International Journal of Biological Macromolecules 60 (2013) 83–92

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International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Review

Galactomannan: A versatile biodegradable seed polysaccharide

Vipul D. Prajapati a,∗ , Girish K. Jani a , Naresh G. Moradiya a , Narayan P. Randeria a ,
Bhanu J. Nagar b , Nikhil N. Naikwadi a , Bhavesh C. Variya c
a
Department of Pharmaceutics, S.S.R. College of Pharmacy, Saily-Silvassa Road, Saily, Silvassa, U.T. of Dadra and Nagar Haveli 396230, India
b
Department of Pharmaceutics, Rofel Shri G. M. Bilakhia College of Pharmacy, Namdha Campus, Namdha Road, Vapi 396191, Gujarat, India
c
Department of Pharmacology, Shri G. H. Patel Pharmacy Building, M.S. University, Fateh gunj, Vadodara 390002, Gujarat, India

a r t i c l e i n f o a b s t r a c t

Article history: Polysaccharides have been finding, in the last decades, very interesting and useful applications in
Received 26 April 2013 the biomedical and, specifically, in the biopharmaceutical field. Galactomannans are a group of stor-
Accepted 16 May 2013 age polysaccharides from various plant seeds that reserve energy for germination in the endosperm.
Available online 23 May 2013
There are four major sources of seed galactomannans: locust bean (Ceratonia siliqua), guar (Cyamopsis
tetragonoloba), tara (Caesalpinia spinosa Kuntze), and fenugreek (Trigonella foenum-graecum L.). Through
Keywords:
keen references of reported literature on galactomannans, in this review, we have described occurrence
Major galactomannans
of various galactomannans, its physicochemical properties, characterization, applications, and overview
Polysaccharides
M/G ratio
of some major galactomannans.
© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction to polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2. Introduction to galactomannans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3. Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4. Physico-chemical properties and characterization of galactomannans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5. Applications of galactomannans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.1. Viscosity development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.2. Gel formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.3. Hydrogen bond formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.4. Water absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6. Major galactomannans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6.1. Locust bean gum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6.2. Guar gum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6.3. Tara gum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
6.4. Fenugreek gum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

1. Introduction to polysaccharides food reserve material (e.g., guar, locust bean, etc.), as mucilages in
the seed coats (e.g., psyllium seed, flaxseed, yellow mustard seed,
Seed polysaccharides are one of the most important categories etc.), and as cell wall materials of seed cotyledons and endosperms
of plant-originated gums used in the food industry, as they play (e.g., tamarind and soybean seeds). The chemical compositions,
important roles in both food processing and improving the mouth fine structures, and physical and functional properties of these
feel and texture of food products. The occurrence of polysaccharides polysaccharides can vary significantly with plant sources, grow-
in plant seeds is mainly in three forms: as nonstarch polysaccharide ing environments, and method of production. Seed polysaccharides
(nonstarch) are also an important source of dietary fiber, which
may exhibit bioactivities such as reducing calorie intakes, control-
∗ Corresponding author. Tel.: +91 0982 4284159; fax: +91 0260 2681104. ling blood glucose and insulin levels, and reducing the risks of heart
E-mail address: vippra2000@yahoo.com (V.D. Prajapati). diseases and colon cancer [1].

0141-8130/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ijbiomac.2013.05.017
84 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92
Fig. 1. General molecular structure of galactomannan.
Carbohydrate molecules have complex structures. These are the
most abundant of the natural products and the source of all bio-
logical energy. Being poly functional in nature, these molecules
participate in a multitude of chemical and biochemical reactions.
They are composed of the polyhydroxy aldehydes, ketones, alco-
hols, acids and their simple derivatives as well as their polymers
having linkages of the acetal type. Carbohydrates can be clas-
sified into monosaccharides, oligosaccharides and polysaccharides.
Monosaccharides are the lower members of carbohydrates, which
cannot be degraded by hydrolysis. Oligosaccharides and polysac-
charides are polymers of monosaccharides and their derivatives,
joined by acetal-type linkages. Oligosaccharides contain between
2 and 10 monosaccharide units, and polysaccharides contain more
than 10 units.
Polysaccharides, also known as Cinderella of biopolymers, hold
a wide range of different functions; sometimes they behave
as energy storage materials and the well-known examples are
starch, glycogen and some plant seed polysaccharides such as
locust bean gum, guar gum, tara gum and panwar gum. Some-
times they contribute to the structural integrity and mechanical
strength of plant tissues by forming a hydrated cross-linked three-
dimensional network (pectins play this role in land plants while
carrageenans, agar and alginate have an equivalent function in
marine species). On the other hand, polysaccharides such as cel-
lulose and chitin and, less frequently, xylans and mannans can
generate hard, solid structures or tough fibers by close packing of
the chains. Polysaccharides may also act as protective substances;
protective polysaccharides are exemplified by the antigenic and
immunogenic exocellular microbial polysaccharides-that are fre-
quently highly specific for particular organisms or by the exudate
gums from plants, which appear to provide a preventive func-
tion by sealing off the injured parts of the plant against bacterial
infections [2].
2. Introduction to galactomannans
Galactomannans are heterogeneous polysaccharides composed
by a ␤-(1–4)-d-mannan backbone with a single d-galactose branch
linked ␣-(1–6) (Fig. 1) [3]. They differ from each other by the
mannose/galactose (M/G) ratio. These gums are mostly obtained
from the endosperm of dicotyledonous seeds of numerous plants,
particularly the Leguminosae. The endosperm has several func-
tions: it serves as food reserve for germinating seeds and it
retains water, preventing the complete drying of the seeds [4,5].
There are four major sources of seed galactomannans: locust
bean (Ceratonia siliqua), guar (Cyamopsis tetragonoloba), tara (Cae-
salpinia spinosa Kuntze), and fenugreek (Trigonella foenum-graecum
L.). Among these, only locust bean and guar gums are of con-
siderable industrial importance. The use of tara and fenugreek
gums is limited due to availability and price. Other sources of
galactomannans have also been explored in the literature, but
no commercial potential can be expected in the near future
[3].
Galactomannan is derived from the seeds of plant C.
tetragonolobus, a pod bearing legume grown commercially in India,
Pakistan and the southwestern United States. The seed is composed
of hull (15%), germ (45%), and endosperm (40%). The ratio of d-
mannopyranosyl to d-galactopyranosyl units is about 1.8:1. The
average molecular weight of the Galactomannan is in the range of
1–2 × 106 Da [6]. Galactomannan forms viscous, colloidal disper-
sion when hydrated in water. It is being used as a viscosity builder
and water binder in many industries such as textile, food, paper,
petroleum, mining, explosives, and pharmaceuticals.
The molar ratio of galactose to mannose varies with plant ori-
gin but is typically in the range of 1.0:1.0–1.1, 1.0:1.6–1.8, 1.0:3.0,
and 1.0:3.9–4.0 for fenugreek, guar, tara, and locust bean gums,
respectively. The conformation of the 1→4-linked ␤-d-mannan
backbone is similar to that of cellulose, so that it does not dissolve in
water. The galactose side groups are considered to sterically disturb
the interchain association and crystallization, thereby imparting
certain water solubility to the galactomannans. As a result, the solu-
bility of the galactomannans increases with the degree of galactosyl
substitution: fenugreek and guar gums are readily dissolved in cold
water, but heating is needed to reasonably solubilize locust bean
gum in water.
The two main groups of galactomannan polysaccharides are
those derived from (a) the endosperm of plant seeds, the vast
majority of which originate in the Leguminosae, and (b) microbial
sources, in particular, the yeasts and other fungi.
3. Occurrence
The majority of galactomannans originate from Leguminosae
family. 70 species of the Leguminosae have been identified con-
taining galactomannans (Table 1). True galactomannans, as defined
by Aspinall (that is, those mannans containing more than 5% of d-
galactose) have also been extracted from members of Annonaceae,
the Convolvulaceae and the Palmae, Ebenaceae and Loganiaceae as
shown in Table 2. The general procedure to obtain galactomannans
from seeds combines extraction and purification processes. Briefly,
the seed hull is removed from the seeds and the germ is separated
from the endosperm. The most used separation procedures are: fil-
tration, sifting and in some cases (e.g., lab scale) they are separated
manually. The endosperm is dissolved in water (at temperatures
that can range between 20 and 120 ◦ C), followed by a precipitation
step using alcohol (in a ratio water:alcohol that can range between
1:1 and 1:3). No effects of the alcohol on galactomannans’ structure
have been reported [6,7].
 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92 85

Table 1 and prevent the mannose cis-OH groups in forming the hydrogen
Galactomannans of various species of Leguminosae and their reported value of M/G
bonds [8].
ratio.
Comparing the different galactomannans, it is obvious that,
Botanical name M/G ratio Reference since additional cross linking via hydrogen bonds goes hand in
Subfamily Species hand with less solubility, an increase in substitution leads to higher
solubility. The best solubility is found with galactomannan-1,1
Caesalpiniacae Cassia absus 3:1 [48]
C. emarginata 2.70:1 [32] in which the high substitution by galactose obviously establishes
C. Fistula 3:1 [45] so much steric hindrance that it dissolves easily in cold water
C. leptocarpa 3.05:1 [6] and prevents attack for some time for degrading enzymes. How-
C. marylandica 3.76:1 [40] ever, galactomannan-1,2 where on average each second mannose
C. nodosa 2.7–3.5:1 [49]
C. occidentalis 3:1 [45]
unit is blocked by galactose, shows so much steric hindrance and
C. tora 3:1 [27] so little hydrogen bonding between the molecular chains that it
Ceratonia siliqua 3.75:1 [34] hydrates instantly. Galactomannan-1,4 does not dissolve in cold
Caesalpinia cacalaco 2.50:1 [5] water but its solubility in boiling water is already better than that
C. pulcherima 2.7:1 [50]
of galactomannan-1,5 due to slightly higher degree of substitution
C. spinosa – [5]
Cercidium torreyanum 3.38:1 [45] by galactose side groups compared to galactomannan-1,5.
Delonix regia 4.28:1 [32] M/G ratio varies considerably depending on the galactomannan
Gleditsia amorphoides 2.5:1 [13] source and typically ranges between 1.1 and 5.0 [5]. Variations in
G. triacanthos 3.2:1 [13] the galactomannans’ structure, particularly in M/G ratio and fine
Gymnocladus dioica 2.71:1 [30]
structure, cause significant changes in the solubility, viscosity and
Parkinsonia aculeate 2.70:1 [45]
in the interactions between galactomannans and other polysaccha-
Mimosaceae Besmanthus illinoensis 2.69:1 [5]
rides. Usually, galactomannans with higher galactose content (such
Leucaena galauca 1.33:1 [5]
as GG) are ready soluble in water and exhibit a lower tendency to
Fabaceae Sophora japonica 5.19:1 [30] form gels as a result of synergistic interactions, when compared
Genista raetam 4.14:1 [32]
with galactomannans with a lower M/G ratio (such as LBG). The
G. scoparia 1.59:1 [27]
G. cretica 1.56–1.67:1 [50] higher solubility of GG has been attributed to the presence of a
G. foenum-graecum 1.2:1 [45] higher number of side chains, which keep the main mannose chains
G. hamosa 1.17:1 [45] far enough to prevent effective intermolecular interactions. On the
G. monspeliaca 1.08:1 [5] other hand, galactomannans with fewer side chains (higher M/G
G. polyserata 1.13:1 [50]
G. radiate 1.17:1 [6]
ratio) can interact with other polysaccharides due to their long
Anthyllis vulneraria 1.33:1 [5] blocks of unsubstituted mannose units [5].
Lotus corniculatus 1.25:1 [6] From the foregone discussion, it can be concluded that galac-
L. pedunculatus 1.04:1 [45] tomannans are rich in hydroxyl groups; this enables them to
L. scoparius 1.13:1 [40]
bind and take up water and rich in cis-OH groups, which allow
Alysicarpus veginalis 1.14:1 [27]
Desmodium pulchellum 2:1 [30] aggregation from chain to chain via hydrogen bonding so that
hydration becomes more complicated if interchange cross linking
can take place. By substitution with galactose, nature establishes
steric hindrance between the molecules and thus enhances water
solubility.
4. Physico-chemical properties and characterization of The characterization of physicochemical properties of galac-
galactomannans tomannans (Table 3) can be performed using different tech-
niques (e.g., gas chromatography, high-pressure anion exchange
For a better understanding of properties of galactomannans one chromatography, size exclusion chromatography, 13 C NMR spec-
should know the basic structure of their building units. It is obvious troscopy, capillary viscometry, shear and extensional rheology).
that mannose is provided with cis-OH groups in the galactoman- The most important parameters that define the nature of a
nan polymer. Therefore, an enhanced deposition to form hydrogen galactomannan are mannose and galactose (M/G) ratio, average
bonds between the polymannan chains is expected as long as neigh- molecular weight, fine structure, and intrinsic viscosity. Mannose
boring groups like galactose do not develop steric hindrance to and galactose ratio, the degree of substitution and the degree of
prevent the galactomannan chains from coming too closer together polymerization have been reported to affect edible films proper-
ties [9]. No effect of the average molecular weight as been reported
for galactomannan films. The monomeric sugars content and M/G
Table 2 ratio are generally determined by gas chromatography or by high-
Galactomannans of various species of non-Leguminosae and their reported value of
pressure anion exchange chromatography after partial or total
M/G ratio.
hydrolysis catalyzed by acid. The molecular weight distributions
Non-leguminosae species of galactomannans M/G ratio Reference can be determined by size exclusion chromatography. The galac-
Family Botanical name tose distribution along the mannan chain can be characterized
by 13 C NMR spectroscopy, or by enzymatic methods with ␤-d-
Annonaceae Annona muricata 4.46:1 [5]
Convolvulaceae Convolvulus tricolor 1.75:1 [48] mannanase that specifically degrades the non-substituted regions
Ipomoea muricata 1.8:1 [52] of galactomannans [10]. Intrinsic viscosity can be determined using
Ebenaceae Diospyros virginiana – [6] a capillary viscometer, by application of Huggins’ and Kramer’s
Loganiaceae Strychnos nux-vomica – [51] equations [11]. Furthermore, the evaluation of the rheological
Palmae Borassus flabellifer 2.4:1 [5]
Cocos nucifera 2.57:1 [45]
behavior plays an important role in the characterization of galac-
Arenga saccharifera 2.26:1 [45] tomannan solutions, since these are often used to modify textural
Phytelephas macrocarpa 50:1 [48] attributes [12]. This characterization can be performed through
Hyphaene thebaica 19:1 [45] shear (steady and dynamic conditions) and extensional rheology
Phoenix dactylifera 10:1 [6]
[13].
86 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92
Table 3
Galactomannans physico-chemical characteristics and its method of determination.
S. No. Characteristics
1 Monomeric sugar content & M/G ratio
2 Molecular weight distribution
3 Galactose distribution
4 Intrinsic viscosity
5. Applications of galactomannans
Galactomannans are widely utilized in the industry due to their
suitable functional properties, such as thickening, binding, and
stabilizing abilities. These functional properties are led by rhe-
ological behavior of galactomannans in an aqueous phase and
also by intermolecular binding in certain conditions. Hydrated
galactomannan molecules occupy a large hydrodynamic volume in
aqueous solution and control the rheological behavior of the entire
solution. Galactomannans themselves are nongelling agents, while
some galactomannans show synergistic interactions with other
polysaccharides such as agar, xanthan, carrageenan, and yellow
mustard gum to form a three-dimensional gel network in appropri-
ate conditions [14–17]. Galactomannans thus find a wide range of
applications as texture modifiers or stabilizers in food and pet food
industries. Applications of commercial and alternative sources of
galactomannans are given in Table 4.
The world figures of galactomannan consumption differ quite
considerably according to different sources. According to one esti-
mate, around 90–100 thousand tons are consumed per year. The
biggest consumption being that of guar gum with 70–80 thou-
sand tons followed by locust bean gum with 12–14 thousand tons.
Reviewing the technical applications, attention is drawn to the
chemical behavior of the different galactomannans. There are appli-
cations, which benefit from the excellent viscosity formation of
some galactomannans or their derivatives and there are also appli-
cations, which benefit from water absorption or from the formation
of hydrogen bonds as well as gel formation.
The three major galactomannans of commercial importance in
food and non-food industries are guar gum (GG, C. tetragonolobo,
M/G ratio: 2:1), tara gum (TG, C. spinosa, M/G ratio: 3:1) and locust
bean gum (LBG, C. siliqua, M/G ratio: 3.5:1) [4,18]. However, the
industry trends demand the introduction of alternative sources of
seed gums and therefore it is important to search for such alterna-
tive renewable sources [19]. In some works galactomannans have
been used in binary mixtures with other polysaccharides such as
xanthan gum, agar and ␬-carrageenan, to form gels with new prop-
erties [7,20–22]. Galactomannans can often be used in different
forms for human consumption. Featuring different physicochem-
ical properties, galactomannans are a versatile material used for
many applications: they are excellent stiffeners and stabilizers
of emulsions, and the absence of toxicity allows their use in the
textile, pharmaceutical, biomedical, cosmetics and food industries
[23–25]. Particularly in the food industry the main applications
Table 4
Commercial and alternative sources of galactomannans and their possible applications.
S. no. Species of galactomannan
1 Ceratonia siliqua (locust bean gum)
2 Caesalpinia pulcherrima
3 Gleditsia triacanthos
4 Cesalpinia spinosum (tara gum)
5 Dimorphandra gardneriana Tul
6 Cyamopsis tetragonolobus (guar gum)
7 Adenanthera pavonina
8 Prosopis pallida (mesquite gum)
9 Mimosa scabrella
10 Trigonella foenum-graecum (fenugreek gum)
Method to determine References
Gas chromatography & high pressure anion exchange chromatography [53]
Size exclusion chromatography [56]
13
C NMR spectroscopy and Enzymatic method with ␤-d-mannanase [54,55]
Capillary viscometer, By application of Huggins’ and Kramer’s equations [11]
of galactomannans are in dairy products, fruit-based water gels,
powdered products, bakery, dietary products, coffee whiteners,
baby milk formulations, seasonings, sauces and soups, tinned meats
and frozen and cured meat foods. This broad range of applica-
tions reflects a great number of different functional characteristics
including high solution viscosity, stabilization of frozen systems
and mixed gel formation with other polysaccharides and proteins
[4].
Recently, some works showed the possibility of using galac-
tomannans in the formation of films and coatings [6].
5.1. Viscosity development
Some galactomannans, especially guar, but also Cassia and
locust bean gum and their derivatives (anionic, cationic and non-
ionic) develop very high viscosity in aqueous solution. In the textile
industry they are used to thicken the dyebaths in printing and
dyeing of fibers, fabrics and carpets. The gums control the flow char-
acteristics of the dye formulations, so that sharp, bright patterns
can be achieved. For different types of cloth and dyestuff, different
types of thickener are used – mostly in combinations. In the field
of explosives, guar gum and derivatives are used to thicken nitrate
salt solutions, which are the basic components of slurry explosive
formulations. These compositions are safer to use and can be for-
mulated to demand as a viscous liquid or even as gels. It is well
known that cracking and opening up the oil or gas bearing zones
with hydraulic pressure can increase the productivity of oil and
gas. Hydroxypropyl guar solution and other derivatives are used in
this process which is known as hydraulic fracturing. In this aspect
another property of galactomannans is also of advantage: the abil-
ity to gel with elements like boron or transition metals in the form
of their salts, which can be used to block or tighten wells. Since this
gelling reaction is reversible with change of pH, it is used to control
fluid loss in well.
The great advantage of galactomannans is their ability to form
very viscous solutions at relatively low concentrations that are
only slightly affected by pH, ionic strength and heat processing
[11]. Galactomannans’ viscosity tends to remain constant over a
broad pH range (1–10.5), mainly due the neutral character of their
molecules, and also is not expected that their properties will change
with ionic strength. However some degradation may occur under
highly acidic and alkaline conditions at high temperatures. The
viscosity and the stability of the galactomannan solutions upon
storage depend on the time and temperature used during the
Applications in various formulation as Reference
Thixotropic, binder, stabilizer, lubricator [57]
Thixotropic, binder, stabilizer, lubricator [6]
Stabilizer, thickener, emulsifier [13]
Stabilizer, thickener, emulsifier [57]
Stabilizer, thickener, emulsifier [10]
Stabilizer, thickener, emulsifier, firming agent [57]
Stabilizer, thickener, emulsifier [6]
Stabilizer, thickener [58]
Stabilizer, thickener [7]
Stabilizer, thickener [57]
 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92
Fig. 2. Locust bean gum (a) pods, (b) seeds and (c) powder.
film-forming solution preparation. Heating the galactomannans at
temperatures above 60 ◦ C tends to provide a high initial viscos-
ity but leads to an inferior stability (in terms of time-dependant
changes in viscosity). The most convenient temperature depends
on the galactomannan source. For example, locust bean gum must
be heated at 80 ◦ C for 20–30 min to guarantee its full dispersion,
while the optimal conditions to disperse guar gum involve heating
at 25–40 ◦ C for 2 h [5]. Galactomannan solutions usually exhibit
a non-Newtonian behavior, in which the viscosity decreases with
the increase of shear rate [26]. The degree of substitution in galac-
tomannans profoundly affects their solution properties [27].
5.2. Gel formation
Galactomannans are able to form gels with certain metal salts.
This effect is used in the field of textiles to print vat-dyestuffs in
two phases, which yields bright and sharp prints. On the other hand
galactomannans affect carrageenan and agar gels which diminish
from one galactomannan to another in the direction of increasing
galactose content. Thus it can be assumed that the mannose residue
of the main chain is mainly involved. Therefore, only galactoman-
nans with little or no steric hindrance by galactose groups may
show this effect. Such properties will be useful not only in food and
pet food but also in technical applications, where gels are used to
bear and bind odors, as in solid air fresheners. Transport of solid
powders like coal or ores suspended in such gels through pipeline
could also be possible as these gels have excellent suspending force,
which can be destroyed immediately when reaching the final point
of destination by heating to only about 50 ◦ C.
5.3. Hydrogen bond formation
Easy hydrogen bond formation is one of the characteristics of
galactomannans. This is used widely in the paper industry where
guar has replaced locust bean as wet end additive.
Galactomannans replace the natural hemicellulose in paper
bonding. Since galactomannans absorb onto the hydrated cellu-
lose fibers, as the hydrogen bonding effect is one of the major
factors in fiber bonding. Machine speed is increased by using galac-
tomannans and the retention of fine fibers during the process is
also increased. Carboxymethyl derivatives of Cassia gum also show
excellent hydrogen bonding effects, especially when used as wet-
end additives and as sizing agent in paper manufacturing. Thus
lightweight papers can be produced with excellent tightness, so
that printing inks cannot strike through. In the mining industry
galactomannans are used as chemical flotation agents by getting
absorbed onto hydrated mineral surfaces. In flotation, the galac-
tomannan functions as depressant to block the absorption of other
87
reagents onto the surfaces of talc and other gangues, which are
mined along with the valuable minerals.
5.4. Water absorption
To protect water sensitive goods, they may be spread with galac-
tomannan powder and then packed. Dry guar is used to cover
substances to prevent water from entering into cartridges filled
with explosive powders, cables and so on. Cross linked galactoman-
nan derivatives can be used in competition with synthetic polymers
as absorbents for hygiene articles.
Obviously, the applications of galactomannans depend more or
less on their ability to form hydrogen bonds, a property which
is counter played by steric effect of galactose side groups, which
help to achieve increased solubility. During the last several years
many plant species have been investigated for their galactomannan
contents to improve their properties by chemical modification and
increase their utilization.
6. Major galactomannans
6.1. Locust bean gum
Locust bean gum (Fig. 2) is a popular natural polymer which is
mostly used in food industry as well as in pharmaceutical indus-
try. This natural polymer is conventionally used as an excipients
in manufacturing different formulation which mainly depends on
its thickening and gelling property [28]. Locust bean gum is a non-
starch polysaccharides consisting of galactose and mannose in the
ratio 1:4 and hence they are known as galactomanan [29]. The man-
nose elements from a linear chain linked with galactopyranosyl
residues at side chain at varying distance depending on the plant
origin [30]. Being a galactomanan locust bean gum has a wide appli-
cation in pharmaceutical field. It is also known as carob bean gum
and is derived from the seeds of the leguminous plant C. siliqua
Linn belonging to family Fabaceae. This gum is widely cultivated in
the Mediterranean region and to smaller extent also in California.
The brown pods or beans of the locust bean tree are processed by
milling the endosperms to form locust bean gum [31].
Locust bean gum consists mainly of a neutral galactomanan
polymer made up of 1,4-linked d-mannopyronosyl units and every
fourth of fifth chain is substituted on C6 with a d-galactopyranosyl
unit (Fig. 3) [32,33]. The ratio of d-galactose to d-mannose differs
and this is believed to be due to the varying origins of the gum
materials and growth conditions of the plant during production.
The physicochemical properties of galactomanan are strongly influ-
enced by the galactose content and distribution of the galactose
units along the main chain. Longer galactose side chains produce
88 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92
Fig. 3. Structure of locust bean gum consisting of mannose and galactose.
stronger synergistic interaction with other polymers and greater
functionality. Since it is a neutral polymer and its viscosity and sol-
ubility are therefore little affected by pH changes within the range
of 3–11 [34,35].
The production of commercial locust bean, guar, and tara gums
is similar, involving separation of endosperms from the seed hull
and germ, followed by grinding and sifting of the endosperm into
fine particle-sized flour. Further purification is made by repeated
alcohol washings. Most commercial gums contain more than 80%
galactomannan. The quality or purity of the final gum product
depends on the extent of endosperm separation and de-hulling.
Remaining fragments of the hull may appear as dark specks and
deteriorate product quality. The carob pod contains approximately
10% of seeds by weight. The endosperm is commonly called splits
because two spherical halves constitute the endosperm surround-
ing the germ. The splits are milled to obtain flours that give a cloudy
solution when dissolved in water. The flour is then dispersed into
hot water and insoluble particles are removed by diatomaceous
earth filtration. The clarified solution is then precipitated using iso-
propyl alcohol, washed with alcohol, pressed, dried, ground, and
sieved. The final product is a white to cream-colored powder that
should give a clear solution when dissolved in water.
Locust bean gum is comprised of a high molecular weight
polysaccharides composed of galactomanans consisting of a (1–4)-
linked ␤-d-mannose backbone with (1–6)-linked side chains of
␣-d-galactose [36], being thus neutral polymers [31]. INEC tech-
nical committee reports that the standard method using the
consumption of sodium chlorite is unsuitable and recommends a
gel permeation chromatography method. This provides a molecular
weight range of 50,000–300,000.
The various galactomanans can be differentiated by the dis-
played mannose:galactose ratio (M/G ratio), the substitution pat-
tern of side chain units and their molecular weight, the latter being
influenced by harvesting and manufacturing practices, among
other factors [37]. The M/G ratio varies, therefore, depending on
Fig. 4. Guar gum (a) pods, (b) seeds and (c) powder.
the distribution of the galactose units over the mannose backbone,
being approximately 4:1 for locust bean gum [38], 3:1 for tara gum
and 2:1 for guar gum [39]. This ratio is main characteristic affecting
galactomanans solubility, as higher water solubility is afforded by
higher galactose content [40], an effect that has been justified by
the introduction of an entropic, and perhaps steric, barrier to the
ordered mannose chains [37]. This observation makes guar gum the
most soluble and also the most widely used of the galactomanans.
6.2. Guar gum
Due to its unique rheology modifying properties, it is being
widely used across a broad spectrum of industries viz. oil well
drilling, textile, paper, paint, cement, cosmetic, food, pharmaceu-
tical, etc. India is the major producer of guar in the world and
its contribution to the world-production is around 80%. In India,
Rajasthan and Haryana States contribute 85% of the total produc-
tion of India. India is a major exporter of guar gum (Fig. 4); the
country’s export of guar gum was 186,718.4 MT worth Rs. 10.50 Bil-
lion (US$ 235 Million) during the year 2005–2006. USA, China and
Germany are the major importing countries accounting for more
than 60% of export of guar gum from India. Chemically, guar gum is
a straight chain galactomannan, which is 75–85% of the endosperm,
has a chain of (1→4)-linked-␤-d-mannopyranosyl units with sin-
gle ␣-d-galactopyranosyl units connected by (1→6) linkages to, on
the average, every second main chain unit (Fig. 5).
The development of guar gum resulted from the shortage of
locust bean gum in the 1940s. The guar plant is an annual sum-
mer legume that is cultivated mainly in western India and eastern
Pakistan, and to a lesser extent in tropical areas, such as South and
Central America, Africa, Brazil, Australia, and the semiarid regions
of the U.S. Southwest. The plant grows to about 1 m in approxi-
mately 5 months and yields pods slightly smaller than the carob
pod. The guar pod contains no more than 10 seeds, in which the
endosperm corresponds to 35% by weight.
 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92
Fig. 5. Structure of guar gum consisting of galactose and mannose.
Guar also known as cluster bean (C. tetragonoloba L.) a drought
hardy leguminous crop. Guar is being grown for seed, green fod-
der, vegetable and green manuring. It is an annual plant, about 4
feet high, vertically stalked, with large leaves and clusters of pods.
Each pod is about 5–8 cm long and has on an average 6–9 small
grayish-white pea shaped seeds. The pods are used as a green veg-
etable or as a cattle feed besides the industrial extraction of guar
gum. Guar grows best in sandy soils. It needs moderate, intermit-
tent rainfall with lots of sunshine. The crop is sown after the first
rains in July and harvested in October–November. It is a short dura-
tion crop and is harvested within 3–4 months of its plantation. Guar
is a rain dependent crop; rainfall influences the yield of the crop. Its
seed consists of seed coat (14–17%), endosperm (35–42%) and germ
(43–47%). It has attained an important place in industry because of
its galactomannan rich endosperm [32].
The gum is commercially extracted from the seeds essentially by
a mechanical process of roasting, differential attrition, sieving and
polishing. The seeds are broken and the germ is separated from
the endosperm. Two halves of the endosperm are obtained from
each seed and are known as undehusked guar split. When the fine
layer of fibrous material, which forms the husk, is removed and
separated from the endosperm halves by polishing, refined guar
splits are obtained. The hull (husk) and germ portion of guar seed
are termed as guar meal. The refined guar splits are then treated
and finished into powders (known as guar gum) by a variety of
routes and processing techniques depending upon the end product
desired.
The molar ratio of galactose to mannose of guar gum is approx-
imately 1:2. The side group substitution occurs irregularly: side
groups are arranged mainly in pairs and triplets. The average
molecular weight varies, typically up to a few million, depend-
ing on growth and manufacturing factors. The persistence length
of molecularly solubilized guar gum has been reported to be ca.
4 nm, similar to that of molecularly solubilized locust bean gum
[37]. It thus seems that the intrinsic flexibility of the mannan
backbone itself is little influenced by galactose substitution. Dif-
ferences in functional properties between locust bean and guar
gums may rather reflect differences in their solubility and tendency
Fig. 6. Tara gum (a) pods, (b) seeds and (c) powder.
89
toward intra- and intermolecular aggregation that are relevant to
the extent of galactose substitution.
Modified Guar gum is widely used in pharmaceutical application
due to its viscosity increasing properties. The therapeutic effect of
Guar gum is due to its ability to swells rapidly in aqueous media to
form viscous dispersions or gels. When inhaled guar gum adsorbed
in stomach and halted or alters absorption of glucose, cholesterol
and possibly drugs.
Guar gum and its derivatives are used as binder and disinte-
grater in tablets to add cohesiveness to drug powder. Today, guar
gum is also used as a controlled-release agent for drug due to high
hydration rate (swelling in aqueous media). It also used as thickener
and stabilizer in pharmaceutical formulation. When mixed with
different ingredients in formulation of tablets it form protective
layer and consequently, drug releases out from the guar gum tablet
in a sustained manner, achieving the desired kinetics effect. And
masked unpleasant taste and odor of drug and improve its stability
and drug release properties.
The role of guar gum and its derivatives to control blood sugar
is well know Diabetes is a chronic disease, which occurs when the
pancreas does not produce enough insulin, or when the body can-
not effectively use the insulin it produces. This leads to an increased
concentration of glucose in the blood (hyperglycemia). The World
Health Organization (WHO) estimates that more than 180 million
people worldwide have diabetes. This number is likely to more than
double by 2030. Dietary fiber decreases postprandial plasma glu-
cose, insulin and triglyceride concentrations, and has a clinically
relevant hypocholesterolaemic effect.
Guar gum is also helpful in weight reduction and cancer therapy
especially colorectal cancer most common form of cancer due to
intestinal disorder.
6.3. Tara gum
The tara tree is a spiny evergreen shrub that grows to 3–10 m.
The tree is found in South American countries, including Bolivia,
Peru, Ecuador, Chile, and Colombia, but the major cultivator is
Peru. The flat pod of tara is about 10 cm long and 1–3 cm wide
and contains several seeds. Tara gum (Fig. 6) is extracted from the
endosperm with warm or hot water. The industrial manufacturing
process is essentially the same as that of locust beam gum and guar
gum.
The molar ratio of galactose to mannose of tara gum is approxi-
mately 1:3 (Fig. 7). The side group substitution is considered to have
random and blockwise distributions [41]. The average molecular
weight typically ranges from 0.2 to 2 million. The persistence length
and the Mark–Houwink–Sakurada exponent of molecularly solubi-
lized tara gum have been reported to be 3 nm and 0.79, respectively
[37], similar to those of locust bean and guar gums. The intrinsic
flexibility of galactomannan backbone thus seems to be insensitive
to the degree of galactose substitution. The galactose substitution
90 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92
Fig. 7. Structure of tara gum consisting of mannose and galactose.
Fig. 8. Fenugreek gum (a) plant, (b) seeds and (c) powder.
ratio of tara gum is in the middle of highly substituted cold-water-
soluble guar and the less substituted locust bean gum, which is only
a little soluble in cold water. Tara gum is partially soluble in cold
water up to about 80% of the dry weight. The thickening ability of
tara gum is higher than that of locust bean gum and comparable
to that of guar gum. The freeze–thaw stability is superior to that of
locust bean gum.
Tara gum also exhibits synergistic interactions with xanthan
and ␬-carrageenan. The magnitude of synergistic increments in gel
strength is larger than the highly substituted guar gum but smaller
than the less substituted locust bean gum. Therefore, there is a
trend in interactions between galactomannans and helixforming
polysaccharides that synergistic effects are progressively enhanced
with decreasing galactose content of the galactomannans. Similar
to the case of locust bean gum–␬-carrageenan mixed gels, X-ray
fiber diffraction patterns of tara gum–␬-carrageenan mixed gels
are essentially identical to those of pure ␬-carrageenan, suggest-
ing the absence of discrete intermolecular binding between the
two polysaccharides [42]. Tara gum is still a little exploited func-
tional food ingredient despite its moderate functional efficiency.
Organoleptic characteristics of tara gum are said to be much better
than those of guar gum.
6.4. Fenugreek gum
Fenugreek (Fig. 8), T. foenum-graecum, is a 60 cm tall annual
leguminous plant native to southern Europe and western Asia and
has a long history as a culinary and medicinal herb since ancient
times. The plant is grown in northern Africa, the Mediterranean,
western Asia, northern India, and currently in Canada [43]. The
fenugreek pod is about 3–10 cm long and 1 cm wide and contains
10–20 seeds with a size of about 2–3 mm. The seed has a strong
aroma and is somewhat bitter in taste. Fenugreek polysaccharide
contains small amount of sugars other than mannose and galactose.
This discrepancy might be due to less efficient methods of purifi-
cation, contamination and the analytical method employed. M/G
in fenugreek gum, in most cases, is ∼1. Thus fenugreek gum has
the highest galactose (∼48%; M/G, 1.02:1) in its molecule, and its
linear mannan backbone has ␣, 1→6 linked single galactose grafts
on nearly all the mannose groups of the main chain. Besides fenu-
greek, Lucerne (Medicago sativa) and clover (Trifolium pratense), less
common galactomannans, have ∼48% galactose. Molecular weight
of fenugreek gum is ∼30,000 Da, corresponding to an average pres-
ence of 180–190 monosaccharide (mannose + galactose) units in a
molecule. On an average, the linear mannan backbone of fenugreek
polysaccharide is built up of 90–95, ␤, 1→4 linked mannopyra-
nosyl units and each backbone monomer carries an ␣, 1→6 linked
galactopyranosyl group (Fig. 9).
Fenugreek seed-endosperm galactomannan was not in indus-
trial production till 1993. Currently some industries are producing
and marketing a sizable amount of fenugreek gum, and other fenu-
greek products are finding increasing applications. Guar and Locust
bean gum have been in industrial use for quite some time. Similar
to guar gum, fenugreek gum is also a product from a widely grown
annual agriculture crop, and hence its sustainable supply is well
assured. Besides, fenugreek seed also contains spicy oil, saponins
and edible protein, thereby making it a cost effective agricultural
crop.
Fenugreek gum is extracted from the endosperm or ground
whole seed with water or dilute alkali, and the yield varies from
13.6 to 38%, depending on the variety/cultivar and extraction
Fig. 9. Structure of fenugreek gum consisting of galactose and mannose.
 V.D. Prajapati et al. / International Journal of Biological Macromolecules 60 (2013) 83–92
methods [2]. Commercial fenugreek gum products, such as
Fenupure and Fenulife, contain over 80% galactomannans with
about 5% proteins. Laboratory preparation involving pronase (a
nonspecific protease isolated from Streptomyces griseus) treat-
ments produces gum products of much higher purity with less
than 0.6% protein contaminants [43].
The molar ratio of galactose to mannose of fenu-
greek gum is approximately 1:1. A reported value
of the molecular weight is 1.4 million, compared to
1.3 and 1.2 million for commercial guar and locust bean gum,
respectively [43]. The radius of gyration of fenugreek gum was
75 nm, which is in agreement with the range obtained by experi-
ments and modeling for a gum with equal galactose and mannose
contents and a molecular weight of 1.4 million [44,45]. Solution
properties of fenugreek gum are typical of a random coil polymer
[43]. In steady-flow rheological tests, fenugreek gum solutions
exhibit pseudoplastic behavior at high shear rates. Mechanical
spectra of locust bean, guar, and fenugreek gums with comparable
molecular weights are similar in shape, but with slightly smaller
moduli values for fenugreek gum. Fenugreek gum is a nongelling
galactomannan and shows resistance against freeze–thaw treat-
ments. In addition, little synergistic interaction was observed
between fenugreek gum and other gums.
Polysaccharides are generally considered to be non-surface
active, although in practice some surface activity of a gum spec-
imen may be observed in experiments. Such apparent surface
activity has been attributed to the presence of small amounts of
protein impurities [46]. Fenugreek gum was reported to possess
substantial surface activity and be able to produce stable oil-in-
water emulsions with moderately small droplet sizes (2–3 ␮m)
[47]. In addition, physical separation of protein residues from the
crude gum sample did not reduce the surface activity. It is there-
fore tempting to assume that the surface activity is an intrinsic
property of the polysaccharide. However, a protease-treated fenu-
greek gum sample containing less than 0.6% protein (calculated
from nitrogen content) exhibited a reduced surface activity. These
conflicting results may solely indicate that the protease treatment
is more effective in eliminating residual proteins. Protein compo-
nents in fenugreek gum ingredients may be tightly associated with
polysaccharide chains and capable of dominating some surface
activity-related functional properties.
7. Conclusion
Galactomannans are widely utilized in the industry due to their
suitable functional properties, such as thickening, binding, and
stabilizing abilities. These functional properties are led by rheo-
logical behavior of galactomannans in an aqueous phase and also
by intermolecular binding in certain conditions. Among all galac-
tomannans, only locust bean and guar gums are of considerable
industrial importance. The use of tara and fenugreek gums is limited
due to availability and price. There are still several seed galac-
tomannans that are not investigated so far and studies on such
sources can make significant contribution in this direction. There-
fore, in the years to come, there will be continued interest in
galactomannans and their potentiality aimed at the development
of better materials for food and non-food industries.
Acknowledgements
The authors are highly thankful to SSR College of Pharmacy,
Silvassa for providing all the necessary support and the essential
library information resources.
91
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