(hydroxyethyl cellu-
lose) (EHEC) by endoglucanases was studied by Richard-
son et al. [43]. Ethyl(hydroxyethyl cellulose) is a nonionic,
water-soluble cellulose derivative produced by introduc-
tion of ethyl and ethylene oxide groups to the hydroxyl
groups of the cellulose backbone. In general, the endoglu-
canases, which are enzymes for the cellulose hydrolysis,
cleave the internal (1–4)-h-D-glucosidic linkages in the
cellulose chain, producing smaller fragments of mono-
and oligosaccharides [44]. From the literature, is known
that endoglucanases hydrolyze unmodified cellulose to
low-molar-mass products such as glucose, cellobiose, and
cellotriose [45]. For EHEC, the authors used two types of
endoglucanase from Trichoderma reesei (Cel7B, Mw f
50,000 Da and Cel12A, Mw f 24,500 Da). The hydrolysis
products were analyzed by size-exclusion chromatography
with multiangle light scattering and refractive index detec-
tion (SEC-MALS-RI). The molar mass distribution for
two samples of EHEC with degrees of substitution (DS;
average number of hydroxyl groups in the monomer unit
substituted with ethyl) 0.9 (E481-02506) and 0.7 (EHMO),
are shown in Fig. 5A and B, respectively. For the EHEC
with DSethyl = 0.7 (EHM0), the molar weight of the
hydrolysis products after being treated with Cel7B and
Cel12A were 83,000 and 102,000 g mol
1, respectively,
which are values significantly lower than those for the
intact EHM0 (Mw = 359,000 g mol
1). However, a higher
Figure 5 Molar mass distribution of (A) intact E481-02506, E481-02506 hydrolyzed by Cel7B, and E481-02506 hydrolyzed by
Cel12A; (B) intact EHMO, EHMO hydrolyzed by Cel7B, and EHMO hydrolyzed by Cel12A. (From Ref. 43.)
Soldi
degradation was observed for the sample with DSethyl =
0.9 (E481-02506) (Fig. 5B). The Mw decreased from
772,000 (intact sample) to 57,000 and 67,000 g mol
1, for
products obtained by hydrolysis with the same enzymes,
respectively. The action of endoglucanase on caboxy-
methylcellulose (CMC) also decreased the molecular
weight when samples with DS 0.6 and 1.2 were submitted
to enzyme degradation (0.2% solution) for 92 hr at 45jC
[46]. For the sample with DS 0.6, the molecular weight
decreased from 249,000 to 10,700 g mol
1. The significant
decrease observed by the authors in the above value, in
comparison to the sample with DS 1.2 in which the Mw
changed from 248,000 to 72,000 g mol
1, indicated that the
endoglucanase accessed more easily the sample with low
DS. However, for EHEC, the greater effect was observed
for the sample with DSethyl 0.9, suggesting that the access of
the enzyme to the internal (1–4)-h-D-glucosidic linkages
was more favorable. These opposite effects indicated that a
more heterogeneous distribution of substituents occurred
in the sample with DSethyl 0.9.
The effects on the viscosity were also described as
being associated with enzymatic degradation processes.
For example, the enzymatic degradation of caboxymethyl-
cellulose (CMC) by endoglucanase significantly decreased
the intrinsic viscosity [46]. For samples with DS 0.6 and 1.2,
the viscosity decreased from 750 to 8.4 mL g
1 and from
690 to 108 mL g
1, respectively. As was pointed out above,
Stability and Degradation of Polysaccharides 401

the viscosity values indicate that the endoglucanase
accessed more easily the sample with a low degree of
substitution. Chitosan and substituted chitosans (methyl
pyrrolidinone chitosan, N-carboxymethyl chitosan) also
showed a rapid decrease in viscosity when samples were
submitted to degradation in solutions with wheat germ
lipase [47].
IV. THERMAL DEPOLYMERIZATION
As was pointed out in the above sections, the depolymer-
ization processes of polysaccharides are normally studied
in terms of hydrodynamic properties such as intrinsic
viscosity ([g]) and average molecular weight (Mw). In
general, both properties decreased during thermal, hydro-
lytic, and oxidative processes and are affected by pH,
heating temperature range (reaction temperature), process-
ing time, mechanical shear, solvent quality, polysaccharide
concentration, and experimental conditions. For structur-
ally related series of polysaccharides, the chemical reac-
tions of degradation are associated with changes in
enthalpy and entropy, which can be described by kinetic
parameters such as Ea (activation energy) and A (pre-
exponential factor) derived from the Arrhenius equation
[(Eq. 2)]. Depolymerization processes are commonly de-
scribed by equations that consider that the chain scission of
the glycosidic linkage of polysaccharides follows a pseudo
first-order reaction [48,49]. The rate constant will be related
to the molecular weight through Eq. (1), which indicates
that the inverse of the molecular weight increased linearly
with the depolymerization time and, in consequence, the
rate constant (k) can be obtained from the slope of the
corresponding plot.
The degradation rate (k) can also be described in terms
of the intrinsic viscosity by Eq. (4), which was derived
combining Eq. (1) and the Mark–Houwink–Sakurada
equation ([g] = KM a), where K and a are constants for a

Figure 6 Apparent viscosity of 1% solutions of thermally degraded chitosan chlorides with degree of acetylation (*) 0.02, (5)
0.16, and (.) 0.35 vs. degradation time at (A) 60jC, (B) 80jC, (C) 105jC, and (D) 120jC. The degradation time for A and B is
given in days, while for C and D it is given in hours. (From Ref. 48.)
402 Soldi

given system. In Eq. (4), [g]t and [g]0 are the viscosities at
time t and 0, respectively
 
1 1 k same time, a more accentuated decreased was observed

¼ t ð4Þ
½g1=a ½g
1=a Mm K1=a
t 0
For processes such as thermal- or acid-catalyzed degrada-
tion, the rate constant can be obtained by plotting the
differences between the inverses of the viscosities vs. the
degradation time. For a given system, the degradation rates
at different temperatures can be used to determine the
kinetic parameters through the Arrhenius equation [Eq.
(2)].
Polysaccharides such as dextran [50], chitosan [11],
chitosan chloride [48], N-succinyl chitosan [26], agarose
[24,49], and n-carrageenan [24,49], are examples in which
the thermal depolymerization was followed by measuring
the apparent and intrinsic viscosity. For example, the
viscosity behavior of 1% solutions of thermally degraded
chitosan chloride [48] at four temperatures and three
acetylation degrees is shown in Fig. 6. An exponential
decrease was initially observed for all the systems studied
independently of the temperature or acetylation degree.
With the extended period of time, the viscosity decreases at
a lower rate as a consequence of the chain scission. At the
with the increase in temperature and degree of acetylation.
The degradation rates were determined by the authors
from the slopes of the D1/[g](1/a) vs. t plots (Fig. 7),
considering Eq. (4). The values increased with both acety-
lation degree and temperature. For example, at 120jC, k
increased from 120  10
6 to 1450  10
6 hr
1 when the
acetylation degree increased from 0.02 to 0.35, respec-
tively. At the same time, for an acetylation degree of 0.35,
k increased from 3.5  10
6 to 1450  10
6 hr
1 when
the temperature increased from 60jC to 120jC. There-
fore the authors observed that regardless of the temper-
ature, the degradation rates of the chitosan chloride with
an acetylation degree of 0.35 was about ten times greater
than those determined for a chitosan with an acetylation
degree of 0.02, indicated a dependence on the chemical
composition. On the other hand, the results also indicated
that the effect on the viscosity was more significant as the
temperature increased.

Figure 7 Time course of thermal degradation of chitosan chlorides with degree of acetylation (*) 0.02, (5) 0.16, and (.) 0.35 at
(A) 60jC, (B) 80jC, (C) 105jC, and (D) 120jC. The degradation time for A and B is given in days, while for C and D it is given in
hours. (From Ref. 48.)
Stability and Degradation of Polysaccharides 403

Food polysaccharides such as agarose and n-carra-

geenan were studied by Lai et al. [49] in terms of the kinetics
of the depolymerization process. As observed in Fig. 8, the
intrinsic viscosity decreased linearly with time, showing a
certain dependence on temperature within a range of 75–
95jC. From the slope of the plots using Eq. (4) (Fig. 9), the
authors determined the rate constants for the depolymer-
ization processes, observing that the values increased by
two- to threefold for a temperature increment of 10jC. The
rate constants were in the range of 0.2–1.6  10
4 and 0.2–
1.3  10
6 sec
1 for agarose and n-carrageenan, respec-
tively, within the temperature range of 75–95jC. Appar-
ently, the access to the glycosidic linkage was more
favorable for agarose.
The thermal degradation of cellulose was studied by
Phillip [10] within the temperature range 100–200jC con-
sidering the effect on the zero-order rate constant. For the
degradation reactions of cellulose in N2 + O2 and N2 +

Figure 9 Time dependencies on viscosity considering Eq. (4)

for agarose (A) and n-carrageenan (B) depolymerized at 75–
95jC. (From Ref. 49.)

H2O, the rate constant values were in the range of 0.6–40 

Figure 8 Plots of intrinsic viscosity, [g], against heating time
for agarose (A) and n-carrageenan (B) depolymerized at 75–
95jC. (From Ref. 49.)
10
5 DP
1 hr
1 when the temperature changed from
100jC to 200jC. However, in comparison to the degrada-
tion reaction in N2 atmosphere, the above rate constants
were up two to eight orders of magnitude higher. Under
these conditions, the chain scission produced different
amounts and species of volatile low-molecular compounds
and of char. When only air was used, the mechanism of
thermal degradation of cellulose was described as having
three stages, which included dehydroxylation (preheating
and preliminary drying for removing absorbed water),
carbonization, and oxidative degradation [51]. Depending
on the heating rate, conjugate stages occurred. In the
process of the thermal degradation of cellulose and chitin
in supercritical acetone, a very slight evolution of gases was
404
observed [6]. The authors assumed that approximately
98% of the cellulose is in fact liquefied.
The intrinsic viscosity and average molecular weight of
high methoxy pectin was evaluated at various temperatures
(20–60jC) [52]. The results presented in Fig. 10A,B, for
viscosity and Mw, respectively, indicated a similar behav-
ior; that is, a decrease with temperature. For viscosity, the
observed effect must be associated with the molecular
breakdown of the chain and a conformational change to
a more compact structure. The decrease in molecular
weight was apparently due to the a h-elimination mecha-
nism suggested by the authors.
The thermal stability of natural polymers, such as,
sodium hyaluronate, xanthan, and methylcellulose in ni-
trogen atmosphere were compared considering the kinetic
and thermogravimetric parameters [53]. The results indi-
cated a higher thermal stability for methylcellulose, which
is a neutral polysaccharide. This conclusion was supported
by both the maximum degradation temperature and acti-
vation energy. Similar behavior was described by Khomu-
tov at al. [54] in studies of thermooxidative degradation of
anionic polysaccharides. They concluded that the thermal
stability increased with a decrease in the charge of the
macromolecule.
Figure 10 Effect of increased temperature on the intrinsic
viscosity, [g] (A) and average molecular weight, Mw (B) for a
high-methoxy pectin in standard phosphate chloride buffer
(pH = 6.8, I = 0.1 M). (From Ref. 52.)
Soldi
In the processes of thermal degradation, the kinetic
parameters (activation energy and pre-exponential factor)
are important to analyze the reaction mechanism and
thermal stability of different macromolecules. In Table 1,
the activation energy and pre-exponential factor associated
with different processes of degradation for a series of
polysaccharides were compared. In general, and regardless
of the degradation conditions, the activation energy change
with the mass loss fraction in polysaccharides, also indi-
cating changes in the reaction mechanism. For example, in
the thermal degradation of sodium hyaluronate, xanthan,
and methylcellulose in nitrogen atmosphere, the activation
energy determined by the Ozawa method [55,56] changed
from ca. 100 to 170 kJ mol
1 [53]. For the above-mentioned
polysaccharides, the activation energy in Table 1 represents
average values. Variation in the activation energy with the
mass loss fraction was also observed for chitosan and a
mercaptan derivative of chitosan in both nitrogen and air
atmospheres [57]. For these systems, the activation energy
varied from ca. 100 to 250 kJ mol
1. Another interesting
aspect relating to the values in Table 1 concerns the
comparison between processes of thermal degradation that
occurred in air (oxidative) and nitrogen atmosphere. Cel-
lulose and starch showed similar activation energy values
(58.5 and 50.0 kJ mol
1, respectively) when the thermal
degradation process occurred in air [58]. In nitrogen atmo-
sphere, the activation energies were 242 and 474 kJ mol
1
for cellulose and starch, respectively. The extremely high
value observed for starch in nitrogen was not expected if we
consider the similarity in the chemical structures of both
polysaccharides. However, the authors explained it by the
small mass loss (carbonaceous residue) observed for cellu-
lose at temperatures above 400jC.
The thermogravimetric curves for sodium alginate in
air showed two main stages of degradation with Tmax
(temperature of maximum degradation rate) at 240jC
and 380jC [59]. The activation energy determined by the
Broido method [60] were 171.4 and 174.4 kJ mol
1 for the
above two stages of degradation, respectively. These values
were about three times higher than those observed for
starch and cellulose under the same conditions (air), indi-
cating a high dependence on the structure, and probably on
the conformation, of the polysaccharides. For copolymers
of sodium alginate with acrylonitrile, methyl acrylate, ethyl
acrylate, and methyl methacrylate, the activation energies
decreased to values in the range 60–90 kJ mol
1 in the first
stage (Tmax = 240jC) and increased up to ca. 240 kJ mol
1
in the second stage.
The activation energy values presented in Table 1
clearly show some differences in magnitude when different
degradation processes are used. For example, in the chem-
ical degradation of chitosan, values in the range 80–100 kJ
mol
1 were determined. When chitosan was degraded by a
thermal process, values of 181 kJ mol
1 (in nitrogen) and
160 kJ mol
1 (in air) were obtained. The significant differ-
ence was apparently associated to the easier access of the
chemical agents (acid) to the glycosidic bonds. Another
interesting point is the similarity in the activation energy
observed for most of the polysaccharides in Table 1,
Stability and Degradation of Polysaccharides 405

Table 1 Activation Energy and Pre-Exponential Factor for Polysaccharide Depolymerization

Polysaccharides E (kJ mol
1) A (min
1) Degradation process Reference
16
Cellulose 58.5 (air) 3.4  10 Thermal 58
83.7 (air) 3.4  109 Thermal 61
242.(N2) 6.3  1020 Thermal 58
189–199.(N2) — Thermal 62
D-glucose 174. (N2) — Thermal 62
Cornstarch 50. (air) — Thermal 58
474.(N2) 2.0  1042 Thermal 58
Sodium alginate 171.4 (air) — Thermal 59
Xanthan 130 — Thermal 53
Sodium hyaluronate 135 — Thermal 53
Methycellulose 140 — Thermal 53
Chitosan 87.1 — Nitrous acid 12
130 — Acid hydrolysis 63
92 — Alkaline hydrolysis 64
181.(N2) 1.6  1014 Thermal 57
160.(Air) 4.8  1012 Thermal 57
Chitosan chloride 109 — Thermal 48
Chitin 124 — Acid hydrolysis 65
n-Carrageenan 105 5.3  1012 Hydrolyze, pH 2 27
113 2.5  1013 Hydrolyze, pH 2 28
126 4.6  1015 Hydrolyze, pH 2 29
120 3.2  1016 Hydrolyze, pH 2 14
97.2 7.0  107 Water, pH 7 49
L-Carrageenan 162 1.3  1021 Hydrolyze, pH 2 27
133 7.4  1017 Hydrolyze, pH 2 14
E-Carrageenan 116 1.9  1013 Hydrolyze, pH 2 27
Dextran sulfate 103 9.7  1010 Hydrolyze, pH 2 27
Agarose 103 7.8  1010 Water, pH 7 49

submitted to thermal degradation in nitrogen atmosphere.
The values varied from ca. 100 to 150 kJ mol
1, suggesting
that the mechanism of degradation was, generally, by
random scission of the chain. This conclusion was consis-
tent with the large number of different products (residue
and volatile products) detected in the degradation of poly-
saccharides which is partially discussed in the next section.
The activation energy values of cellulose (242 kJ mol
1)
and starch (474 kJ mol
1) determined by thermal degra-
dation in nitrogen atmosphere were in apparent discrep-
ancy with most of the polysaccharides in Table 1.
V. PRODUCTS OF DEGRADATION
Products of degradation in polysaccharides have been
determined mainly in systems submitted to thermal and
pyrolytic degradation or chemical degradation at high
temperatures [33,51,53,66–75]. In this section, some exam-
ples concerning these processes are analyzed.
Cellulose has been one of the most extensively studied
polysaccharides not only in terms of the processes of
degradation, but also in terms of the reaction products of
degradation and pyrolysis under different conditions. For
example, the amount of water evolved from cellulose
heated isothermally at 250jC was determined through
thermogravimetry-Fourier transform infrared (TG-FTIR)
techniques (Fig. 11A) [51]. The water is produced in a great
amount in comparison with other products as shown in
Fig. 11A. Another significant effect was observed when
cellulose was heated to 170jC in air (oxygen) (Fig. 11B)
[51]. The water evolution was observed to be much higher
in air than in nitrogen, because under these conditions,
hydroperoxide groups are formed, which can dissociate to
give hydroxyl radicals. The water is formed from hydroxyl
radicals by hydrogen abstraction. A detailed mechanism of
cellulose degradation was described by Scheirs et al. [51]
considering the water evolution from cellulose after heat-
ing to different temperatures. Up to ca. 300jC, a dehydra-
tion process occurred that corresponded to the evolution of
physical and chemical water. As suggested by the authors,
the evolution of chemical water occurs by intramolecular
elimination (from carbons 2 and 3 of the monomeric unit)
with the formation of anhydrocellulose (enol or keto
forms). At the same temperature, cross-linking by ether
linkages due to the intermolecular elimination between the
hydroxyl groups may occur. The degradation at temper-
atures higher than 300jC induced elimination of water
from the carbon 6 forming a vinylene group. Other reac-
tions such as ring rearrangement, which apparently oc-
406
Figure 11 Water evolution from (A) cellulose as measured
by TG-FTIR technique. (B) Heating cellulose at 170jC in
oxygen and nitrogen. (From Ref. 51.)
curred after the initial water elimination, lead to further
water loss producing furanic species.
Richards [66] used gas chromatography and 1H NMR
techniques to identify the pyrolysis products of filter paper
(cellulose) under nitrogen at 350jC. Glycolaldehyde, for-
mic acid, 1-hydroxypropan-2-one, acetic acid, and ethylene
glycol were identified as the main reaction products. Gly-
colaldehyde was the major product of the pyrolysis with
yields up to 9.2%. As described in the literature [67], the
formation of glycolaldehyde includes two initial steps: (1)
the formation of levoglucosan from cellulose and (2)
glucose from levoglucosan. Reaction products, such as
formic, acetic, glycolic, and lactic acids (in a total yield of
30% based on cellulose), were formed by alkaline degra-
dation of cellulose [33]. In the presence of 10% sodium
chloride, the yield of glycolaldehyde decreased to 4.8%, the
yield of 1-hydroxypropan-2-one (4.2%) increased at the
same time, suggesting that in the presence of salt, lactone
Soldi
was preferentially formed. These results were supported by
previous studies related to the pyrolysis of curdlan a
(1!3)-h-D-glucan in which the presence of sodium chlo-
ride favored lactone formation [68]. The degradation of
glucose in alkaline media [aqueous solution of Ca(OH)2] at
100jC produced a complex mixture with more than 50
compounds (saccharinic acids) [69].
Recently, Chen et al. [70] analyzed the volatile com-
pounds generated by the thermal degradation of gluco-
samine and N-acetylglucosamine, which are the monomer
forms of chitosan and chitin, respectively. Gas chromatog-
raphy and gas chromatography/mass spectrometry tech-
niques were used to identify the main degradation products
after maintaining the samples at 200jC for 30 min. The
degradation of N-acetylglucosamine produced mainly 3-
acetoamido-5-acetylfuran and 2-acetylfuran. According to
the authors, the formation mechanism for the above com-
pounds basically included successive dehydration steps
that occurred when the monomeric unit was maintained
at 200jC. Another 13 compounds were identified in the
same degradation reaction, which to include furans, pyr-
idines, pyrroles, and pyrazine derivatives. Studies related to
the thermal degradation of glucosamine were previously
reported by Chen and Ho [71]. They identified a series of
furyl-substituted pyrazines.
The glucan pyrolysis produced one-, two-, and three-
carbon compounds: glycolaldehyde, acetol (hydroxipropa-
none), acetic and formic acids [72]. The pyrolytic behavior
for all the glucans studied was the same [73]. This behavior
suggests that the nature of the glycosidic linkages in a given
glucan has little effect on major reaction pathways.
The FTIR analysis of the residual products of the
thermal degradation of sodium hyaluronate was described
by Villetti et al. [53]. The analysis at 280jC (the tempera-
ture of maximum degradation rate) indicated that the
bands associated with exocyclic groups (1150, 1079, and
1042 cm
1) and NH stretching (1320 cm
1) disappeared
characterizing the cleavage (scission) of the glycosidic
linkage in the main chain. With a temperature increase
(>400jC), the scission of strong links in the backbone
occurred.
Radlein et al. [74] considered the existence of two
decomposition pathways in the pyrolysis of cellulose. At
temperatures lower than 300jC (slow decomposition), the
pyrolysis reaction produced mainly char and gases, con-
firming previous results described by Shafizadeh [75], which
suggested that in the range 150–190jC, a reduction in the
degree of polymerization, elimination of water, formation
of carbonyl, carboxyl and hydroperoxide groups, and
evolution of carbon mono- and dioxide occurred. Practi-
cally the same products were identified by TG-FTIR (Fig.
11A) from cellulose heated isothermally to 250jC [51]. A
second pathway was related to the pyrolysis at temper-
atures higher than 300jC (fast decomposition). At temper-
atures close to 500jC, for example, the main products of
degradation were hydroxyacetaldehyde and levoglucosan
with yields up to 15.3% and 38.4%, respectively, depending
on the cellulose source and temperature. Other prod-
Stability and Degradation of Polysaccharides
ucts such as acetic acid, formic acid, and acetol were
identified by the authors with yields in the range of 5–10%.
VI. CONCLUSIONS
In this chapter, three different polysaccharide degradation
processes were analyzed in terms of effects on viscosity and
the average molecular weight. The processes clearly indi-
cate a dependence on experimental conditions (pH, tem-
perature, reactive agents) and, on the structure and
conformation of the polysaccharides. The effects on vis-
cosity and average molecular weight were quite similar if
we consider that both decreased with the extent of degra-
dation (treated time). In chemical and thermal degradation
processes, the predominant mechanism for the chain scis-
sion is the breakdown of the glycosidic bonds in the
macromolecule, which occurs in a wide range of polysac-
charides. In biodegradation, the local order of the macro-
molecule seems to be important. As initially only one bond
is hydrolyzed by enzymatic attack, unordered macromole-
cules are more susceptible to hydrolysis. Secondary cleav-
ages occur on one of the fragments produced by the initial
scission. Enzymatic degradation does not follow any of the
typical modes (random, gaussian) of chain scission. Dif-
ferently to the biodegradation, the thermal degradation of
polysaccharides occurs by random scission of the chain as
indicated by the activation energy values that are higher
than 100 kJ mol
1 for most of the polysaccharides. Simi-
larly, the degradation of guar, agarose, and carrageenans
by ultrasound occurs also by random scission of glycosidic
linkages [23–25]. In the degradation of cellulose and starch
in the presence of air, the activation energy has been found
to be lower than 100 kJ mol
1 (58.5 and 50.0 kJ mol
1,
respectively), indicating a lower thermal stability for both
polysaccharides. In terms of the products of degradation
resulting from thermal processes, polysaccharides produce
mainly acids and other specific compounds depending on
the structure and conformation of the macromolecules and
experimental conditions. For example, glycolaldehyde is
formed in great yields from cellulose degradation. As
glycolaldehyde is formed from the glucose monomeric unit,
two initial steps occur: the formation of levoglucosan from
cellulose and of glucose from levoglucosan.
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