Food Chemistry 256 (2018) 419–426

Contents lists available at ScienceDirect

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

Review

Modifications of konjac glucomannan for diverse applications T

Fan Zhu
School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1142, New Zealand

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

Keywords: Konjac glucomannan (KGM) is a major polysaccharide from the corm of Amorphophallus konjac. Native KGM has
Film limited uses and has been chemically/physically/enzymatically modified to expand the range of functional
Encapsulation properties. This mini-review summarises the recent advances of modifying KGM for diverse food and nonfood
Biodegradable applications, focusing on the chemical and physical modifications. The chemical methods include substitution,
Chemical and physical modifications
grafting, cross-linking, oxidation, and deacetylation, whereas the physical modifications are electrospinning,
Super absorbent
microfluidic spinning, γ-irradiation, extrusion, and electric field processing. The modified KGM has been used in
Konjac glucomannan
Underutilized species a range of different applications, including biodegradable film, emulsion, medical and pharmaceutical material,
encapsulation and controlled release, fish feed and functional food ingredient, separation medium, aerogel,
liquid crystal, absorbent for removal of pollutants in waste water, and so on. These KGM-based products tend to
be biodegradable, biocompatible, and non-toxic with improved functional performance.

1. Introduction
Konjac (Amorphophallus konjac) of the Araceae (aroid) family is
native to warm subtropical and tropical Asia. It is widely grown as a
cash crop with high yields in countries such as China, India, and Japan
(Behera & Ray, 2017). Apart from starch, glucomannan is the major
component of the konjac corm which may accounts for ∼70% of the
dry weight of refined flour (Behera & Ray, 2017; Huang, Jin, Ye, Hu, &
Wang, 2016; Zhu, 2016). Konjac glucomannan (KGM) is consisted of D-
mannose and D-glucose residues (linked by β-1,4 bonds) with a ratio of
1.6:1 or 1.4:1, depending on the genotypes (Behera & Ray, 2017;
Zhang, Chen, & Yang, 2014). On average, there is an acetyl group on
the C-6 position of the backbone per every 9–19 sugar residues. Side
chains may exist with a degree of branching of ∼8%. The molecular
weight of KGM ranges from 500 k to 2000 k, depending on the plant
source and processing methods. KGM tends to have a homogeneous size
distribution with a polydispersity (MW/Mn) of 1.21 (Behera & Ray,
2017; Zhang et al., 2014).
KGM has good water binding and gelation capacity as well as film
forming property (Zhang et al., 2014). These functional properties
make konjac corm powder and KGM excellent food ingredients. Konjac
powder has been a food item in China and Japan since ancient times.
There are a few KGM based food products from the markets such as
noodles and cakes which are locally popular. KGM is a GRAS (generally
regarded as safe) food additive as approved by Health Canada in Ca-
nada and FDA (Food and Drug Administration) in USA. It is also ap-
proved by European Union as E425 (Tester & Al-Ghazzewi, 2016).
There are various health effects associated with the consumption of
KGM and related products. The health effects include weight loss and
satiety, oral health, enhancing the growth and viability of beneficial
organisms in colon, binding of nutrients (e.g., cholesterol), and so on
(Tester & Al-Ghazzewi, 2016). There has been increasing interest in
using KGM for the formulation of functional foods.
Apart from food applications, KGM has been used in other areas
such as for biomedical and environmental uses. Compared with syn-
thetic and fossil oil based polymers, natural polysaccharides including
KGM tend to be renewable, environmentally friendly (biodegradable),
and biocompatible (Zia, Zia, Zuber, Ahmad, & Muneer, 2016). KGM has
been a research focus in the last few years. This is partially reflected by
some recent reviews on various aspects of KGM (Behera & Ray, 2017;
Tester & Al-Ghazzewi, 2016; Zhang et al., 2014; Zia et al., 2016). For
example, Zhang et al. (2014) reviewed the modifications of KGM for the
uses in oral colon targeting drug delivery systems. Zia et al. (2016)
reviewed the properties and applications of KGM based polyurethanes.
The nutritional properties and health effects of KGM and the hydro-
lyzed products have also been reviewed lately (Behera & Ray, 2017;
Tester & Al-Ghazzewi, 2016). These reviews pointed out that native
KGM has a very limited range of functionalities. It is commonly mod-
ified to expand the functional variation for diverse applications (Zhang,
Xie, & Gan, 2005). During the last few years, many different types of
chemical and physical modification methods such as grafting and
electrospinning have been used to create new properties of KGM for
desired applications (e.g., as wound dressing hydrogel and for the re-
moval of heavy metals from waste water) (Chen, Zhang, Ding, Lin, &

Abbreviations: CKGM, carboxymethyl KGM; DS, degree of substitution; DP, degree of polymerization; KGM, konjac glucomannan; TEMPO, 2,2,6,6-tetramethyl-1-piperidiny-1-oxyl
E-mail address: fzhu5@yahoo.com.

https://doi.org/10.1016/j.foodchem.2018.02.151
Received 6 September 2017; Received in revised form 21 November 2017; Accepted 27 February 2018
Available online 06 March 2018
0308-8146/ © 2018 Elsevier Ltd. All rights reserved.
F. Zhu
Lu, 2017; Shahbuddin, Bullock, MacNeil, & Rimmer, 2014). A review
on the recent progress in this field would greatly support the current
exploitation of KGM as versatile biomaterial.
The present mini-review summarises the chemical and physical
modifications of KGM and the various applications, focusing on the
literatures from the past 5 years. The basics of KGM such as extraction,
structure, and physicochemical properties have been reviewed pre-
viously (Behera & Ray, 2017; Zhang et al., 2014), and thus, are not
covered in this review. Readers are encouraged to refer to the previous
publications to gain the basic background information on KGM. There
has been a rather large number of publications on the chemical and
physical modifications of KGM from the last 5 years or so. Therefore,
only representative papers have been intentionally selected in the
current review in order to comprehensively cover the various mod-
ifications and applications of KGM, while not exceeding the word limit
of the Journal. The applications of the modified KGM, instead of the
modification/synthesis process (e.g., reaction conditions), are empha-
sized to give the paper a focus. In some of the reported cases, combined
modifications were employed (e.g., both physical and chemical), which,
in this review, is categorised according to the major and emphasized
type of modification. In general, this review is categorised into sub-
sections primarily based on the types of modifications. For example,
within the chemical modification section, subsections on substitution-,
chain elongation-, and depolymerisation-type modifications are pro-
duced. Readers are also encouraged to refer to the Supplementary
material (figures and tables) for much increased readability and clarity.
The enzymatically modified KGM, which has been recently reviewed
(Tester & Al-Ghazzewi, 2016), is not covered here. This review may
provide a basis to further develop konjac as a sustainable crop.
2. Chemical modifications
Many types of chemical modification methods and the combinations
have been conducted on KGM (Supplementary Table 1 and Fig. 1). The
major modifications include substitution, chain elongation, and de-
gradation with some examples of the themes illustrated (Supplementary
Fig. 1). These modified KGM have been used in diverse applications as
described below.
2.1. Substitution
2.1.1. Acetylation for film formation
Environmental concerns require the production of biodegradable
films to replace the fossil oil based products. KGM triacetate and acetate
with different degrees of substitution (DS) were prepared for thermo-
plastic film production (Enomoto-Rogers, Ohmomo, & Iwata, 2013). At
a DS of 3, the number based molecular weights of the KGM triacetate
was 3 × 105 and the degree of polymerisation (DP) was 1 × 103. In-
creasing DS of both acetates increased the decomposition temperatures
of KGM. Increasing DS also decreased the glass transition temperature
of the acetates (e.g., from 219 °C at DS of 1.3 to 178 °C at DS of 3),
probably due to the effect on hydrogen bonding. The KGM acetate was
made into films by casting the solution. The films were transparent.
Increasing DS decreased the elongation at break and the tensile strength
of the films as illustrated in Supplementary Fig. 2A, which may be due
to the effect of acetylation on hydrogen bond formation and inter-
molecular interactions of KGM molecules (Enomoto-Rogers et al.,
2013). Huang, Takahashi, Kobayashi, Kawase, and Nishinari (2002)
studied the effect of acetylation on the gelation properties of KGM and
found that increasing DS increased the elasticity of KGM gel. This ap-
peared to be similar to the result that increasing DS decreased the
tensile strength of KGM film (Enomoto-Rogers et al., 2013), though it
should be noted that film and gel are different structural systems. Only
one study so far reported the production of KGM acetate based film
(Enomoto-Rogers et al., 2013).
An additional group (butyryl) was attached to the KGM acetate to
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Food Chemistry 256 (2018) 419–426
produce mixed esters varying in the DS (Danjo, Enomoto-Rogers,
Takemura, & Iwata, 2014). The mixed esters had number based mole-
cular weights of 3–6 × 105 and DP of > 1 × 103. The mixed esters had
a much higher decomposition temperature (∼360 °C) than KGM
(274 °C). The acylation of hydroxyl groups of KGM much decreased the
intramolecular dehydration, improving the thermostability. The mixed
esters of KGM were made into transparent films (Danjo et al., 2014).
Increasing DS of acetylation increased the tensile strength of the films,
whereas increasing DS of butyrylation enhanced the elongation at
break. This is possibly due to the plasticizing effect of butyryl group.
The resulting films had comparable mechanical properties to those of
commonly used polymers such as PMMA, suggesting the potential
commercial applications of KGM based films (Danjo et al., 2014).
2.1.2. Acylation with acyl carbon chains for film formation
Apart from KGM acetate and butyrate as described in the previous
section, KGM was acylated with acyl carbon chains (n from 2 to 12)
(Enomoto-Rogers, Ohmomo, Takemura, & Iwata, 2014), which has
been the only systematic study on KGM acrylated with different carbon
chain lengths so far. DS of these KGM esters reached 3 with DP varying
from 0.9 × 103 (KGM laurate) to 2.6 × 103 (KGM propionate). In-
creasing carbon number of acyl chains decreased the glass transition
temperature (Tg) of the samples. KGM acetate (described in the above
section) was also acylated with acyl carbon chains (n from 3 to 18).
These mixed esters had DS ranging from 0.7 (KGM acetate stearate) to
2.2 (KGM acetate propionate) and DP varying from 100 (KGM acetate
palmitate) to 330 (KGM acetate butyrate). Therefore, KGM was par-
tially degraded during the synthesis of the mixed esters. The mixed
esters of KGM had higher Tg than those of respective homoesters. The
acyl groups introduced onto KGM may disrupt the molecular interac-
tions and the hydrogen bond formation. The esters were insoluble in
ethanol and water but soluble in tetrahydrofuran, ethyl acetate, and
chloroform. The esters were dissolved in chloroform and casted into
transparent and colorless films (Enomoto-Rogers et al., 2014). In-
creasing chain length of acryl groups increased the elongation at break,
while decreasing the Young’s moduli and tensile strengths of the films.
Overall, it becomes obvious that the functional properties of the films of
KGM esters could be mostly controlled by the type and DS of acryl
groups (Danjo, Enomoto-Rogers, Takemura, & Iwata, 2014; Enomoto-
Rogers et al., 2013, 2014).
2.1.3. Carboxymethylation for film formation, paper strengthening, and
controlled release
Carboxymethyl KGM (CKGM) is one of the most commonly used
modified KGM. The introduced carboxymethyl group decreased the
interactions (intermolecular hydrogen bonding) among KGM, rendering
the KGM more liquid like (Kobayashi, Tsujihata, Hibi, & Tsukamoto,
2002). The effect of carboxymethylation on the water binding proper-
ties of KGM was further studied (Xiao, Dai, Wang, Ni, & Yan, 2015). The
modification decreased the equilibrium moisture content (25 °C), water
absorption, and solubility of KGM. Atomic force microscopy (AFM)
analysis showed that the modification increased the folding of the KGM
molecules, possibly making them less interactive with water molecules
(Xiao et al., 2015).
CKGM was mixed with soy protein isolate (SPI) to produce biode-
gradable films (Wang et al., 2014). Both hydrogen bonding and Mail-
lard reactions occurred between CKGM and SPI, making the two com-
ponents compatible. The interactions increased the tensile strength and
elongation at break, while decreasing the oxygen permeability of the
composite films. Increasing CKGM proportion decreased the surface
roughness and water adsorption, while increasing the surface wett-
ability of the films (Wang et al., 2014). The decreased water adsorption
could be attributed to the increased hydrophobicity of KGM by car-
boxymethylation as described by Xiao et al. (2015).
CKGM has been used as a paper strengthening agent (Wang, He,
Wang, & Song, 2015). Addition of CKGM (0.9%) increased the density,
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burst and tensile indexes, and folding endurance of the paper. CKGM
increased the bonding force between the paper fibers due to electro-
static interactions. An excessive amount of CKGM caused charge re-
pulsion, weakening the paper structure (Wang et al., 2015). In addition
to CKGM, polyamide-epichlorohydrin (PAE) was used to synergistically
increase the wet strength of the paper. Increasing degree of carbox-
ymethylation of KGM increased both the dry and wet tensile indexes of
the paper, which could be attributed to the altered charges of CKGM
(Wang et al., 2015).
CKGM (negatively charged), together with 2-hydroxypropyl tri-
methyl ammonium chloride chitosan (HACC) (positively charged), have
been used to produce nanospheres/microspheres through electrostatic
interactions for controlled release applications (Shi et al., 2016). The
size and zeta potential of the composite spheres ranged from 600 to
1460 nm and 39 to 50 mV, respectively. A maximum of encapsulation
efficiency of ovalbumin (as a model ingredient) at 72% was achieved
through process optimization. In vitro controlled release test (at pH 7.4)
showed that ovalbumin was released over a period of 24 h (Shi et al.,
2016). Such a composite sphere system can be used for controlled re-
lease of macromolecules such as proteins and vaccines, though in vivo
and clinical studies remain to be conducted.
2.1.4. Cationization for waste water treatment and paper strengthening
Cationic KGM was produced by reacting with (2-methacryloylox-
yethyl)trimethylammonium chloride and 3-chloro-2-hydroxypropyl
trimethylammonium chloride as a flocculant for waste water treatment
and as a paper strengthening agent, respectively (Ren, Zhang, Qin, & Li,
2016; Wang, He, Yan, & Song, 2017). The reaction partially decom-
posed KGM and the grafting was initiated by free radicals on the KGM
skeleton. The modified KGM had DS ranging from 0.09 to 0.3. The
cationic KGM showed good flocculating capacity at pH of 1–9 and in the
presence of salt. In a model system, the cationic KGM with a DS of 0.2
decreased the turbidity of a kaolin suspension (0.1%) by up to 90% at
pH 7. The flocculating capacity of cationic KGM could be due to the
electrostatic interactions with the negatively charged contaminants in
water (Ren et al., 2016). Similarly, cationic KGM also interacted with
negatively charged surface of pulp fibers, improving the paper making
performance (Wang et al., 2017). Quantitively, addition of cationic
KGM (1%) enhanced the tensile (by 11%) and burst (by 13%) indexes as
well as the folding endurance (by 72%) of the paper. Scanning electron
microscopy (SEM) analysis showed that the paper fibers became more
compact with the addition of the cationic KGM (Wang et al., 2017).
2.1.5. Cyanoethylation for liquid crystal formation
Cyanoethyl KGM with various DS (0.1–2.1) were synthesized by
adding acrylonitrile in N, N-dimethylformamide solution (Shen, Li,
Zhang, Wan, & Gao, 2012). The successful introduction of cyanoethyl
groups was confirmed by FTIR (Fourier-transform infrared spectro-
scopy) and NMR (nuclear magnetic resonance) spectroscopy analysis
which are the routine type of analysis for verifying the modification.
Cyanoethyl KGM with a DS of 2.1 dissolved in 1-allyl-3-methylimida-
zolium chloride (AMIMCl) exhibited liquid crystalline behaviors when
the concentration reached 16%. Rheological analysis revealed the for-
mation of crystalline regions in isotropic phase, mesophase, and ani-
sotropic phase (Shen et al., 2012). The advantages of this kind of liquid
crystal polymers over the synthetic ones can be non-toxicity, biode-
gradability, and the clearly defined thermotropic and lyotropic meso-
phase behaviors.
2.1.6. Esterification for emulsification
KGM has been esterified with different functional groups to produce
emulsifiers (Long, Pan, & Yao, 2016; Meng, Zheng, Wang, Liang, &
Zhong, 2014). KGM-oleic acid ester with a DS of 0.37 was produced
through a lipase-catalyzed reaction in isooctane (Long et al., 2016). The
KGM ester is amphiphilic and may have potential applications as food
flavoring agents, surface coating materials, and medical material for
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Food Chemistry 256 (2018) 419–426
DNA and drug delivery where emulsion systems are needed (Long et al.,
2016). KGM octenyl succinate was produced by a microwave based
method under alkaline conditions (Meng et al., 2014). Emulsifying
capacity and emulsion stability (up to 90 days) of the KGM octenyl
succinate were excellent, which indicates the potential use of this KGM
product in emulsion based food/controlled release systems.
Gurusmatika, Nishi, Harmayani, Pranoto, and Sugahara (2017) showed
that octenyl succinate of glucomannan from A. oncophyllus possessed
immunomodulatory activity by stimulating macrophages in vitro.
Therefore, it may be expected that KGM octenyl succinate, apart from
being an emulsifier, also has this biological activity.
2.1.7. Phthalation for waste water treatment
One study so far reported the phthalation of KGM for waste water
treatment (Zhang, Han, Yao, Pang, & Luo, 2013). KGM was reacted with
phthalic anhydride using pyridine as the catalyst to form KGM phtha-
lates with different DS up to 0.55. The synthetic process is illustrated in
Supplementary Fig. 1A. The KGM phthalate as a solid biosorbent was
used to remove the copper ions in waste water (Zhang et al., 2013). Cu
(II) adsorption capacity of the KGM phthalate depended on the DS, pH,
and the amount of phthalate present. The Cu(II) adsorption was mostly
of chemisorption and the equilibrium was established within 2 h. At an
acidic pH, a maximum adsorption of 17 mg/g was achieved for KGM
phthalate, which was higher than that of common biosorbents (e.g.,
that of grape stalks was 12 mg/g). When the pH was higher than 10, a
KGM phthalate (100 mg/L) effectively removed 99% of Cu(II) from the
solution. The KGM phthalate appeared to be an efficient biodegradable
absorbent to remove Cu(II) in waste water (Zhang et al., 2013).
2.1.8. Sulfation for drug
KGM was hydrolyzed by sulfuric acid before sulfation reaction with
piperidine-N-sulfonic acid in DMSO or with SO3-pyridine complex in
pyridine at high temperature (60 °C) (Bo, Muschin, Kanamoto,
Nakashima, & Yoshida, 2013). KGM sulfates with DS of 1.3–1.4 and
molecular weights of 0.4 × 104–1.0 × 104 were prepared (Bo et al.,
2013). The in vitro anti-HIV and anti-coagulant activities of KGM sul-
fates were tested. The anti-HIV capacity of the sulfate was comparable
to that of an anti-HIV drug (ddC), whereas the blood anti-coagulant
activity was similar to that of curdlan and dextran sulfates. Mechanistic
studies suggested that these bioactivities were much due to electrostatic
interactions between the amino groups of targets and the KGM sulfate
(Bo et al., 2013). A previous study showed that curdlan (a naturally
occurring polysaccharide with a linear 1,3-β pyranoside structure)
sulfate also possessed anti-AIDS virus activity (Yoshida et al., 1990).
Curdlan sulfate had an EC50 (50% effective concentration of sulfated
glucomannan on HIV) of 0.1 μg/mL, which was lower than KGM sulfate
(0.7 μg/mL). Therefore, the advantage of using KGM sulfate as an anti-
AIDS drug remains to be explored in a comprehensive way.
2.2. Chain elongation
2.2.1. Cross-linking
2.2.1.1. Modifying rheology. KGM was cross-linked by borate for
rheological modifications (Ratcliffe, Williams, English, & Meadows,
2013). Rheological analysis of small strain deformation showed that the
cross-linking greatly slowed the network dynamics while increasing the
network connectivity (Ratcliffe et al., 2013). Such a modification in
KGM rheology may only provide a fundamental basis for the
formulation of food and health products, which remains to be linked
to any practical application.
2.2.1.2. Waste water treatment. KGM was cross-linked with calcium
oxide in the presence of graphene oxide (GO) to form hydrogel (Gan,
Shang, Hu, Yuen, & Jiang, 2015). SEM analysis showed that the
hydrogel of KGM and GO mixtures had a much more compact
structure with a rougher surface than that of KGM. The hydrogel of
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cross-linked KGM was used to remove dyes (methyl blue and methyl
orange) in waste water. The incorporation of GO greatly enhanced the
dye adsorbing capacity of hydrogel. The adsorption behaviors of the
hydrogel for both dyes followed a pseudo-second-order and were well
described by the Freundlich isotherm model (Gan et al., 2015). The
resulting hydrogel may be used for water purifications.
2.2.1.3. Protein desalting. Another study reported the cross-linking of
KGM using epoxy chloropropane as the cross-linker (Xu, Yao, Yu, Zhou,
& Zhao, 2014) (Supplementary Fig. 1B). Nanospheres with the
diameters of 40–50 nm were produced from the cross-linked KGM
through emusification. The nanospheres can be easily dispersed with
good flowing property. They also have high moisture adsorption and
desorption capacities. These properties suggested that they may be used
as adsorbents which can be easily recycled (Xu et al., 2014). Acid-
hydrolysed KGM was also cross-linked to produce microspheres
(Supplementary Fig. 2B) (Xiong, Zhou, Sun, Li, & Zhao, 2014). The
pre-treatment by acid hydrolysis greatly reduced the viscosity of KGM
solution. The microspheres showed great stability in a range of pH
(1–14) and in commonly used buffer solutions as well as to autoclaving.
Protein-desalting experiments showed that the cross-linked KGM
microspheres showed similar performance to a commerical gel
(Sephadex G25). The modified KGM can be an economic alternative
in the protein desalting application (Xiong et al., 2014).
2.2.2. Graft copolymers
2.2.2.1. Biomedical application. Three KGM based hydrogels were
produced (Shahbuddin et al., 2014). KGM was cross-linked by
termination of radicals from oxidation with Ce(IV). Semi-IPN (semi
interpenetrating network) was formed from copolymerization of
PEGDA [poly(ethylene glycol)-diacrylate] and NVP (N-
vinylpyrrolidone) with KGM. Graft-conetworks were also formed by
cross-linking KGM with Ce(IV). SEM analysis showed that the samples
had smooth surfaces with differences in the cross-section morphology.
The semi-IPNs and the graft-conetwork had porous structure possibly
due to phase separation during the reactions. The hydrogels were
cytocompatible, while the graft-conetworks can stimulate fibroblast
metabolic activity and the migration of keratinocytes and fibroblasts.
Therefore, the KGM based hydrogels can be used for wound healing
(Shahbuddin et al., 2014).
2.2.2.2. Encapsulation. CKGM was grafted with poly(ethylene glycol)
(PEG) to form graft copolymers (CKGM-g-PEG) (Li, Xia, Branham, Ha, &
Wu, 2011). The CKGM-g-PEG (0.2%) was mixed with α-cyclodextrin
(6%) for self-assembly to encapsulate glucose oxidase (GOX) in solution
(Supplementary Fig. 1C). The self-assembly appeared in the form of
hollow nanospheres/microspheres with the size ranging from 340 nm to
1.2 μm, depending on the DS (PEG substitution) and the concentration.
Transmission electron microscopy (TEM) analysis revealed the
distinguishable outer shell and central core of the particles. A
maximum of encapsulation efficiency (67%) was recorded. The
leakage rate of GOX from the spheres was as low as 2%, while the
substrate (glucose) easily penetrated into the spheres to get oxidized by
the encapsulated GOX. The encapsulation greatly increased the
thermostability, the pH range for optimal enzymatic activity, and the
storability of GOX. The spheres showed great in vitro biocompatibility
with the L929 cells (MTT viability assay), suggesting potential
biomedical uses (Li et al., 2011).
CKGM (hydrophilic) was conjugated with cholesterol (hydrophobic)
to become amphiphilic (Ha, Wu, Wang, Peng, & Ding, 2011)
(Supplementary Fig. 1D). The amphiphilic conjugates formed self-ag-
gregates with very low critical aggregation concentrations of
2.59 × 10−3–5.89 × 10−3 mg/mL. The size of the self-aggregates
ranged from 391 nm to 1 μm as revealed by dynamic laser light-scat-
tering technique. The amphiphilic conjugate was used to encapsulate
etoposide (a hydrophobic drug as a model bioactive compound)
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Food Chemistry 256 (2018) 419–426
through self-aggregation with the aid of sonication (Ha et al., 2011).
The size of the formed particles was dependent on pH and ionic
strength. In vitro release test showed a sustainable releasing behavior of
etoposide from the encapsulation system (Ha et al., 2011), though in
vivo test remains to be conducted for any practical application.
2.2.2.3. Enhancing oil recovery. KGM-g-AM (acrylamide)-g-AA (acrylic
acid)-g-APEG (allyl polyoxyethylene ether) was produced through free-
radical copolymerization (Gou et al., 2017) (Supplementary Fig. 1E).
Structural analysis showed that the resulting graft-copolymer had a
much reduced crystallinity than the KGM and had a porous
microstructure. The graft-copolymer showed good biodegradability
with over 60% of the mass degraded in 4 weeks by a bio-degradation
test. Compared to partially hydrolyzed polyacrylamide, the copolymer
showed better salt resistance, anti-shearing capacity, temperature
tolerance, and desired viscoelasticity. The resistance factor
(RF = 14.1) and residual resistance factor (RRF = 4.95) of the
copolymer were obtained from a core flood test, which are indicative
of the ability for mobility control and flooding effect with improved oil
recovery (by 14%). The results suggested that the KGM-g-AM-g-AA-g-
APEG copolymer could replace the acrylamide based conventional
copolymers for enhanced oil recovery in oil field mining (Gou et al.,
2017).
2.2.2.4. Molecular-imprinting for extraction of bioactive compound. KGM
based molecular-imprinted copolymer (MIP) was produced using
acrylic acid as a functional monomer and N,N′-
methylenebisacrylamide as a cross-linker (Tian, Zhou, Xiong, & Lu,
2017) (Supplementary Fig. 1F). Caffeine was used as the template for
formation of the molecular-imprinted copolymer. SEM analysis showed
that the molecular imprinting process produced much more
aggregation for the copolymers to form larger particles. The
molecular imprinting technique greatly improved the adsorption
(from 22 to 63 mg/g) and selectivity (selective factor increased from
0.9 to 2.5) of the copolymer for caffeine extraction. Langmuir equation
well described the adsorption isotherms of the MIP. The selective
adsorption of caffeine by the MIP was successfully applied in a range of
beverage samples with high recovery rates from 91 to 99%. The MIP
obtained is cost-effective for rapid and sensitive extraction of caffeine
from beverage samples (Tian et al., 2017). It may be expected that other
types of bioactive compounds can be extracted by KGM based MIPs,
which remains to be tested. Molecularly imprinted biopolymers based
on other types of polysaccharides such as chitosan have been developed
for extraction of targeted chemical components (Wang et al., 2014). It is
not clear if the KGM based MIP has any advantage over MIPs based on
other types of natural polysaccharides. Comparative studies are needed
to explore this aspect.
2.2.2.5. Waste water treatment. CKGM was conjugated with
polydopamine as an absorbent to remove Pb(II) in waste water (Chen
et al., 2017). This modified KGM is placed in this subsection rather than
in the carboxymethylation section (Section 2.1.3) because the grafting
is the major reaction resulting in the function described here (for waste
water treatment). The KGM based copolymer showed a high adsorption
capacity (a maximum of 95 mg/g at 25 °C) and can be easily recovered
by using HCl (0.001 M) as the desorbing agent. The Pb(II) adsorption
process was well described by Langmuir linear model. The process was
endothermic and spontaneous in nature. The kinetics was well
described by the intra-particle diffusion model and a pseudo-second
order equation. Possible interactions were electrostatic attraction and
chelation between the functional groups (eOH/eNH2) of the
copolymer and Pb(II) in solution (Chen et al., 2017).
2.2.2.6. Water adsorption. KGM was conjugated with acrylic acid and
acrylamide (KGM-AA-AM) or acrylic acid, acrylamide, and kaolin
(KGM-AA-AM-K) through a frontal polymerization technique (Li, Ji,
F. Zhu
Xia, & Li, 2012). SEM analysis revealed very porous microstructure of
both co-polymers. The copolymer KGM-AA-AM-K was used as a water
absorbent, and showed great water adsorption capacity (1.9 kg/g in
distilled water and 93 g/g in saline). The porous structure, numerous
OH groups of KGM, and the charge on kaolin contributed to the high
water adsorption of the KGM based copolymer (Li et al., 2012). Li et al.
(2009) synthesized KGM-g-acrylic acid polymers using a frontal
polymerization technique, and found that the maximum water
absorbency reached 1.3 kg/g, which is not as high as the result of Li
et al. (2012). Chen, Zhang, and Li (2015) prepared a superabsorbent of
KGM graft-acrylic acid polymers using trimethylolpropane
trimethacrylate as a cross-linker. The swelling of this co-polymers
reached a maximum at pH 7.4, though the water absorbency was not
studied. Yang, Zhang, Yang, Yan, and Jiang (2017) found that the
aggregate size of KGM based super-absorbents greatly affected the
water adsorption capacity, though the structure of the studied
absorbents was not specified. Small particles with a lower adsorption
capacity reached the maximum of adsorption faster than large particles
which tend to have a higher adsorption capacity (Yang et al., 2017).
Overall, it appeared that KGM based graft copolymers can possess great
water adsorption capacity which may be maximized by altering their
structural properties. There are super-absorbents based on other types
of natural polysaccharides such as starch (Zhong et al., 2013).
Comparative studies are needed to reveal if KGM based super-
absorbents may have any advantage over those of other natural
polysaccharides.
2.3. Depolymerization
2.3.1. Deacetylation for wound dressing, moisture-resistant film, and waste
water treatment
KGM is deacetylated in an alkali solution [e.g., Ca(OH)2] and the
deacetylated KGM has been used to formulate wound dressing and
moisture-resistant films (Huang, Chu, Huang, Wu, & Tsai, 2015; Wei
et al., 2015), aerogel for arsenic removal in solution (Ye, Jin, Huang,
Hu, & Li, 2017), and biosorbent for the removal of copper(II) from
waste water (Liu, Zou, Peng, Hu, & Liu, 2016). The deacetylated KGM
can more easily form junction zones and network due to the reduced
steric hindrance (Huang et al., 2015). The Ca(OH)2-modified KGM
showed great in vitro biocompatibility with L929 fibroblast and HaCaT
keratinocyte cells. In vivo tests employing male Sprague-Dawley rats
were also conducted. The results showed that the films of deacetylated
KGM inhibited the activation and absorption of platelets, while pro-
moting wound contractility at an early stage of healing. Collagen se-
cretion and development of epithelial coverage and granulation tissues
in the wounds of rats treated with the films were recorded for 2 weeks
after the surgery. Overall, the deacetylated KGM has great potential for
wound dressing applications (Huang et al., 2015).
Deacetylated KGM solution was casted into film which was further
coated with shellac and stearic acid mixtures by brushing (Wei et al.,
2015). The moisture resistant properties of the resulting composite
films were studied. The shellac based coating, where the stearic acid
was dispersed, intimately adhered onto surface of the films of deace-
tylated KGM through physical interactions. The coating, which is hy-
drophobic, greatly improved the moisture barrier properties and tensile
strength of the films. Increasing concentration of stearic acid greatly
decreased the water vapor permeability of the composite film, while
increasing the water contact angle. The high moisture-resistant prop-
erties of the coated KGM based films may find applications in food
products which need strict moisture management (Wei et al., 2015).
Deacetylated KGM was mixed with graphene (GO), iron, and man-
ganese oxide (FMO) in solution before freeze-drying to form composite
aerogel (Supplementary Fig. 2C) (Ye et al., 2017). SEM analysis showed
that the aerogels are highly porous with very rough surface. The
aerogels with the addition of GO had great mechanical strength, which
was attributed to the molecular interactions between KGM and GO
423
Food Chemistry 256 (2018) 419–426
through hydrogen bonding. The composite aerogel showed great ca-
pacity to remove arsenite [As(III)] (up to 30 mg/g) and arsenate [As
(V)] (up to 12 mg/g) in solution (pH 7, 50 °C) (Ye et al., 2017). KGM
based aerogels, which are biodegradable, may be used as filter tip of
cigarettes to reduce the impact on the environment and to filter away
some harmful substance of the smoke. Another study also explored the
potential of deacetylated KGM-soy protein isolate (SPI) conjugate for
the removal of Cu(II) which is one of the most common pollutants in
waste water (Liu et al., 2016). Comparative analysis showed that the
incorporation of SPI into the deacetylated KGM greatly increased the Cu
(II) adsorption capacity in solution by 5 times (up to 63 mg/g at 25 °C).
This increase could be attributed to the strong chelating property of SPI
for the ion. The adsorption process also followed a pseudo-second-order
equation. Luo, Liu, Deng, and Lin (2011) explored the application of
carboxylic acid functionalized deacetylated KGM for the removal of
copper(II) from aqueous solution in a fixed-bed column system. The
cylinder shaped KGM based material was prepared by a single screw
extruder. SEM analysis showed that the material was porous. The ad-
sorption–desorption analysis of copper(II) removal showed that a
maximum adsorption of 35 mg/g was achieved. The adsorbed copper
ions could be easily desorbed by using HCl solution (0.01 mol/L) with
an efficiency of 98% (Luo et al., 2011). The above mentioned studies all
showed that different deacetylated KGM based material have great
potential for the removal of heavy metals from waste water. However,
in order to be commercially successful, cost estimation and technolo-
gical feasibility for large scale production should be analyzed to reveal
which one of these reported KGM polymers may be practically em-
ployed.
2.3.2. Oxidation for encapsulation, and fish feed and hard capsule
formulation
Oxidized KGM has been used as shell material for hard capsule
preparation, encapsulation of bioactives for controlled release, and as
an ingredient for fish feed formulation (Chen, Zhao, Liu, Li, & Liu, 2016;
Shi et al., 2017; Zhang et al., 2013). KGM was TEMPO (2,2,6,6-tetra-
methyl-1-piperidiny-1-oxyl)-oxidized on the C-6 position of sugar units
to various degrees (up to 80%) (Chen et al., 2016). Degree of oxidation
at 80% gave increased transparency and solubility of KGM, while de-
creasing the viscosity. The increasing number of carboxyl groups may
enhance the charge repulsion among the KGM molecules and disrupt
their interactions for decreased viscosity (Chen et al., 2016). The oxi-
dized KGM was made into films for hard capsule formulation. SEM
analysis showed that the oxidation process increased the smoothness of
KGM films. The oxidation increased the hydrophobicity, tensile
strength, and elongation at break of the films. The introduced COO−
groups may efficiently bind more water which may be a plasticizer for
the films to increase the elongation. In vitro drug (erythromycin stearate
as a model compound) dissolution test (0.1 M HCl and 37 °C) showed
that the shell rupture time for the KGM of 80% oxidation was 5–10 min
with 80% of the drug being released within 30–45 min. Overall, the
oxidized KGM appeared to be suitable for making the gastric soluble
hard capsules (Chen et al., 2016).
The COO− groups of TEMPO-oxidized KGM were cross-linked by
Fe3+ to form microspheres for the encapsulation of anthocyanins (hy-
drophilic) and β-carotene (hydrophobic) through ultrasonic emulsifi-
cation (Shi et al., 2017). The microspheres were further coated with
chitosan (positively charged) for targeted delivery. The co-encapsula-
tion of both bioactives was confirmed by confocal laser scanning mi-
croscopy. The controlled release of both bioactives were studied in vitro
using a simulated gastrointestinal tract (Shi et al., 2017). The co-en-
capsulation system effectively retained both anthocyanins and β-car-
otene in the gastric environment, and released them under the in-
testinal conditions. The co-encapsulation also increased the thermal
stability of the antioxidants (Shi et al., 2017).
KGM was oxidized by H2O2 to be used as a feed ingredient for a type
of fish (Schizothorax prenanti) (Zhang, Wu, Wang, & Wang, 2013). Up to
F. Zhu
8 g/kg of oxidized KGM was added into the fish diet. Various physio-
logical and biochemical markers of the fish, such as specific growth
rate, erythrocyte phagocytic index, and content of IgM, were monitored
and compared with those of the control group. The addition of the
modified KGM into the feed significantly improved the growth and aslo
the immune functions of the fish (Zhang et al., 2013). These effects may
be related to the improvement of oxidized KGM on the gut health of the
fish. Two more similar studies confirmed that oxidized KGM could
improve intestinal morphology and enhance the growth performance,
while modulating intestinal microflora of S. prenanti (Zhang, Wu, Xu, &
Yao, 2017; Zheng, Wu, & Xu, 2015). However, the structure of the
oxidized KGM should be studied to explore the structure–function re-
lationship of the product.
3. Physical modifications
There has been increasing demand for non-chemically and physi-
cally modified ingredients from the market due to consumers’ pre-
ference for “natural and healthy” products. A range of physical mod-
ifications, including electrospinning, microfluidic spinning, extrusion,
electric field processing, and γ-irradiation, have been conducted on
KGM to create a range of novel functionalities (Supplementary Table 2).
Some of the physical modifications such as extrusion and γ-irradiation
also induce chemical changes on KGM, altering the functional proper-
ties.
3.1. Electrospinning for biomedical scaffold
KGM and chitosan (ratio of 60/15–50/25 with a total solid con-
centration of 1.5%) were mixed in a diluted acetic acid solution (10%,
v/v) for electrospinning to form nanofibers (Nie, Shen, Zhou, Jiang, &
Chen, 2011). Increasing chitosan concentration decreased the diameter
of the nanofibers from 350 to 180 nm (Supplementary Fig. 2D). KGM in
aqueous solution was also electro-spun to form nanofibers, and in-
creasing KGM concentration from 0.6 to 1.2% increased the diameters
of the nanofibers from 150 to 350 nm. The in vitro biocompatibility of
the resulting nanofibers was studied to reveal their potential biomedical
uses. The resulting nanofibers showed great adherence to bone me-
senchymal stem cells than the bulk films (prepared from solution
casting) due to the nanofibrous and highly porous nature (Nie et al.,
2011). Zhu, Lin, Zhang, and Luo (2015) prepared KGM grafted with
styrene (St)/butyl acrylate (BA) (KGM-g-St/BA) and used the graft co-
polymer for electrospinning. The grafting greatly increased the hydro-
phobicity of the electrospun fiber films of KGM-g-St/BA, which remains
to be tested for any specific application (Zhu et al., 2015). Overall, the
electrospun nanofibers based on KGM have potential for biomedical
applications, which remains to be tested in clinical situation.
3.2. Microfluidic spinning for wound dressing and micro-reactor for
fluorescence reaction
A KGM and sodium polyacrylate (PAAS) mixture (1:1, w/w) was
made into microfibers through a microfluidic spinning technology
(0.1 mL/h and 800 rad/min) (MST) (Mu, Ni, Wang, Yuan, & Yan, 2017)
(Supplementary Fig. 2E). The microfibers are consistent in size with a
width of 100 μm. They can be easily arranged into microgrids and
microarrays for the recognition of amines and targeted reactions. The
KGM based microfibers were uniformly loaded with ofloxacin (an an-
tibiotics) for potential wound dressing applications (Mu et al., 2017).
3.3. Electric field processing for composite gel formation
KGM (up to 0.5%) and tungsten composite gels were prepared under
direct current electric fields (treatments up to 30 V and 15 min) with
sodium tungstate (up to 0.5%) (Wang, Zhuang, Li, Pang, & Liu, 2016).
Mechanistic studies showed that under acid condition the isopoly-
424
Food Chemistry 256 (2018) 419–426
tungstic acid ions got cross-linked with the OH groups of the C-6 po-
sition of KGM sugar units (Wang, Jiang, Lin, Pang, and Liu, 2016). A
maximum of springiness of 1.21 mm for the composite gel was obtained
under optimized conditions (sodium tungstate concentration of 0.3%,
KGM concentration of 0.5%, voltage of 25 V, and treatment time of
12 min). SEM analysis showed that the gel was made of thin strands and
was highly porous with non-uniformed pore size. The gels showed
pseudo-plastic behaviors and had low flow behavior indexes. The
freeze-dried gels showed a high porosity with a homogeneous dis-
tribution of pores. The KGM-tungsten gels were produced on positive
electrode and may be used to carry bioactives/drugs with negative
charges for targeted delivery (Wang, Zhuang, et al., 2016). Preparation
of gels using electric fields may become a facile technique in creating
novel properties of KGM based products.
3.4. Extrusion for modified rheology and water binding properties
KGM was extruded under 4 different conditions (solid content of 24
or 33%, temperature at 90 or 110 °C, with or without die restriction)
before grinding (Tatirat, Charoenrein, & Kerr, 2012). The extrusion
somewhat increased the size (e.g., from 112 to 144 μm) and roughness
of the KGM particles, while decreasing the water adsorption up to one
third of the original value. The degree of crystallinity increased when
the die restriction and high temperature (110 °C) were used. The visc-
osity of KGM solution (0.5%) decreased, which could be readily at-
tributed to the decreased molecular weight induced by extrusion (from
1.2 × 106 to 2.7 × 105). The shearing and higher temperature of ex-
trusion conditions mostly affected the properties of KGM. The extruded
KGM with reduced water absorption and viscosity may reduce the
choking risk of ingesting KGM-containing products (Tatirat et al.,
2012). The extruded KGM may be used in the formulation of food,
health and nutraceutical products with much reduced choking risk.
3.5. γ-Irradiation
3.5.1. Degradation
Prawitwong, Takigami, and Phillips (2007) studied the impact of γ-
irradiation (0.5–100 kGy) on molar mass and properties of KGM. In-
creasing irradiation dosage increased the free radical yield which
caused chain scission. The molecular weight and intrinsic viscosity of
KGM were decreased greatly by the treatment. No new chemical groups
were introduced except for a small amount of carbonyl groups. KGM
was degraded by γ-ray at 50 kGy with or without H2O2 (Pan et al.,
2013). γ-Ray and H2O2 synergistically degraded the KGM as revealed
by molecular weight analysis. This may be due to the free radical re-
actions, resulting in molecular scissions. The treatment also reduced the
degree of crystallinity and viscosity of KGM. The polydispersity index of
the resulting KGM reached 1, suggesting a much uniformed molecular
size distribution (Pan et al., 2013). The degraded KGM with much re-
duced viscosity may give reduced choking risk as well as altered texture
for formulation healthy food and nutraceutical products.
3.5.2. Antioxidant material
KGM was subjected to γ-irradiation at 100 kGy to obtain the de-
graded products with a good dispersibility (Jian et al., 2017). The ir-
radiation greatly reduced the number average molecular size of KGM
from 8.3 × 105 (native KGM) to 4.2 × 104 (at 100 kGy), while some-
what increasing the polydispersity from 1.1 to 1.3. The antioxidant
capacity of the degraded KGM against H2O2 induced damage on LO2
cells was studied. The cells pretreated with the degraded KGM product
had increased survival rates and activities of GSH-Px (glutathione
peroxidase) and CAT (catalase). The pretreatment also reduced the
accumulation of reactive oxygen species in the cells. The in vitro anti-
oxidant capacity of the degraded KGM could be due to the radical
scavenging effect (Jian et al., 2017). There are diverse health benefits of
hydrolysed KGM such as enhancing the immune response in human
F. Zhu
body and binding nutrients like cholesterol (Tester & Al-Ghazzewi,
2016). Therefore, it may be expected that γ-irradiated KGM also pos-
sesses these biological activities, which remain to be better studied. The
degraded KGM product may be used as an ingredient in functional food
formulations for health promoting.
4. Comparative studies are needed
In some cases, different modifications of KGM are related to the
same type of applications as described in the above 2 sections (Sections
2 and 3) (Supplementary Tables 1 and 2). A few examples are given
here. For waste water treatment, modified KGM based on cationization
(e.g., as flocculant) (Wang et al., 2017), phthalation (e.g., for Cu(II)
removal) (Zhang et al., 2013), cross-linking [e.g., for removal of dyes
(methyl blue and methyl orange)] (Gan et al., 2015), graft copolymers
[e.g., for Pb (II) removal] (Chen et al., 2017), and deacetylated KGM
based aerogel (e.g., for arsenite removal) (Ye et al., 2017) were sug-
gested. Both KGM-oleic acid ester and KGM octenyl succinate showed
good emulsifying capacity (Long et al., 2016; Meng et al., 2014). KGM
graft copolymers (Shahbuddin et al., 2014), deacetylated KGM (Huang
et al., 2015), and microfluidic spun KGM (Mu et al., 2017) were sug-
gested to have great potential for wound dressing and biomedical ap-
plications. KGM acylated with different functional groups (Enomoto-
Rogers et al., 2013), acetylated KGM (Enomoto-Rogers et al., 2014),
and CKGM-protein composite (Wang et al., 2014) were shown to have
good film forming capacity. All the studies claimed that the modified
KGM was suitable for some specific applications mentioned above.
Therefore, comparative studies/analysis are needed to confirm which
type of modified KGM is best suitable for specific applications.
Another consideration is that if the modified-KGM based products
described in this review have any advantage over products based on
other types of natural polysaccharides (e.g., starch). For example, both
KGM sulfate and curdlan sulfate showed anti-HIV activity (Bo et al.,
2013). Both KGM and chitosan based MIP could be used for the ex-
traction of chemical components (Tian et al., 2017; Wang et al., 2014).
Therefore, comparative studies are needed to reveal if there is any
advantage of using KGM based products over those of other natural
polysaccharides and also over the commerical products (e.g., anti-HIV
drugs).
Overall, comparison between the resultant modified-KGM (de-
scribed in this review) and the current/commercial products should be
conducted to reveal any technological advantage as well as possible
disadvantage of KGM based products. Cost estimation, technological
feasibility, and the impact of the synthetic process as well as the final
KGM products on the environment should be taken into consideration.
Clinical studies and pilot-scale trials should be conducted to distinguish
if the reported studies are mainly due to the pure academic curiosity or
if they have any potential industrial applications.
5. Conclusions and future research directions
KGM has been modified by various chemical and physical methods
or the combinations. The chemical methods include substitution-type
modifications (acetylation, carboxymethylation, cationization, cya-
noethylation, esterification with oleic acid, octenyl succination,
phthalation, and sulfation), chain elongation-type modifications (cross-
link and grafting), and degradation-type modifications (deacetylation
and oxidation). The physical methods include electrospinning, micro-
fluidic spinning, extrusion, electric field processing, and γ-irradiation.
The resulting modified KGM has been used in many different applica-
tions. They include thermoplastic film formation, paper strengthening
agent, emulsifier, biosorbent for water and pollutants in waste water,
drug formulation, protein desalting, wound dressing, encapsulation of
functional ingredient for controlled release, enhanced recovery of fossil
oil, molecular imprinting polymer for extraction, fish feed ingredient,
micro-reactor for fluorescence reaction, and enhanced antioxidant
425
Food Chemistry 256 (2018) 419–426
activity. KGM can be abundantly and sustainably obtained from konjac
cultivation with high yields. The modified KGM tends to be biode-
gradable and biocompatible with little impact on the environment. It
becomes evident that modified KGM has great potential to be used in
various food and non-food applications.
It is obvious that there are many research opportunities to better
develop KGM for diverse applications. KGM from other konjac species
such as A. guripingensis tends to have different functional properties
from that of A. konjac. The KGM of other species may also be modified
to create a wider range of functionalities which may expand the ap-
plications. Furthermore, the correct konjac species from which KGM is
derived should be specified in the report, requiring input from plant
biologist. Compared with other well-known and better studied plant
polysaccharides such as starch, cellulose, and pectin, KGM is still to be
modified by a range of different methods. Especially, physical mod-
ifications such as ultrasound and pulsed electric field, which appear to
be green and appealing to the public, remain to be more conducted on
KGM. A combination of different types of modifications (physical,
chemical, and enzymatic) may be used to create a wide range of KGM
functionalities. In some cases, different modifications of KGM led to
similar uses. For example, both cationic and carboxymethyl KGMs can
be ingredients for paper strengthening. Comparative studies should be
conducted to verify which modified KGM can better achieve the mission
in a holistic view. There is a need to compare KGM based products with
those based on other natural polysaccharides such as chitosan and
starch for the same categories of applications. So that any advantages of
using KGM based products may be revealed to support commercial
exploitation. Some of the studies reported the synthesis of the modified
KGM and only suggested some potential applications (e.g., oleic acid
ester). The actual application of these modified KGMs should be further
tested. In some applications of modified KGM such as encapsulation and
controlled release, in vivo and clinical studies should be conducted to
verify the usefulness of the reported results. The majority of the reports
reviewed here are laboratory-based. For commercial applications, the
performance of the modified KGM should be compared with that of
samples which are commonly used from the current market. For food
and pharmaceutical/biomedical applications, the safety and toxicity of
the modified KGM products (e.g., KGM based emulsifiers) should be
vigorously tested for potential clinical applications and to meet the
regulations and approval from government agencies such as FDA (Food
and Drug Administration). Finally, at a more fundamental level, the
structure-functionality/application relationships of modified KGM
should be systematically explored to provide a strong scientific basis to
better develop KGM as a versatile natural polysaccharide.
Declaration
The author declares no conflict of interest.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.foodchem.2018.02.151.
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