June 2008 Published by the American Chemical Society Volume 9, Number 6

 Copyright 2008 by the American Chemical Society

Reviews
Sustainable Films and Coatings from Hemicelluloses: A Review
Natanya M. L. Hansen and David Plackett*
Risø National Laboratory for Sustainable Energy, Technical University of Denmark, P. O. Box 49, DK-4000
Roskilde, Denmark
Received January 17, 2008; Revised Manuscript Received March 5, 2008

This review summarizes the results of past research on films and coatings from hemicelluloses, biopolymers that
are as yet relatively unexploited commercially. The targeted uses of hemicelluloses have primarily been packaging
films and coatings for foodstuffs as well as biomedical applications. Oxygen permeability of hemicellulose films,
an important characteristic for food packaging, was typically comparable to values found for other biopolymer
films such as amylose and amylopectin. As expected, the modification of hemicelluloses to create more hydrophobic
films reduced the water vapor permeability. However, modified hemicellulose coatings intended for food still
exhibited water vapor permeabilities several magnitudes higher than those of other polymers currently used for
this purpose. Research on hemicelluloses for biomedical applications has included biocompatible hydrogels and
coatings and material surfaces with enhanced cell affinity. Numerous possibilities exist for chemically modifying
hemicelluloses, and fundamental studies of films from modified hemicelluloses have identified other potential
applications, including selective membranes.

Introduction glycosidic linkages occur in certain seaweeds. Heteroxylans

Sustainable sources of materials to supply the needs of society
in the coming decades are much needed at present as the world
becomes increasingly aware of the limited nature of fossil fuels.
In response to this situation, lignocellulosic biomass from trees,
grasses, cereals, and other plants, has become the main focus
of the developing biorefining industry.1 Plant materials are
primarily made up of three main types of biopolymer: cellulose,
lignin, and hemicellulose, and of these, cellulose and lignin have
received by far the most attention in terms of material applica-
tions. While cellulose has a unique structure, the term hemi-
cellulose is used to describe a number of noncrystalline hexose
and pentose sugars. Traditionally, hemicellulose is defined as
the alkali-soluble material after the removal of pectic substances
from plant cell walls.2 Four main groups of hemicelluloses may
be defined according to their primary structure: xyloglycans
(xylans), mannoglycans (mannans), β-glucans, and xyloglucans.3
Subgroups are further defined within the main groups.
In most cases, xylans consist of a β(1f4)-D-xylopyranose
(Figure 1) backbone with side groups on the 2- or 3-position.
Nonbranched homoxylans with β(1f3, 1f4) or β(1f3)
* To whom correspondence should be addressed. E-mail: david.plackett@
risoe.dk.
10.1021/bm800053z CCC: $40.75
Published on Web 05/06/2008
include glucuronoxylans and arabinoxylans as well as structures
with more complex substitution patterns often referred to simply
as heteroxylans. Glucuronoxylans have a side chain on the
2-position of either R-D-glucuronic acid or its 4-O-methyl
derivative, while arabinoxylans are substituted on position 2
and/or 3 with R-L-arabinofuranosyl residues.
Two types of mannans exist, namely, galactomannans con-
sisting of β(1f4) linked D-mannopyranoses and glucomannans
comprised of D-mannopyranose and D-glucopyranose with
β(1f4) linkages. Both types of mannoglycans have varying
degrees of branching with D-galactopyranose residues in the
6-position of the mannose backbone. β-glucans have a D-
glucopyranose backbone with mixed β linkages (1f3, 1f4)
in different ratios and can form highly viscous solutions and
gels.3
Xyloglucans have a backbone of β(1f4) linked D-glycopy-
ranose residues with a distribution of D-xylopyranose in position
6. The distribution of the side chains divides the xyloglucans
in two categories: one with two xylopyranose units followed
by two glucopyranose units (termed XXGG) and one with three
xylopyranose units followed by a single glucopyranose unit
(termed XXXG). Additionally, a number of side chains occur
 2008 American Chemical Society
1494 Biomacromolecules, Vol. 9, No. 6, 2008
Figure 1. Main constituents of hemicelluloses.
on xyloglucans, including R-L-arabinofuranose, which makes
the characterization of this group of hemicelluloses especially
challenging.
Research on some of the hemicelluloses has been extensive.
Konjac glucomannan derived from the tuber Amorphophallus
konjac is an example. This hemicellulose has been utilized
commercially for many years,4 but research has recently
intensified because of the gel- and film-forming properties as
well as biocompatibility and biodegradability of this polysac-
charide. These properties have found use in numerous applica-
tions in areas such as drug delivery, cellular therapy, encapsu-
lation, and emulsification.5 Another example of an extensively
used hemicellulose is xyloglucan from tamarind seed, which is
also utilized in drug delivery. The use of this and other
polysaccharides for hydrogels in release formulations is the topic
of a recent review by Coviello et al.6
Hemicellulose in the plant cell wall is bound to cellulose and
lignin and detailed isolation procedures are required to separate
these components from plant raw material. The composition of
hemicellulose varies between different feedstocks, as well as
between sources, depending on factors such as origin and growth
stage. An example is a recent study of four rice varieties, which
showed significant variations of the main components arabinose
(5–23%), xylose (17–40%), and glucose (36–55%) between the
different cultivars.7 A number of methods are used to obtain
hemicelluloses from plant sources, including extraction with
alkali, dimethyl sulfoxide, or methanol/water, as well as steam
or microwave treatment.8 The composition of the extracted
hemicellulose can be highly dependent on the isolation process
and, for example, deacetylation, degradation, and contamination
with lignin can occur. Work by Sun et al.9 illustrates the
dependency of composition on the isolation procedure, as the
pretreatment of wheat straw samples with various organic
solvents before extraction resulted in markedly different hemi-
cellulosic products (Table 1).
This review is written in the context of ongoing biofuels
research at Risø DTU10–12 and an interest in exploring higher
value uses for hemicelluloses generated as a byproduct from
bioethanol production. For this reason, a review of past research
on material applications of plant-derived hemicelluose was
considered appropriate so that potential new research directions
might be identified. In the following, we review past research
on the use of hemicelluloses to form films and coatings. Existing
patents and filed patent applications in the field are also
discussed.
The formation of films from hemicellulose acetates was
reported as early as 1949 by Smart and Whistler.13 Films and
coatings from renewable materials have numerous potential
applications in the food and medicinal industry including active
food packaging, wound dressings, and drug capsules.14–19 The
use of a plasticizer is often necessary to ensure flexibility and
the most commonly used for hemicellulose films are sorbitol,
glycerol and xylitol (Figure 2).
Hansen and Plackett
Hemicelluloses are hydrophilic in nature and films produced
from these materials are generally hygroscopic, resulting in poor
properties in environments with high humidity. As recently
described in review papers, chemical modification of the
polymer by either bulk or surface modification is a way to
circumvent these problems.3,8,20,21 Hemicellulose, like cellulose,
has an abundance of free hydroxyl groups distributed along the
backbone and side chains and is, therefore, an ideal candidate
for chemical functionalization. By forming hemicellulose de-
rivatives through functionalizing available hydroxyl groups,
properties such as crystallinity, solubility, and hydrophilicity
may be modified. Researchers have explored these options using
techniques such as esterification, etherification, or grafting
methods. Hemicellulose esters have been formed through
reactions with acid chlorides or anhydrides. For example,
acetylation of hemicellulose can be performed under similar
conditions as for cellulose with an expected increase in
hydrophobicity. Sulfation has been used to enhance biological
activity. Etherification reactions including carboxymethylation,
alkylation, and benzylation have been explored, while cationic
moieties have been introduced by various pathways. The free
hydroxyl groups in hemicellulose have been used as initiator
sites to perform polymerizations of a number of monomers to
form grafts.8
Packaging
The use of renewable resources for the production of food
packaging in particular has recently received increased interest.22–24
Depending upon the application, low oxygen permeability as
well as mechanical strength and flexibility can be important
target properties for such packaging films.
The ultimate goal of a study performed by Höije et al.25 was
to produce oxygen barrier films or coatings. However, the main
focus of the investigations was the influence of the pretreatment
utilized in the isolation of hemicellulose from barley husks.
Arabinoxylan was subjected to four different types of pretreat-
ment before alkaline extraction: enzyme pretreatment, acidic
pretreatment, or acidic pretreatment combined with either
chlorite or organosolv (ethanol) delignification. The purpose of
the prehydrolysis step was to remove proteins and delignification
was shown to be essential to achieve this objective. The type
of treatment had a great impact on the yield of arabinoxylan as
well as the molecular weights of the final product (Mw )
35000–45000 g mol-1). The four extracted arabinoxylans were
soluble in hot water and could be cast as colored films. The
chlorite delignification was deemed to be the most efficient (57%
yield), and films cast from this arabinoxylan were studied
extensively. The films were strong, with a stress at break of
more than 50 MPa, elongation at break of 2.5%, and a Young’s
modulus of 2900 MPa. Furthermore, the films were shown to
be highly hygroscopic with a primarily amorphous structure.
Oxygen barrier properties of glucuronoxylan from aspen
wood have been examined by Gröndahl et al.26 Films from
unmodified xylan were brittle (Tg ∼ 180 °C), and therefore,
sorbitol and xylitol were used as plasticizers in concentrations
of 20, 35, and 50 wt %. The glass transition of the plasticized
films was determined by differential scanning calorimetry (DSC)
to be below ambient temperature. All the films were semicrys-
talline (44–47%), regardless of plasticizer content. Tensile
testing showed that the addition of 20 wt % plasticizer resulted
in stress at break of more than 40 MPa; however, the elongation
was only 2%. Increasing the plasticizer content resulted in a
reduction of strength and concurrent increase in elongation.
Sustainable Films and Coatings from Hemicelluloses
Table 1. Sugar Composition (Weight: % of Total Weight Hemicellulose) of Wheat Straw Samples Subjected to Different Organic Solvent
Pretreatmentsa
acetic acid-H2O formic acid-acetic acid-H2O
(80/20, v/v) (20/60/20, v/v/v)
arabinose 3.0
xylose 80.3
mannose 0.4
galactose 1.1
glucose 15.1
uronic acids 5.5
Mw 14650
Mw/Mn 6.0
a
With 0.1% HCl as catalyst at 85 °C for 4 h. Post-treatment with 1.8% H2O2-0.18% NH2CN at 50 °C and pH 10 for 4 h.9
Figure 2. Commonly used plasticizers for the formation of films from
hemicellulose.
Figure 3. Gas-phase fluorination of hydroxyl groups of arabinoxylan
with trifluoroacetic anhydride.28
Sorbitol addition had the most pronounced effect on elongation.
The storage modulus decreased with humidity, while increased
plasticizer amount had the same effect. An oxygen permeability
of 0.21 cm3 µm m-2 d-1 kPa-1 at 50% RH was reported for a
film plasticized with 35 wt % sorbitol, which was identical to
the value found for a poly(vinyl alcohol) (PVOH) film under
the same conditions. PVOH is an excellent barrier material with
good thermal and mechanical properties that, furthermore, is
water soluble and biodegradable.27
Surface fluorination of arabinoxylan (AX) films was proposed
by Gröndahl et al.28 as a method to produce hydrophobic films
with a potential as food packaging. Arabinoxylan from barley
husks was cast as films and then subjected to gas-phase
fluorination with trifluoroacetic anhydride (Figure 3). The
attachment of the fluorinated moiety was confirmed by FT-IR,
while attenuated total reflectance IR (ATR-IR) verified the
functionalization of the surface and not of the bulk. Static contact
angle measurements demonstrated the change in character of
the films, as the water contact angle increased from 30° for an
untreated film to 70° for a film with a content of 7% fluorine.
The hydrophobic modification furthermore resulted in a decrease
in the equilibrium moisture content from 18 to 12%.
The hemicellulose O-acetylgalactoglucomannan (AcGGM)
originating from wood was studied by Hartman et al. as a
potential oxygen barrier.29 AcGGM was obtained by concentra-
tion of process water from thermomechanical pulping. A water
soluble product with Mw ∼ 10000 g mol-1 (PDI ∼ 1.3) was
isolated by ultrafiltration. Films of 30–60 µm were cast with
21–25 wt % of one of the plasticizers glycerol, sorbitol, or
xylitol. In addition, mixtures (2:1 on weight basis) of AcGGM
with alginate (Mw ) 100000–200000 g mol-1) or carboxy-
methylcellulose (CMC) (Mw ) 100000–150000 g mol-1) were
utilized for film formation. The plasticized films showed a
decrease in storage modulus with increasing humidity, which
was especially pronounced for the AcGGM film containing
Biomacromolecules, Vol. 9, No. 6, 2008 1495
pretreatment
methanol-H2O ethanol-H2O
(60/40, v/v) (60/40, v/v)
5.3 16.5 15.9
74.3 67.7 67.8
1.8 1.9 1.0
3.6 4.1 3.9
14.9 9.8 11.8
5.2 6.6 6.3
13350 42710 44080
4.5 8.4 8.9
glycerol (Table 2). The hybrid films consisting of polymer
blends exhibited better mechanical behavior than the plasticized
AcGGM films, retaining their mechanical properties at elevated
humidity as well as generally having larger storage moduli. A
blend film of alginate and AcGGM was plasticized with glycerol
and demonstrated intermediate mechanical properties compared
to the equivalent two-component films. The elongation of the
films after DMA measurements mirrored the mechanical stabil-
ity, as the highest elongation, 195%, was found for glycerol
plasticized AcGGM, while the hybrid samples containing
alginate or CMC gave elongations of 4 and 3%, respectively.
Oxygen permeabilities were the lowest for the AcGGM-alginate
and AcGGM-CMC films. The sorbitol-containing AcGGM film
had an oxygen permeability of 2.0 cm3 µm m-2 d-1 kPa-1,
which was markedly lower than the value of 4.4 cm3 µm m-2
d-1 kPa-1 found for the xylitol-plasticized film. It was not
possible to perform measurements on the glycerol-plasticized
film; however, the alginate-AcGGM film containing this
component (17.5 wt %) had the highest oxygen permeability:
4.6 cm3 µm m-2 d-1 kPa-1.
A second study of AcGGM was performed by Hartman et
al.30 and an overview of the films formed in this work is given
in Figure 4. AcGGM was mixed with alginate or CMC at a
ratio of 7:3 (weight basis) and the blends were cast as films.
The formed films were modified by either vapor-phase
grafting with styrene or plasma treatment followed by styrene
grafting to increase hydrophobicity. Benzylation of AcGGM
was undertaken with benzyl chloride in alkaline solution
(NaOH of varying concentration), which resulted in deacety-
lation of the ester groups, rendering them susceptible to
benzylation (Figure 5).
The benzylated AcGGM (BnGGM) formed films that were
transparent, strong, and flexible. A blend of alginate and
AcGGM was additionally benzylated and then cast as film.
BnGGM was laminated on to an AcGGM-alginate film by
dipping the latter in a solution of the former component. To
our knowledge, lamination is a novel approach to forming
multilayer films based on hemicellulose. The oxygen perme-
abilities of the BnGGM films were several magnitudes higher
than those found for the blend films, as values of 130 and 559
cm3 µm m-2 d-1 kPa-1 were found at 50% RH (Table 3) and
permeability increased with DS. The AcGGM-alginate and
AcGGM-CMC blend films exhibited significantly lower oxygen
transmission rates under the same conditions but were moisture-
sensitive at higher humidity (83% RH), while the BnGGM films
retained their oxygen barrier properties. An excellent oxygen
permeability value of 8 cm3 µm m-2 d-1 kPa-1 was measured
for BnGGM-laminated AcGGM-alginate film. Comparison of
an unmodified AcGGM film with a BnGGM film in DMA
1496 Biomacromolecules, Vol. 9, No. 6, 2008 Hansen and Plackett

Table 2. Properties of O-Acetylgalactoglucomannan (AcGGM) and Blend Films29

storage modulus storage modulus O2 permeability elongation after
material plasticizer 30% RH (MPa) 60% RH (MPa) (cm3 µm m-2 d-1 kPa-1) DMA (%)
a
AcGGM glycerol 2.8 1.8 195
AcGGM sorbitol 2.8 2.6 2.0 17
a
AcGGM xylitol 3.0 2.4 4.4
AcGGM-CMCb 3.1 3.0 1.3 3
AcGGM-alginate 3.2 3.2 0.6 4
AcGGM-alginate glycerol 3.4 3.0 4.6 17
a b
Could not be obtained. CMC: carboxymethylcellulose.

Figure 4. Overview of the utilization of AcGGM for the formation of films.30 The emphasized boxes each represent a produced film and, in some
cases, the label of the film is indicated in italics.

equipment, procedures, and units in which to express perme-

Figure 5. Benzylation of AcGGM performed by Hartman et al.30
measurements demonstrated that while the storage modulus was
lower for the BnGGM sample at 20% RH (2.5 MPa vs 3.5 MPa)
this film retained its mechanical properties at increased humidity
(up to 70% RH), which was not the case for the AcGGM film.
Static contact angle measurements on all the films showed that
the hydrophobicity was not altered to a great extent by the
chemical modifications, as water contact angles ranged from
45 to 78° (Table 3) and a contact angle of 63° was measured
for untreated AcGGM. There was a difference in terms of water
droplet adsorption time as, unlike the other films, water droplets
were retained on the BnGGM film surface even after 10 min.
The unmodified films dissolved rapidly when immersed in water,
whereas only minor weight losses (16–28%) were registered
for the BnGGM films after a prolonged period of immersion.
The films with surface-grafted styrene were also water soluble;
however, dissolution was much slower than for the unmodified
films.
Oxygen permeability data for a number of biobased polymers
as well as more traditional packaging materials are shown in
Table 4. Although it can be difficult to compare permeability
data obtained by various research groups using different
ability results, the data in Table 4 give an indication of the
oxygen permeability of the materials. Comparing the oxygen
barrier properties of materials derived from hemicellulose with
the other materials, the former are seen to be very promising as
new materials in the field. Films from amylose and amylopectin
obtained from starch have good barrier properties with perme-
ability values in the same range as the studied hemicellulose
films (i.e., 7 and 14 cm3 µm m-2 d-1 kPa-1, respectively31).
Chitosan, poly(vinyl alcohol) PVOH, and ethylene vinyl alcohol
(EVOH) films have excellent oxygen barrier properties with
values below 0.5 cm3 µm m-2 d-1 kPa-1 in all cases, which
was matched by the xylan film produced by Gröndahl et al.26
Comparable but slightly higher oxygen permeabilities were
found by Hartman et al.29 for an AcGGM film as well as for
blend films of AcGGM with CMC and alginate (with and
without grafted styrene). Research in the area of oxygen barrier
materials from hemicellulose is ongoing and seems to hold great
promise for future practical applications.
Coatings
Edible coatings for foodstuffs are often necessary to prolong
shelf life and maintain important properties such as texture, taste
and mouthfeel. The uptake of moisture is often a crucial factor
in the rate of degradation of a given product, therefore coatings
acting as moisture barriers are of the utmost interest in the food
industry. Two parameters are defined, whereby the barrier
properties of a film or coating may be assessed: the water vapor
transmission rate and the water vapor permeability. Both
parameters are determined by gravimetrically measuring the
Sustainable Films and Coatings from Hemicelluloses Biomacromolecules, Vol. 9, No. 6, 2008 1497

Table 3. Properties of O-Acetylgalactoglucomannan (AcGGM) and Blend Films Subjected to Different Treatments30
O2 permeability 50% RH O2 permeability 83% RH contact
film abbreviation material treatment (cm3 µm m-2 d-1 kPa-1) (cm3 µm m-2 d-1 kPa-1) angle (°)
b b
AcGGM none 63
AcGGM-CMCa none 1.28 c
54
c
G30A AcGGM-alginate none 0.55 78
b b
AcGGM-alginate benzylated 45
AcGGM benzylated 130 170 70
BnGGM1 AcGGM benzylated 559 546 57
b
G30A film laminated with BnGGM1 solution 8d 63
c
G30A film vapor phase grafting with styrene 1.75 72
a b
CMC: carboxymethylcellulose. Not measured. c Not obtained. d
Measured at 73% RH.

Table 4. Oxygen Permeabilities of Packaging Material Measured at 23 °C, 50% RH

O2 permeability
material plasticizer (cm3 µm m-2 d-1 kPa-1) reference
AcGGMa sorbitol (21 wt %) 2.0 Hartman et al.29
AcGGM-alginate (7:3) 0.6 Hartman et al.29
AcGGM-alginate (7:3) vapor phase 1.8 Hartman et al.29
grafted with styrene
AcGGM-CMCa 1.3 Hartman et al.29
amylopectin glycerol (40 wt %) 14 Rindlav-Westling et al.31
amylose glycerol (40 wt %) 7 Rindlav-Westling et al.31
chitosan glycerol (25–50 wt %) 0.1–0.4b Butler et al.32
ethylene vinyl alcohol (EVOH) 0.3b,c van Tuil et al.33
low-density polyethylene (LDPE) 7900b,c van Tuil et al.33
poly(lactic acid) (PLA) 160b,c van Tuil et al.33
poly(hydroxyalkanoate (PHA) 150b,c van Tuil et al.33
poly(vinyl alcohol) (PVOH) 0.21 Gröndahl et al.26
whey protein glycerol (25–60 wt %) 50–325c Sothornvit et al.34
xylan sorbitol (35 wt %) 0.21 Gröndahl et al.26
a
AcGGM: O-acetylgalactoglucomannan; CMC: carboxymethylcellulose. b Values recalculated from the original paper. c Values estimated from diagrams
in the original paper.

transport of water through a film specimen. The water vapor
transmission rate, WVTR is defined as
∆m
WVTR )
∆t × A
where ∆m is the change in weight, ∆t is the elapsed time, and
A is the area of the tested film.
The water vapor permeability (WVP) is defined as
WVTR × L
WVP )
∆p
where L is the film thickness and ∆p is the difference in vapor
pressure on the two sides of the film.
In the following, a number of studies on hemicellulose for
edible food coatings are discussed. β-glucan extracts (75–79%)
from hulled barley, hull-less barley, and oats were tested as
water vapor barriers by Tejinder.35 These hemicelluloses were
plasticized with glycerol (30 or 40 wt %) and cast on plexiglass
plates to yield potentially edible films. The films were opaque,
with opacity values depending on the concentration of the cast
solution (2 or 4 w/v %). The tensile strength was also dependent
on solution concentration, with higher values found with higher
concentration (approximately a 2-fold increase). β-glucan source
also influenced film tensile strength. Values for films cast from
4 w/v % solutions were expressed in Newtons (N), with the
highest value found for oats (13 N) and the lowest for hulled
barley (2.3 N). Water vapor permeability (WVP) of films also
increased with an increasing solution concentration. A WVP
of 4.5–6.1 g mm m-2 h-1 Pa-1 was found for films cast from
4 w/v % solutions, while WVP values of 2.5–3.2 g mm m-2
h-1 Pa-1 were found for the films cast from less-concentrated
solutions. Water vapor transmission rates were similar for all
films and in the range 0.47–0.60 g m-2 h-1. The β-glucan-
based films from oats were highly water soluble, whereas the
films of β-glucans from barley were less soluble, with the hull-
less barley samples being intact after immersion in water for
24 h.
Skendi et al.36 tested water soluble β-glucans from different
types of oats as potential materials for edible films. Molecular
weights of 27000–85000 g mol-1 were obtained for products
isolated by aqueous extraction, and these molecular weights were
reduced to 18000–78000 g mol-1 after acidic treatment. Intrinsic
viscosities increased with molecular weights with values of
4.9-6.4 dL g-1 calculated for samples ranging from 27000 to
85000 g mol-1 (different work-up methods). Rheological
measurements showed that β-glucan solutions were viscoelastic
fluids and exhibited shear thinning behavior. The β-glucans
adopted gel properties in oscillatory measurements, behaving
as an elastic gel network, with the gelation time increasing with
increasing molecular weight (43 h for 78000 g mol-1). Tensile
strengths of 20-80 MPa were observed for films cast from a
sample of Mw ) 71000 g mol-1, where an increase in moisture
and sorbitol (15 wt %) resulted in increased elongation and
reduced tensile strength. For the above-mentioned films as well
as films from a sample of Mw ) 18000 g mol-1 elongations in
the range 1–22% and Young’s modulus of up to 6000 MPa
were observed.
Corn hull arabinoxylan (Mw ) 50600 g mol-1) was the main
component of edible films produced by Zhang and Whistler.37
Films plasticized with propylene glycol, glycerol, or sorbitol
(0–22 wt%) were cast on glass plates to thicknesses of 22–32
µm. Arabinoxylan films plasticized with propylene glycol were
brittle and the properties were almost independent of plasticizer
content with elastic moduli of 1290–1314 MPa, tensile strengths
ranging from 53 to 61 MPa and elongations between 6 and 8%,
which was reported to be similar to results for cellulose films
1498 Biomacromolecules, Vol. 9, No. 6, 2008
containing this plasticizer. The properties varied much more
with plasticizer content for the glycerol- and sorbitol-plasticized
films with tensile strengths of 10–47 MPa and 20–48 MPa,
respectively, while elongations ranged from 6 to 12% and 6 to
9%, respectively. The best moisture barrier properties were
found for sorbitol-plasticized films with WVP ) 0.23 × 10-10
g m-1 Pa1- s-1 (13% sorbitol), while values of 0.31 × 10-10
and 0.36 × 10-10 g m-1 Pa1- s-1 were found when using
propylene glycol (16%) and glycerol (5%), respectively, as
plasticizers. A high content of glycerol (>10%) resulted in an
increase in permeability due to the hygroscopic nature of the
plasticizer. The reduction of moisture loss from grapes was
tested with these films as coatings. The films were stable,
smooth, and transparent and demonstrated good moisture barrier
properties over a period of seven days with a reduction of weight
loss from 82 to 59%. Furthermore, the coatings proved more
efficient as moisture barriers than coatings of corn amylopectin
and carboxymethyl cellulose films produced for comparison.
Xylans from birchwood, grass, and corncob were used by
Kayserilioglu et al.38 as additives in wheat gluten to form
potentially edible composite films. The birchwood xylan was
commercially available, whereas the grass and corncob xylans
were isolated by alkaline extraction. Weight fractions of 0-40%
birchwood xylan were mixed with wheat gluten and cast under
acidic and alkaline conditions (pH of 4 and 11, respectively)
and films were dried at ambient and elevated temperature (80
°C). Tensile testing showed tensile strength was not significantly
dependent on composition but that values were 2–3 times higher
for films cast at pH ) 11 than at pH ) 4, which could be due
to the more uniform films formed during the casting process at
high pH. In addition, drying at room temperature seemed to
give the best tensile properties. The opposite effect was seen
for the elastic modulus and the elongation, which both increased
with lower pH and higher drying temperature. Films with 20
wt % xylan from grass or corn cob were cast from alkaline
solution at ambient temperature and compared to the analogous
birchwood xylan-containing film. A tensile strength of ap-
proximately 8 MPa was measured for the latter film (close to
the value found for pure gluten), while considerably lower values
were found for films from grass or corn cob (1.5–3 MPa). Corn
cob xylan-containing films were the most stretchable with E ∼
10 MPa and elongation of 600% (approximately 50% for the
other two). In addition, corn cob xylan films were found to be
the most homogeneous by SEM analysis. The xylan-gluten films
did not lose their integrity in aqueous solution after 24 h and
solubility was seen to depend on the drying conditions of the
film as well as the source of xylan. Water vapor transfer rates
were slightly lower for films cast at elevated temperature than
for those cast at ambient temperature. However, values were
of the same order of magnitude ranging from 6 × 102 to 8 ×
102 g m-2 per 24 h.
Numerous approaches to producing edible water vapor
barriers have been attempted by a collaboration based in
France.39–43 In all cases, arabinoxylan was extracted from maize
bran and plasticized with glycerol (15 or 20 wt %). The first
modifications entailed mixing the hemicellulose/glycerol (15 wt
%) with palmitic acid (C16), oleic acid (C18), triolein, or a
hydrogenated palm oil (HPKO).39 Emulsification of the lipids
was ensured with the addition of glycerol monostearate and
treatment with a homogenizer. Films of 65–100 µm thickness
were cast from the emulsified lipids in AX-glycerol mixtures,
as well as the plasticized AX. The films based on emulsified
lipids were more opaque than the parent AX film. WVP of the
homogeneous AX film was 1.8 × 10-10 g m-1 Pa1- s-1, while
Hansen and Plackett
Figure 6. Water vapor transmission rates (WVTR) and water vapor
permeabilities (WVP) of films of arabinoxylan (AX), arabinoxylan
containing hydrogenated palm kernel oil (AX-HPKO), palmitic acid
(AX-C16), oleic acid (AX-C18), and triolein (AX-triolein), cellophane,
and low-density polyethylene (LDPE).39
the lipid-containing films exhibited significantly lower values
in the range of 1.2-1.5 × 10-10 g m-1 Pa1- s-1 (Figure 6).
Similar behavior was observed for the water vapor transfer rate
(WVTR) of AX-based films, where values of 2.7-3.5 × 10-3
g m-2 s-1 were found for the AX films with emulsified lipids
compared to 3.9 × 10-3 g m-2 s-1 for the nontreated film.
The lowest value for WVTR was found for the AX-HPKO film,
while AX-triolein and AX-C18 performed best regarding perme-
ability. Values of WVP were 3–100 times larger than for
commercial cellophane and LDPE films investigated for com-
parison. Contact angles of water droplets on the film surfaces
showed large differences in character, with measurements
ranging from 39 to 94° (71° for AX), indicating dissimilarity
in hydrophobicity. Tensile strength and elastic modulus were
both reduced with the introduction of the lipids. The tensile
strength of the AX film was 27 MPa but only 6–9 MPa for the
mixed films. Similarly, the elastic modulus was reduced from
72 MPa to 26–59 MPa. Elongation was increased with the
addition of triolein and HPKO, whereas it was reduced with
palmitic (C16) and oleic (C18) acid.
HPKO was the most promising lipid and studies of the AX
films with emulsified HPKO were therefore continued.40 Four
sucroesters with hydrophilic–lipophilic balance (HLB) values
varying from 2 to 15 were utilized as emulsifying agents to
obtain different globule sizes of the lipid so that the influence
of this parameter on barrier properties could be assessed. Two
or more sizes of lipid globules were present in all the emulsions
as seen by laser light-scattering granulometry. The smaller
globules were 0.5-0.9 µm in size, while the sizes of the larger
ones were dependent on the nature of the emulsifying agent.
The emulsion stability was governed by the concentration of
the sucrose ester and to a lesser extent by the solubility of this
compound in the aqueous phase. No direct correlation between
globule diameter and water vapor permeability was found, as
the former depends on the nature of the emulsifying agent. The
most lipophilic sucroester SP10 (HBL ) 2) gave the best
emulsion stability during drying and also the lowest WVP of
9.5 × 10-11 g m-1 Pa1- s-1, which was almost identical to the
value found for an HPKO-containing film without sucrose ester
and very close to 1.0 × 10-10 g m-1 Pa1- s-1 found for a
hydroxypropylmethylcellulose (HPMC) film prepared in parallel
to the AX films. This indicated that barrier properties may be
improved by (1) stabilizing the emulsion during drying, (2)
ensuring an even distribution of the lipid globules, or (3) by
destabilization of the emulsion by aggregation (i.e., formation
of a bilayer film structure with HPKO at the surface). Some
WVP values found for the AX films are shown in Figure 7 in
which the values measured for HPMC as well as for com-
Sustainable Films and Coatings from Hemicelluloses
Figure 7. Water vapor permeability values found for arabinoxylan films
plasticized with glycerol, with and without added hydrogenated palm
kernel oil (HPKO).40 Films produced by the same method from
hydroxypropylmethylcellulose (HPMC) were prepared for comparison.
Commercial cellophane and low-density polyethylene (LDPE) were
also included in the study.
mercially obtained cellophane and low-density polyethylene
films are also given.
Studies on the influence of drying temperature of AX-based
films were undertaken with the two sucrose esters SP10 and
SP70 (HLB ) 15).41 Temperatures of 30, 40, and 80 °C were
chosen as these are below, slightly above and much higher than
the melting point of HPKO, respectively. Emulsion stability was
seen to decrease with drying temperature resulting in the
formation of bilayer films when drying at 80 °C. Increase in
drying temperature also gave a slight decrease in permeability
as well as an increase in static water contact angle. The presence
of the sucrose esters gave rise to increased water absorption
rates compared to the films containing plasticizer (glycerol) and
lipid (HPKO), which was especially pronounced for the hydro-
philic SP70. The mechanical properties were found to deteriorate
with the addition of the lipid, realized by the reduction of both
elongation and strength at break. Tensile strength at break was
0.8-3.0 times less than that determined for homogeneous AX
film. Strength at break for the latter film was approximately 22
and 16 MPa at drying temperatures of 40 and 80 °C, respec-
tively. Using a drying temperature of 80 °C reduced the strength
at break and increased elongation compared to drying at 40 °C.
Peroval et al.42 attempted a different approach with the AX
films by grafting the monomers stearyl acrylate (SA) and stearyl
methacrylate (SM) on to the films by electron beam treatment.
Three distinct processes were carried out: (A) cold plasma
treatment of glycerol-plasticized AX films followed by impreg-
nation with monomer and grafting by electron beam, (B)
emulsified films (i.e., films from blends of monomer, glycerol,
glycerol monostearate, and AX) were electron-beam treated, (C)
pretreatment of AX films with electron beam followed by
impregnation with monomer and grafting by electron beam.
Treatment A was also performed with HPKO as monomer,
resulting in potentially edible films. Comparison of the films
showed that the monomer in all cases induced increased
hydrophobicity with static water contact angles increasing from
71° up to a maximum of 123° in the case of an SM-grafted
film. Water permeability was decreased with the introduction
of the monomers and was furthermore dependent on the grafting
process. For SA and SM, treatment A was the least effective in
reducing permeability. WVTR and WVP of SA-grafted films
were lower or equivalent to values found for SM-grafted films
in all cases. The lowest values found were for SA monomer,
Biomacromolecules, Vol. 9, No. 6, 2008 1499
which had undergone treatment C and these were WVTR )
1.5 × 10-3 g m-2 s-1 and WVP ) 6.8 × 10-11 g m-1 Pa1-
s-1. The plasma treatment followed by monomer impregnation
and grafting (treatment A mentioned above) was also undertaken
with omega-3 fatty acids from fish as well as linseed oil.43
Grafting levels of 5.1-6.4% were obtained with the oils. Contact
angle measurements showed an increase for two of the fish oils
and a decrease for the third, while linseed oil did not influence
this parameter. The change in static contact angle over time
varied for the oils indicating different modifications (surface
vs bulk) when grafting with the various oils. Water vapor barrier
properties were improved with grafting and most significantly
with linseed oil, where WVTR of 2.9 × 10-3 g m-2 s-1 and
WVP of 1.1 × 10-10 g m-1 Pa1- s-1 were found. AX was
plasticized with 20 wt % glycerol (as opposed to 15 wt % used
in the previous experiments) giving values of 4.5 × 10-3 g m-2
s-1 and 2.1 × 10-10 g m-1 Pa1- s-1 for WVTR and WVP,
respectively, for the untreated film.
Xylan, isolated from cotton stalks containing residual lignin,
was used by Goksu et al.44 to form films intended for food
packaging applications. To our knowledge, this is the only
example in the literature of the formation of coherent films from
xylan without the use of an additive or plasticizer. Complete
lignin removal from xylan was shown to be detrimental to the
film-forming properties, resulting in cracked films. Com-
mercially obtained birchwood xylan was used as model com-
pound to determine the lower limit of lignin needed to generate
films. By adding lignin to birchwood xylan solutions a
concentration of 1% (w/w, lignin/xylan) was assessed to be
necessary for the formation of films. Solutions of 8, 10, 12,
and 14% (w/w) cotton stalk xylan containing lignin in the
aforementioned amount were cast to form films with thicknesses
of 0.29–0.38 mm. Film thickness, tensile strength, strain at
break, and elastic modulus generally increased with the con-
centration of the casting solution (Table 5). Values of WVTR
were normalized to eliminate effects from varying film thickness,
and these values decreased significantly from 917 (g m-2
day-1)/mm thickness for the 8% solution film to 574 (g m-2
day-1)/mm thickness for the 14% solution film. Films plasticized
with glycerol (2% w/w) were furthermore prepared from a 10%
xylan solution. These films were observed by SEM to have
rougher surfaces than the nonplasticized films. The authors
suggested that plasticizer addition could increase the free volume
within the film and enhance water evaporation, leading to
decreases in film thickness. WVTR was increased slightly by
the addition of plasticizer, and tensile strength was reduced
considerably from 1.34 to 0.76 MPa. All the generated films
were water soluble (98–99% solubility).
Past research in producing barrier films from hemicellulose
(Table 6) demonstrates the difficulties of modifying a hygro-
scopic material to form a moisture barrier; however, modified
hemicelluloses showed major improvements in the barrier
properties compared to the parent compounds. Table 7 shows
the water vapor barrier properties of several commercial
polymers as well as a number of biomaterials. WVP and WVTR
values of LDPE, polyethylene terephthalate (PET), PS, and PLA
are several orders of magnitude lower than the corresponding
values for the different hemicellulose films (Table 6). Corn hull
arabinoxylan films37 exhibited slightly better barrier properties
than cellophane. Films from cotton stalk xylan44 as well as from
maize bran arabinoxylan with various hydrophobic modifica-
tions39–43 had comparable barrier properties to those of cel-
lophane and HPMC. All the hemicellulose films targeted for
coatings were superior to amylose and amylopectin films in
1500 Biomacromolecules, Vol. 9, No. 6, 2008
Table 5. Water Vapor Transfer Rate (WVTR) and Strength Properties of Films Based on Cotton Stalk Xylan44
xylan concentration thickness tensile strength
(% w/w) (mm) (MPa)
8 0.29 1.08
10 0.32 1.34
12 0.37 1.27
14 0.38 1.39
10, 2% (w/w) 0.30 0.76
glycerol
terms of WVP values. Although improvements in barrier
properties can be significant for modified hemicelluloses, these
films are not yet capable of competing with commercial films
from nonrenewable sources such as PET, LDPE, and PS in terms
of water vapor barrier properties.
Biomedical Applications
Considerable research has been done in the area of hemicel-
luloses for biomedical purposes due to the biocompatibility,
biodegradability, and high stability of these compounds. As
previously mentioned, a number of hemicelluloses are already
widely used in the pharmaceutical industry,5,6 while others are
as yet relatively unexploited.
The formation of hydrogels using xylan extracted from birch
wood has been studied by Gabrielii and Gatenholm.46 Films
with thicknesses of 50 µm were cast with 0–35 wt % of chitosan
under acidic conditions. Self-supporting films were formed with
a chitosan content of 10 wt %, while hydrogels were obtained
with 30 wt % chitosan. Dynamic mechanical measurements
indicated the presence of two phases, substantiated by atomic
force microscopy (AFM), in which the observed fibrils were
believed to be the chitosan phase. Water uptake increased with
chitosan content, most markedly between 15 and 30 wt %.
Gabrielii et al.47 generated hydrogels utilizing hemicellulose
from aspen wood. Xylan (Mw ) 73100 g mol-1, Mn ) 48000
g mol-1) with 12% branching (determined by two-dimensional
NMR) was isolated by alkaline extraction. Self-supporting films
were formed from mixtures of xylan with chitosan (10–100 wt
%). Highly swellable hydrogels were formed with the addition
of up to 20 wt % chitosan, while water-soluble films were
formed at higher chitosan content. Pure xylan yielded brittle
aggregates and was unable to form free-standing films. Crystal-
linity was reduced from 37 to 0% by increasing the chitosan
amount from 0 to 100%, as seen by wide-angle X-ray
spectroscopy.
β-(1f3)(1f6)-glucan from Shiitake mushrooms was coated/
grafted onto the surface of poly(D,L-lactic-co-glycolic acid) film
to enhance the cell affinity of the surface.48 The coating process
was performed with and without plasma pretreatment, with the
former procedure yielding the best results in terms of human
dermal fibroblast cell proliferation on the surface. These films
were envisioned to regenerate skin tissue effectively.
Magnetite microparticles intended for oral intake and applied
as magnetic markers for monitoring gastrointestinal motility
were coated with xylan from corn cobs.49 The purpose of the
polymer coating was to reduce dissolution of the particles in
the patient’s stomach, ensuring passage into the colon. Com-
parison of coated and uncoated microparticles showed a
difference in both size and size distribution. The coated spherical
microparticles exhibited a more narrow, monomodal distribution
with larger particle size (5-fold increase) than the uncoated
particles. The superparamagnetic properties of the magnetite
microparticles were found to be unaltered by the xylan coating.
Hansen and Plackett
strain at elastic modulus normalized WVTR
break (%) (MPa) ([g m-2 day-1]/mm thickness)
45.6 0.11 917
48.7 0.37 832
52.5 0.44 699
56.8 0.49 574
88.9 0.08 905
Dissolution of magnetite was decreased significantly with the
coating, as 28.5% of the uncoated particles were dissolved after
120 min in acidic media, whereas only 2.3% of the content was
lost from the coated particles under the same conditions.
As progress in the pharmaceutical industry leads to increased
demands on materials for specific applications, more specialized
drugs and methods of drug delivery will be necessary to fulfill
requirements. A number of hemicelluloses such as guar gum
(a galactomannan) are already commonly used in this field,50
but other less investigated hemicelluloses may find application
in the future.
Fundamental Studies on Hemicellulose Films
While many studies on hemicellulose films and coatings have
described well-defined commercial targets, there are also a
number of research papers that are focused on more fundamental
research topics. This is especially characteristic of some of the
work on chemically modified hemicelluloses, in which func-
tionalization itself can appear to be the objective. In some cases,
films have been cast from the resulting products and the
properties of these have been assessed.
Esterification was used by Moine et al.51 for the generation
of hydrophobic films from beechwood xylan and maize bran
heteroxylan. The beechwood xylan was identified as 4-O-
methylglucuronoxylan, while the heteroxylan consisted of a
mixture of xylose, arabinose, galactose, glucuronic acid, and
its 4-O-methyl derivative. Lauroyl chloride was used to
introduce esters on the hydroxyl groups of the xylans by a
microwave-activated reaction in N,N-dimethylacetamide/LiCl
catalyzed by dimethylaminopyridine. The degree of substitution
(DS) was 1.3, as determined by 1H NMR for xylan, with a
similar value of 1.2 found for the heteroxylan. FT-IR was used
to confirm the substitution of the hemicelluloses. Elastic moduli
of 366 and 157 MPa and stress at break of 15 and 6 MPa were
found for dodecyl-grafted xylan and heteroxylan, respectively.
Both the functionalized xylans showed elastic deformation up
to 80 °C with a constant storage modulus observed in dynamic
mechanical testing, which was also used to determine Tgs of
133 and 132 °C.
Maize bran heteroxylan was used by Fredon et al.52 to
produce hydrophobic films. The heteroxylan (Mw ∼ 28000 g
mol-1) consisted of arabinose, xylose, galactose, glucuronic
acid, and glucose monomer units. In addition to these hemi-
cellulose components, some residual starch was also detected.
Modification entailed oxidation with sodium periodate followed
by reductive amination with dodecylamine and sodium cy-
anoborohydride. The result was ring opening and incorporation
of dodecylamine on the remaining hemicellulose backbone
(Figure 8). Thus, modified heteroxylans were obtained with DS
) 0.6–1.1, which were subsequently cast as films. Tgs were
assessed to be between -30 and 0 °C, rendering plastic films
at ambient temperature. DS influenced the mechanical properties,
as elastic moduli of 118 and 87 MPa were found for substituted
Table 6. Water Vapor Permeability (WVP), Water Vapor Transfer Rate (WVTR), and Strength Properties of Edible Hemicellulose Films
WVP
test (10-11 g m-1 WVTR tensile elastic
hemicellulose source modification additives temperature (°C) Pa1- s-1) (10-3 g m-2 s-1) strength (MPa) modulus (MPa) reference
β-glucan barley, oat none glycerol (30/40 wt %) 30 68–169a 7.5–10.0a 0.91–13.02b Tejinder35
xylan birch, grass mixing with wheat glycerol (2 wt %) 23 6.9–9.3a 1–9c 10–200c Kayserilioglu et al.38
corncob gluten (major component)
arabinoxylan corn hull none glycerol, propylene 22 2.3–4.3 9.7–60.7 365–1320 Zhang et al.37
glycol, sorbitol
(0–20 wt %)
none 4.7 53.8 1316
arabinoxylan maize bran emulsified films are generated glycerol (15 wt %) 25 11.8–15.2 2.71–3.52 6.4–8.8 25.84–59.2 Peroval et al.39
with globules of stearic or
palmitic acid, triolein, palm
Sustainable Films and Coatings from Hemicelluloses

oil
none glycerol (15 wt %) 17.7 3.92 26.5 72.4
arabinoxylan maize bran grafting with fatty acids from glycerol (20 wt %) 25 10.9–19.1 2.86–3.89 Peroval et al.43
fish oils on the formed film
by plasma and electron beam
treatment
none glycerol (20 wt %) 20.5 4.45
arabinoxylan maize bran grafting with stearyl (meth) glycerol (20 wt %) 25 6.8–17.2 1.50–3.77 Peroval et al.42
acrylate on the formed film by
plasma and/or electron beam
treatment
none glycerol (20 wt %) 17.7–20.5 3.92–4.45
arabinoxylan maize bran mixing with sucroesters as glycerol (15 wt %) 25 9.31–13.82 Phan The et al.40
emulsifiers and hydrogenated
palm oil as hydrophobic
phase
arabinoxylan maize bran mixing with sucroesters as glycerol (15 wt %) 25 7.72–13.70 Phan The et al.41
emulsifiers and hydrogenated
palm oil as hydrophobic
phase
xylan cotton stalk residual lignin 1% (w/w glycerol (2 wt %) 20 3.14a 0.76 0.08 Goksu et al.44
lignin/xylan)
none 2.52–3.08a 1.08–1.39 0.11–0.49
a b c
Values recalculated from the original paper. Tensile strength given in N (as in the original paper). Values estimated from diagrams in the original paper.
Biomacromolecules, Vol. 9, No. 6, 2008
1501
1502 Biomacromolecules, Vol. 9, No. 6, 2008
Table 7. Water Vapor Permeability (WVP) and Water Vapor Transfer Rate (WVTR) of Selected Polymer Films
test temperature
material (°C) (10-11 g m-1 Pa1- s-1)
amylose 23
amylopectin 23
cellophane 25
low-density polyethylene (LDPE) 25
hydroxypropylmethyl-cellulose (HPMC) 25
polyethylene terephthalate (PET) 37.8
polystyrene (PS), oriented 37.8
poly(lactic acid) (PLA), oriented 37.8
a
Values recalculated from the original paper.
Figure 8. Oxidation followed by reductive amination of vicinal hydroxyl
groups of arabinofuranose to yield dodecylamine functionalized
heteroxylan.52
Figure 9. Esterification of xylan with furan-2-carboxylic acid assisted
by N,N′-dicarbonyldiimidazole.53
xylans with DS of 0.7 and 1.1, respectively, while the corre-
sponding elongations at break were 8 and 22% for these films.
The casting method affected the film properties as seen by
comparison of solution-cast and tape-cast films (DS ) 1.1). The
tape-cast film exhibited increased elasticity with E of 57 MPa
and an elongation of 38%.
Hesse et al.53 synthesized furan-2-carboxylic esters of a
number of polysaccharides targeted as potential macroporous
membrane materials. 4-O-Methylglucuronoxylan from birch
wood (Mw ) 13000 g mol-1) was among the chosen polysac-
charides in addition to cellulose, curdlan, dextran, and starch.
Esterification was performed with furan-2-carboxylic acid in
the presence of N,N′-dicarbonyldiimidazole to yield photo-
crosslinkable polymers (Figure 9). Xylans with DS of 0.09 to
0.86 were obtained, of which the most substituted was soluble
in DMSO and could be cast as self-supporting films. Atomic
force microscopy was used to determine surface roughness, and
this was found to be dependent on the backbone structure, with
the most branched structures yielding the roughest films: Ra ∼
150 nm and Rmax ∼ 1500 nm were determined for the xylan
furoate. Pore sizes of 250-750 nm were found for this film by
scanning electron microscopy (SEM). The pore size differed
from the glass-film contact side to the film-solvent contact
side, which was also the case for the other polysaccharide esters.
Schwikal et al.54 functionalized 4-O-methylglucuroxylan from
birch wood with 2,3-epoxypropyltrimethylammonium chloride
to yield cationic xylan derivatives (Figure 10). The reaction was
performed in aqueous NaOH and DS of 0.2-1.6 was obtained
by varying base concentration, reaction temperature, and molar
Hansen and Plackett
WVP WVTR
(10-3 g m-2 s-1) reference
119a Rindlav-Westling et al.31
144a Rindlav-Westling et al.31
6.9 6.2 Peroval et al.39
0.19 0.13 Peroval et al.39
10.0 Peroval et al.40
0.28 0.04a Auras et al.45
0.42 0.06a Auras et al.45
1.34 0.18a Auras et al.45
Figure 10. Generation of cationic xylan derivatives by etherification
with 2,3-epoxypropyltrimethylammonium chloride.54
Figure 11. Conversion of xylan to hydroxypropyl xylan (HPX) and
further to acetoxypropyl xylan (APX).56
ratio of the reactants. Turbidity tests indicated that the substituted
xylans were water soluble, with a DS > 0.4. Films with
thicknesses of 50 and 100 µm had pore sizes ranging from 250
to 1500 nm, depending on the concentration of the cast solution
and the thickness of the final film. Thus, porous films with
permanent positively charged ammonium groups as well as
carboxylic acid groups were generated.
Buchanan et al.55 produced composite films of esters of
arabinoxylan and cellulose. Two hemicellulose fractions were
isolated from corn fiber: hemicellulose A (Mw < 25000 g mol-1,
water soluble at pH > 10) and hemicellulose B (Mw > 500000
g mol-1, water soluble). Acetate, propionate, and butyrate
arabinoxylan esters were synthesized from the corresponding
anhydrides. Pure hemicellulose A could not be substituted,
whereas pure hemicellulose B and mixtures of the two could
be modified with DS ) 1.6–2.3. Onset of degradation for the
three esters was found to be above 225 °C by thermogravimetric
analysis (TGA) with the highest thermal stability for the butyrate
ester. Esterification reduced Tg of the xylan and this was most
pronounced with butyrate functionalization, resulting in a
reduction from 198 to 61 °C. Commercial cellulose acetate (CA),
(DSA ) 2.47) was mixed with arabinoxylan acetate in solution
and used to cast optically clear films with composition-
dependent Tgs, as seen by DSC. The blends were comprised of
one or two phases depending on the type and concentration of
solvent. Storage experiments indicated that phase separation also
took place over time (8 months). In contrast, mixtures of
arabinoxylan butyrate and cellulose acetate butyrate (DSA )
1.03, DSB ) 1.72) exhibited macroscopic phase separation and
formed opaque films under all casting conditions.
Jain et al.56 functionalized xylan from barley husks with
propylene oxide to yield hydroxypropyl xylan (HPX), which
in turn was acetylated with acetic anhydride to produce
acetoxypropyl xylan (APX) (Figure 11). HPX formed tough
transparent films, which were water soluble at low DS (0.2–0.5)
and exhibited tensile strengths of 35–45 MPa. In contrast, films
Sustainable Films and Coatings from Hemicelluloses
cast from APX were soluble in a number of organic solvents.
No Tg was observed for the unsubstituted xylan, while an
increase in DS of both HPX and APX clearly had a diminishing
effect on Tg due to internal plasticization. Both types of
substituted xylan were used as thermoplastic additives in
polystyrene (0–20%) revealing a decline in dynamic shear
viscosity with increasing xylan content. APX was furthermore
injection molded with polystyrene and studied by dynamic
thermomechanical analysis (DTMA), whereby the plasticizing
properties of the additive were demonstrated.
A number of functional groups have successfully been
introduced on the hydroxyl groups of various hemicelluloses
by esterification, etherification and amination. The resulting
products have altered properties compared to the parent
compounds in terms of strength, elasticity, hydrophobicity and
thermoplastic properties. The films from the presented work are
potentially relevant in a number of applications such as barrier
and membrane materials.
Patent Literature
In this section we review filed patent applications and existing
patents on the formation of films and coatings from hemicel-
luloses. References are only cited if the given examples
specifically include hemicellulose, as numerous sources include
hemicellulose in the patent claims while solely focusing
experimental work on cellulose. Results given in the examples
are included here to the extent that they are considered relevant
for this review.
Films. Crosslinking was used to ensure water insolubility of
hemicelluloses in a Japanese patent application from 1992.57
Chemical crosslinking agents such as acid chlorides were
employed to form highly swellable gels. Transparent films with
tensile strengths of approximately 500 kg/cm2 were produced
with oxygen permeability of 1.7–1.8 cc/(cm2 24 h atm.) for 50
µm thick films.
The formation of water soluble films from hardwood hemi-
celluloses is claimed in a patent from 1974, where the reaction
of the hemicellulose (DP < 400) in alkaline medium with
epichlorohydrin, and either an alkanolamine or glycerol lead to
the formation of transparent, colorless, and relatively strong
films.58
Laminated films consisting of at least two layers have recently
been patented in Japan,59 where one layer is comprised of a
thermoplastic film, more particularly polyester, while the other
consists of carbon nanotubes and hemicellulose. The latter
component is preferably extracted from Abelmoschus monihot
or Hydrangea paniculata obtaining polymers with DP of 100
to 10000. The carbon nanotubes were uniformly dispersed in
the hemicellulose films giving conducting and mechanically
strong films.
Arabinoxylan from Sorgo was utilized in a French applica-
tion60 for the fabrication of water-soluble films (solubility above
200 g/L). The films were swellable, with a water uptake between
10 and 25% and had mechanical yield strengths of 15-40 MPa.
Oxygen barrier films were produced from xylans (Mw )
15000 and 34000 g mol-1) in a recent Swedish patent
application.61 The films were plasticized with xylitol, sorbitol,
or water, and blends of xylan with polyvinyl alcohol or cellulose
were also generated. Oxygen permeabilities of 0.18–1.10 cm3
µm m-2 d-1 kPa-1 were obtained for the films. Stress at break
decreased with plasticizer content (3–39 MPa), while strain at
break increased up to approximately 10% (50% plasticizer). The
addition of cellulose to xylan increased stress at break to 103
Biomacromolecules, Vol. 9, No. 6, 2008 1503
MPa. Successful coating of a polystyrene film was furthermore
obtained with a coating thickness of 1 µm.
Heteroxylans, more specifically arabinoxylan, were used to
manufacture films for the formation of hard or soft capsules
intended for use in the pharmaceutical, phytotherapeutic, and
food sectors.62 Viscosity of the AX-solutions showed better
stability at high stresses than gelatine; however, the obtained
values were also slightly lower. The overall gelling procedure
was faster with the AX-based capsules than with gelatine or
hydroxypropyl cellulose. Glycerol content was varied to form
hard or soft capsules (2.4 or 25 wt %, respectively). Flat films
were also produced with thicknesses of 100–130 µm and rupture
strengths of 31–62 N.
Coatings. Hemicellulose from grain hulls was used as
material for seed coatings in a very recent patent application.63
Seeds of corn and soybean were successfully covered with
hemicellulose by spraying, which did not hinder germination
of the seeds. The coating could contain additives such as
insecticides, herbicides, and so on, thereby acting as a barrier
for species that are detrimental to seed growth.
Heteroxylans extracted from maize (Mw ) 100000–250000
g mol-1) were used in a French patent application64 to form
edible films for encapsulation of flavoring or other components
in foodstuffs. The performance of the films was comparable to
gum Arabic in the sugar coating of almonds in terms of stability,
texture, taste, and appearance. Seeds of carrots, cabbage, and
salad (chicory) were coated with the heteroxylan films, and while
the initial germination rate was reduced, the final level and speed
of growth was equivalent to uncoated seeds and superior to
commercial cellulose-based seed coatings. Similar results were
found when incorporating insecticides or fungicides in the films.
From the examples in the patent literature, it can be seen
that many different applications of hemicellulose have already
been investigated. It is, however, also obvious from the recent
dates of many of the applications that this is an area in which
there is still ongoing work, and all the possibilities have certainly
not been exploited. We will probably see many other applica-
tions of hemicelluloses in both the food and the pharmaceutical
industry in the future.
Summary
Cellulose, lignin, and hemicellulose derived from trees or
agricultural crop residues form the basis for the present
biorefinery concept that is now much discussed in the context
of the rapidly developing biofuels industry. Although there is a
long history of research and development on new chemicals
and materials from cellulose and lignin, hemicellulose has
remained relatively unexplored in this sense until quite recently.
The material applications for hemicellulose that have been
identified include packaging films, food coatings, and biomedical
uses.
Food packaging material derived from sustainable resources
is now receiving considerable interest, not least because of
growing public awareness of environmental issues and the
advantages in product marketing. Low oxygen permeability can
be a key requirement for food packaging materials in addition
to good mechanical properties in terms of high strength and
flexibility and hemicellulose-derived packaging materials have
been produced with oxygen permeability values that compare
favorably with those of other biopolymers such as amylose,
amylopectin and chitosan as well as PVOH and EVOH. There
are also a number of recent patent applications on oxygen
barriers from hemicellulose.
1504 Biomacromolecules, Vol. 9, No. 6, 2008
Moisture barriers in the form of edible coatings have been
produced with moderate success from hemicellulose. The main
obstacle in this field is the hygroscopic nature of the initial
material resulting in poor moisture barrier properties. Increased
hydrophobicity may be achieved by either chemical modification
(e.g., grafting) or addition of hydrophobic compounds (mixing
or emulsification). In some cases, WVTR and WVP have been
improved significantly, but the performance has generally not
been comparable with that observed for nonedible commercial
films such as LDPE. The patent literature discloses the use of
heteroxylans for coatings for seeds and candy and these were
claimed to be superior to cellulose-based coatings.
Some hemicelluloses such as konjac glucomannan and guar
gum have been used for many years in the pharmaceutical
industry, while others have not yet been employed commercially.
The formation of hydrogels from xylan in combination with
chitosan has been demonstrated and these gels might be suitable
for biomedical purposes. Ingested nanoparticles coated with
xylan have been shown to be capable of withstanding acidic
media ensuring passage to the colon of a patient, where the
nanoparticles might be used as magnetic markers. Although
considerable research on hemicelluloses for biomedical purposes
has been performed, the increasing need for specialized medicine
and forms of customized drug delivery may open up new
applications.
A significant amount of research has been aimed at modifying
hemicellulose chemically to alter the characteristics in com-
parison to the parent compounds. Modifications have led to
stronger, more elastic, and more hydrophobic or thermoplastic
products, and the resulting films may find a variety of potential
applications such as in selective membrane materials.
Although there has been extensive work on films and coatings
from hemicelluloses and derivatives, there are still many
potential pathways that have yet to be investigated, and
therefore, it can be argued that application of hemicelluloses in
fields such as packaging and biomedicine still holds considerable
promise for the future.
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