A review study on chemical composition and molecular structure of newly plant gum exudates and seed gums

A review study on chemical composition and molecular structure of newly plant gum exudates and seed gums

Food Research International 46 (2012) 387–398 Contents lists available at SciVerse ScienceDirect Food Research International journal homepage: www.e...

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Food Research International 46 (2012) 387–398

Contents lists available at SciVerse ScienceDirect

Food Research International journal homepage: www.elsevier.com/locate/foodres

Review

A review study on chemical composition and molecular structure of newly plant gum exudates and seed gums Hamed Mirhosseini ⁎, Bahareh Tabatabaee Amid Department of Food Technology, Faculty of Food Science and Technology, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

a r t i c l e

i n f o

Article history: Received 1 June 2011 Accepted 29 November 2011 Keywords: Polysaccharides Plant gum exudates Seed gum Thickening agent Foaming agent Emulsifying agent

a b s t r a c t A large number of plants can produce the complex polysaccharides commercially known as ‘plant-based gums’. Several studies on various plant-based gums (mainly plant gum exudates and seed sums) have resulted in the identification of valuable natural sources of complex carbohydrate polymers that promote the desired quality, stability, texture and appearance. The plant gum exudates and seed gums are the complex polysaccharides/ carbohydrate polymers commonly used as a dietary fiber, thickening agent, foaming agent, film, emulsifier, stabilizer and drug delivery agent. The physical and functional properties of plant-based gums depend on their chemical compositions and molecular structures. Recently, there is a substantial interest to elucidate the relationship between the chemical composition, molecular structure and physical characteristics and functional properties of plant gum exudates and seed gums. The present study also summarized the molecular structure, chemical composition and functional properties of various types of plant gum exudates. © 2011 Elsevier Ltd. All rights reserved.

Contents 1. 2.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . Gums sources . . . . . . . . . . . . . . . . . . . . . . . 2.1. Plant-based gums . . . . . . . . . . . . . . . . . . 2.1.1. Chemical composition and molecular structure 2.1.2. Classification of plant-based gums . . . . . . 3. Summary . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . of plant-based . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction The polysaccharide gums represent one of the most abundant raw materials. The researchers have mainly studied the polysaccharide

Abbreviations: BSG, Basil seed gum; CBG, Carob bean gum; CSG, Cassia seed gum; cLBG, Crude locust bean gum; G/M, Galactose/mannose; DDS, De-hulled durian seed; DSG, Durian seed gum; FG, Fenugreek gum; FSG, Flaxseed gum; GG, Guar gum; KG, Karaya gum; LBG, Locust bean gum; MNG, Malva nut gum; M/G, Mannose/galactose; MSG, Mesquite seed gum; OHC, Oil holding capacity; rLBG, Refined locust bean gum; SDG, Secoisolariciresinol diglucoside; TKP, Tamarind kernel powder; TKSG, Tamarind kernel seed gum; TSP, Tamarind seed polysaccharide; TG, Tara gum; WHC, Water holding capacity; WDS, Whole durian seed. ⁎ Corresponding author. Tel.: +60 3 89468390; fax: +60 3 89423552. E-mail addresses: [email protected] (H. Mirhosseini), [email protected] (B.T. Amid). 0963-9969/$ – see front matter © 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodres.2011.11.017

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gums due to their sustainable, biodegradable and bio safe characteristics (Rana et al., 2011). The term “gum” is used to describe a group of naturally occurring polysaccharides that come across widespread industrial applications due to their ability either to form the gel or make the viscous solution or stabilize the emulsion systems (Williams & Phillips, 2000). Water-soluble gums — also known as ‘hydrocolloid’ are used for various applications as dietary fiber, texture modifiers, gelling agents, thickeners, stabilizers and emulsifiers, coating agents and packaging films (Anderson & Andon, 1998; Williams & Phillips, 2000; Koocheki, Kadkhodaee, Mortazavi, Shahidi, & Taherian, 2009; Mirhosseini & Tan, 2010 a, b; Mirhosseini, Tan, & Naghshineh, 2010). Various parts of plant (e.g. plant cell walls, tree exudates, seeds, tuber/roots, seaweeds) have surface cells containing gums, mucilage, and fiber and protein compounds. Some of plant seeds have surface cells containing gums, mucilage, fiber and protein. Plant gum exudates are produced by several plants as a result of the protection mechanisms against mechanical or microbial injury (Rana et al., 2011).

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A number of fruits are also known to contain notable amount of miscellaneous compounds with respect to the level of structural and non-structural carbohydrates, depending on the fruit, its ripening period and storage time. There are several examples such as mango (Mangifera indica L., family Anacardiaceae), papaya (Carica papaya L., family Caricaceae), banana (Musa acuminata, family Musaceae), carambola (Averrhoa carambola L., family Oxalidaceae), and guava (Psidium guajava L., family Myrtaceae) (Chin, Ali, & Lazan, 1999). A considerable number of the leguminous and convolvulus plant seeds are the valuable sources of seed gums. In addition, there is a distinct difference which applies to their structure and characteristics — from species to species (Pazur, 1986). The considerably growing interest in plant gum exudates is due to their diverse structural properties and metabolic functions in food, pharmaceutical, cosmetic, textile and biomedical products (Nishinari, Zhang, & Ikeda, 2000). Plant polysaccharide gums can be used as dietary fiber, texture modifiers, gelling agents, thickeners, emulsifiers, stabilizers, coating agents and packaging films (McClements, 2005). In the recent years, the demand for plantbased gums in food systems, medicines and drug delivery systems has been considerably increased because they are the most notable ingredient in liquid and semisolid foods (Williams & Phillips, 2000). However, the market still desires new sources of plant-based gum to meet the demand for ingredients with more usefulness in food systems. Through the past years, a sensible increase in research interest is observed within the category of extractable seed components — e.g. carbohydrates and saponin (Sauvaire, Ribes, Baccou, & LoubatieresMariani, 1991; Taylor et al., 1997). Recently, there has been increased interest in the physical and functional properties of plant gum exudates and seed gums from various sources (Chen, Xu, & Wang, 2006; Palanuvej, Hokputsa, Tunsaringkarn, & Ruangrungsi, 2009; Somboonpanyakul, Wang, Cui, Barbut, & Jantawat, 2006). However, there is limited information about the chemical structure, physicochemical and functional properties of the plant gum exudates and seed gums. The present work summarized the relationship between the chemical composition, molecular structure and physical characteristics and functional properties of plant-based gums. The functional properties of the plant gums significantly affect the scope of their application. The gum functional properties are sensitive to the processing conditions. Therefore, the main objective of the present study was to study the chemical composition and molecular structure of plantbased gums (mainly plant gum exudates and seed gums). 2. Gums sources The natural gums are categorized based on their origins, behaviors and chemical structures. Gums are known as complex polysaccharides from various sources e.g. endosperm of plant seeds (guar gum), plant exudates (e.g. tragacanth), tree or shrub exudates (e.g. gum Arabic, karaya gum (KG) and tragacanth), sea weed extracts (e.g. agar), bacteria (e.g. xanthan gum), and animal sources (chitin) (Table 1) (Laaman, 2011; Williams & Phillips, 2000). 2.1. Plant-based gums Plant gums are the polysaccharides originated from various parts of plant (e.g. plant cell walls, tree exudates, seeds, tuber/roots, seaweeds) (Hydrocolloids Cosmetics, 2011). There are a large number of plant species that are being “cultivated” that are capable of producing gums which can be implemented in the food industry as additives. Most of plant gums belong to the Leguminosae family such as Acacia senegal as a source of gum acacia or gum Arabic; Astragalus spp., as a source of tragacanth; Cyamopsis tetragonolobus, as a source of guar gum; Ceratonia siliqua, as a source of locust bean gum (LBG) (Ibańez & Ferrero, 2003). Recently, many plants have been chemically analyzed and introduced as a potential source of plant gum exudates. These plant gums include guar with 19–43% gum (Undersander et al.,

Table 1 Main sources of natural gums. Williams and Phillips (2000). Botanical

Algal

Microbial Animal

• Trees Cellulose • Tree gum exudates Gum arabic, gum karaya, gum ghatti, gum tragacanth • Plants Starch, pectin, cellulose • Seeds • Tubers Konjac manan • Red seaweeds Agar, carrageenan • Brown seaweeds Alginate • Xanthan gum, curdlan, • dextran, gellan gum, cellulose • Gelatin, caseinate, whey protein, chitosan

1991), Cassia brewsteri with 33.7 ± 0.4% gum (Cunningham & Walsh, 2002) and mesquite with 24.9% gum (Estévez et al., 2004). Plant gums have more advantages than the other gum from animal and microbial sources, due to the friendly image toward consumers (Glicksman, 1969). Previous researchers have studied the chemical structure of various plant gums such as Malva nut gum (MNG) (Chen, Cao, & Song, 1996; Somboonpanyakul et al., 2006), mesquite seed gum (MSG) (Ibańez & Ferrero, 2003; Vernon-Carter, Beristain, & Pedroza-Islas, 2000), fenugreek gum (FG) (Stephen & Churns, 1995; Garti, Madar, Aserin & Sternheim, 1997), flaxseed gum (FSG) (Chen et al., 2006; Cui & Mazza, 1996), and carob bean gum (CBG) (Dakia, Blecker, Roberta, Watheleta, & Paquota, 2008; Kawamura, 2008). Table 2 also shows a list of mucilage polysaccharides and gum exudates from selected plants. From the chemical point of view, these water-soluble gum exudates are either polysaccharides (i.e. gum Arabic, guar gum, carboxymethylcellulose, carrageen, starch and pectin) or proteins (such as gelatin). 2.1.1. Chemical composition and molecular structure of plant-based gums Structural study is a basic requirement for understanding the rheological behaviors, gelling properties, and other physical behaviors of gums, which are directly related to the structural features (Chaubey & Kapoor, 2001). The physical and structural features of plant gum exudates are defined by molecular weight, monosaccharide composition, sequence of monosaccharide, conformation, configuration and position of glycoside linkages, particle size, solubility and rheological properties (Cui, 2005; Zhang, Cui, Cheung, & Wang, 2007). The hydrocolloids are made up of monosaccharide (sugar units) linked through glycoside linkage, by removing the water. The chemical composition and molecular structure of hydrocolloids often depend on the source, extraction methods and any further processing conditions. The chemical composition can be derived either from the same sugar monomers (cellulose and starch), two different monomer units (alginate and hyaluronan) or different monosaccharide (galactose, arabinose, rhamnose and uronic acid) such as gum Arabic (Williams & Phillips, 2000). Many Table 2 Mucilage polysaccharides from selected plants. Palanuvej et al. (2009). Plants

Used parts

% Yield

Basella alba Linn. Hibiscus esculentus L. Litsea glutinosa Lour. Ocimum canum Sims. Plantago ovata Forssk. Scaphium scaphigerum G. Don. Trigonella foenum-graecum L.

Aerial parts Fruits Leaves Seeds Seeds Fruits Seeds

3.5 5.6 12.0 17.6 19.0 23.0 15.0

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scientists have reported the presence of galactose, arabinose, rhamnose, uronic acids, galactoronic acid, protein, Ca and Mg as the main structure constituents of plant gums (Williams & Phillips, 2000).

Table 4 Sources, basic properties and major specifications of commercial galactomannans (FAO/WHO). Fox (1992), Wielinga (1990).

2.1.2. Classification of plant-based gums Plant source

2.1.2.1. Galactomannan. Galactomannan is known as a linear polysaccharide. It is an energy reserve polysaccharide in all endosperm leguminous plant seeds (Meier & Reid, 1982). They are composed of “a linear β-(l → 4)-mannane backbone attached to single D-galactopyranosyl residues via α-(l → 6) linkages” including ‘side chains of galactose remains’ (Da Silva & Gonçalves, 1990; Estévez et al., 2004). They are highly water soluble hydrocolloids providing highly viscous and stable aqueous solutions (Neukom, 1988). They exhibit different physicochemical and rheological properties depending on mannose/ galactose (M/G) ratio, distribution of galactose residues along the mannan backbone, molecular weight, and molecular weight distribution (Robinson, Ross-Murphy, & Morris, 1982). Galactomannans have broad applications in different food, cosmetic and pharmaceutical products as matrix tablets (Baveja, Rao, & Arora, 1991; Pauly, Freis, & Pauly, 1999), coating material in tablets, and microcapsules in pharmaceutics. They have been also used as a thickener and stabilizer in emulsion and suspension systems (Kapoor, Pandey, Khanna, Dwiredi, & Singh, 1999) and emulsifier and gelling agent in gel-based products (Asgharian, 2000). They have been also used as dietary fiber, low-energy fat replacers in low fat mayonnaise and gelling agents in fruit-based water gels (Cruz Alcedo, 1999). They are also used as food ingredients in bakery goods (icings and cake mixes), dietary products, coffee whiteners, baby milk formulations, dressings, sauces, soups, frozen, and cured meat foods (Reid & Edwards, 1995). Galactomannans are mainly extracted from the endosperm of Leguminosae seed for commercial purposes that bear a protective shelter made of seed coat (i.e. C. tetragonolobus L. (guar), C. siliqua (locust bean) and Caesalpinea spinosa (Tara)) (Table 3) (Azero & Andrade, 2002; Üner & Altınkurt, 2004). In fact, galactomannans are the ground endosperm of the Leguminosae seeds in different particle sizes (Wade & Weller, 1994). They contain xylose and arabinose and no starch and reducing sugars. The galactomannan content of endosperm and seeds ranged 68–85% (Manzi, Mazzini, & Cerezo, 1984) and 20–26% (Klyosov, & Platt, 2003), respectively. The ratio of galactose/mannose (M/G) in galactomannans varies as the species differ from one to another (M/G: 1.6:1 to 4.5:1) (Gonçalves, Torres, Andrade, Azero, & Lefebvre, 2004; Singh, Mishra, Khare, & Gupta, 1997). There are two distinct galactomannans with quite well-known commercial significance: guar gum (GG) from C. tetragonolobus, and LBG from C. siliqua. The average M/G ratio in LBG is approximately 3.5 compared to guar gum (average ratio of M/ G = ~1.8) and Tara gum (average ratio of M/G= ~3) (Table 4) (Batlle & Tous, 1997; Bourriot, Garnier, & Doublier, 1999; Cruz Alcedo, 1999; Fox, 1992; Morris, 1998). Carob galactomannan has the lowest galactose content (20%) among the substantial available galactomannans (i.e., carob bean gum (CBG), guar gum (GG) and Tara gum (TG)) (Richarsdon, Willmer, & Foster, 1998).

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Approx. seed size (mm) Seed components % Endosperm Cotyledon Seed coat M/G ratio E-number Loss on drying (%) Total ash (%) Acid insoluble matter (%) Protein Starch Arsenic

Carob gum

Guar gum

Tara gum

Ceretonia siliqua 10 250 42–46 23–35 30–33 3.5–4 E4 10 b 14 b 1.2 b4 b7

Cyamopsis tetragonolobus 4 35 38–45 40–46 14–16 1.5–2 E4 12 b15 b1.5 b7 b10 Not detectable Not more than 3 mg/kg Not more than 10 mg/kg Not more than 20 mg/kg

Caesalpinia spinosa 10 250 20–22 38–40 38–40 2.5–3 E4 17 b15 b1.5 b2 b3.5

Lead Heavy metals

Water solubility of galactomannans is easily influenced by the degree of galactose substitution and M/G ratio. As also stated by Lazaridou, Biliaderis, and Izydorczyk (2000), the molecular size and structure (i.e. M/G ratio, galactose distribution in the mannose linear chain) are the most notable factors affecting “solubility mechanism” and “ability to self-associate” (i.e. intra-chain and inter-chain interactions). In particular, a higher mannose to galactose (M/G) ratio leads to higher thickening properties (Lazaridou et al., 2000). In this respect, guar gum would be soluble in cold water; whereas LBG shows inconsiderable solubility at room temperature. 2.1.2.1.1. Malva nut gum (MNG). Malva nut gum (MNG) is extracted from a plant belongs to Sterculiaceae family including several species such as Scaphium macropodum Beumee and Sterculia lychnophora Hance. Malva nut fruit (Scaphium scaphigerum) grows in Vietnam, China, Malaysia, Indonesia and Thailand. It is known as Pungtalay or Sumrong in Thailand (Yamada et al., 2000). Malva nut fruit contains a large amount of mucilaginous substance used as a traditional medicine in South-East Asia (Somboonpanyakul et al., 2006). The purified mucilage from Malva nut fruit (Sterculia lychnophora Hance) is known as a complex carbohydrate polymer with the molecular weight of 162,200 (Da) (Chen et al., 1996). Somboonpanyakul et al. (2006) showed that the MNG obtained under alkaline extraction contained 62.0% carbohydrates, 8.3% ash and 8.4% protein. As shown in Table 5, the prime constituent monosaccharides of MNG included 31.9% arabinose, 29.2% galactose, 29.5% rhamnose, 6.4% uronic acid and small content of glucose, xylose and mannose (Somboonpanyakul et al., 2006). The monosaccharide composition of MNG exudates contains galactose, arabinose and rhamnose with the molar ratio of 1.00:1.67:1.01, where rhamnose is linked via α-(1/3) glycoside linkage in the backbone of

Table 3 Structural properties of main galactomannans. Mahungu and Meyland (2008). Substance

Structure

Mannose:galactose

Molecular weight

Cassia gum

1,4-β-D-mannopyranose units with 1,6-α-D-galactopyranose units attached to every fifth mannose. 1,4-β-D-mannophyranose units with 1,6-α-D-galactopyranose units attached to every alternate mannose. 1,4-β-D-mannopyranose units with 1,6-α-D-galactopyranose units attached to every fourth fifth mannose. 1,4-β-D-mannopyranose units with 1,6-α-D-galactopyranose units attached to approximately every third unit.

5:1

200,000–300,000

2:1

50,000–8,000,000

4:1

50,000–3,000,000

Approximately 3:1

Not reported

Guar gum4 (CAS No. 9000-30-0) Locust (Carob) bean gum5 (CAS No. 9000-40-2) Tara gum6 (CAS No. 39300-88-4)

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Table 5 Chemical composition and deduced linkages of partially methylated alditol acetates (PMAA) of the alkaline extracted Malva nut gum. Somboonpanyakul et al. (2006). Chemical name

Deduced linkage

Molar ratioa (n)

Molar ratioa (y)

4-O-acetyl-(1-deuterio)-1,2,3,5-tetra-O-methyl-arabinotol 1,3,4-tri-O-acetyl-(1-deuterio)-2,5-di-O-methyl-arabinotol 1,4,5-tri-O-acetyl-(1-deuterio)-2,3,6-tri-O-methyl galactol 1,2,4,5-tetra-O-acetyl-(1-deuterio)-3,6-tri-O-methyl galactol 1,2,3,4,5-penta-O-acetyl-(1-deuterio)-rhamnitol

Terminal Araf 1,3-L-Araf 1,4-D-Galp 1,2,4-D-Galp 1,2,3,4-D-Rhamp

1.24 1.00 0.21 Nd Nd

1.97 1.00 1.56 0.25 0.36

Monosaccharide compositions

(%, w/w)

Arabinose Galactose Rhamnose Glucose Xylose Mannose

31.9 ± 0.2 29.2 ± 0.2 29.4 ± 0.1 2.7 ± 0.2 2.1 ± 0.1 4.8 ± 0.3

n, without uronic acid reduction; y, with uronic acid reduction; and Nd, not detectable. a Relative molar ratio calculated from the ratio of peak area.

gum (Chen et al., 1996). Methylation analysis revealed that alkaline extracted MNG was primarily composed of terminal L-Araf, 1,3-linked L-Araf, 1,4-linked D-Galp, 1,4-linked D-GalAp with little amounts of branching units (Somboonpanyakul et al., 2006). In recent years, Malva nut seeds have been also used in sweetened beverages and deserts. It was reported to provide health benefits such as the reduction of body weight (Srichamroen & Chavasit, 2011). The mucilaginous substance from Malva nut is a water soluble polysaccharide gum with beneficial effects for the human body (such as reducing serum cholesterol levels and reducing the risk of heart disease) (Somboonpanyakul et al., 2006; US Food & Drug Administration, 1994). It has been used for laxative benefits in Thailand. The principal application of MNG is in relief of canker sore and cough. It has been also used as a traditional drug for the prevention of pharyngitis, treatment of tussis and constipation in China (Wang et al., 2003). The health benefits of mucilage from Malva nut seed are linked to its gelling property (Srichamroen & Chavasit, 2011). MNG can be also used as a gelling agent in jelly sweetened dessert (Somboonpanyakul et al., 2006). 2.1.2.1.2. Fenugreek gum (FG). Fenugreek (Trigonella foenum graecum) is an annual herb, which belongs to the legume family widely grown in India, Egypt and Middle Eastern countries. Fenugreek gum (FG) is extracted from the endosperm of the Fenugreek seeds. The main polysaccharide present in Fenugreek seed endosperm is a galactomannan (galactose and mannose) which resembles the other galactomannans such as locust bean, guar gum and Tara gum (Stephen & Churns, 1995; Youssef, Wang, Cui, & Barbut, 2009). FG was shown to reduce the glucose level in blood and regulate the cholesterol content in the liver (Srinivasan, 2006). It also revealed the hypoglycemic effects on diabetes mellitus types 1 and 2 (Hannan et al., 2007). FG has been used as a thickener, stabilizer and emulsifier in many food products (Işikli & Karababa, 2005). However, the slow hydration rate, unpleasant flavor and difficulty in producing a homogeneous dispersion containing FG are the negative aspects of its applications in the industry (Chang, Cui, Roberts, Ng, & Wang, 2011). FG is composed of α (1/4)-β-D-mannan backbone attached to single α-D-galactopyranosyl groups at the O-6 position of D-mannopyranosyl residues (Brummer, Cui, & Wang, 2003; Dea & Morrison, 1975). Fig. 1 shows the primary structure of fenugreek gum. The mannan backbone of FG is almost fully substituted with galactose side chains (Brummer et al., 2003; Dea & Morrison, 1975). The hyper entanglement of unsubstituted mannan regions in FG becomes nearly impossible due to the presence of disaccharide repeating sequence in its primary structure (Fig. 1) (Doyle et al., 2009). As reported by Brummer et al. (2003), the ratio of galactose to mannose in the extracted fenugreek galactomannans varied from 1.00:1.02 to 1.00:1.14 (Table 6).

Brummer et al. (2003) investigated the effect of different extraction methods on the chemical composition of FG. They reported that the cool water extraction yielded the gum with low protein content (2.36%) as compared to the solvent extraction using boiling hexane. The protein level was further decreased to 0.57% using the pronase hydrolysis. The hydrolysis process did not influence the molecular weight of FG. They reported that the content of sucrose, raffinose and stachyose present in the ethanol–soluble sugar mixture was found to be 0.7, 0.5 and 2.84%, respectively (Table 6). Mansour and El-Adawy (1994) also reported the presence of 0.49% raffinose and 2.01% stachyose in FG. Previous researchers (Garti, Madar, Aserin & Sternheim, 1997; Huang, Kakuda, & Cui, 2001) reported that the extracted FG contained 0.8% residual protein, thereby prohibiting the function of surface activity to the hydrophilic gum alone. Huang et al. (2001) found that FG had the highest stabilizing capacity amongst other 11 commercial gums and 5 laboratory synthesized gums (i.e. Gellan, carrageenan, pectin, methylcellulose, gum Arabic, microcrystalline cellulose, locust bean gum, guar, xanthan, mustard, oat gums, flaxseed and oat gums). 2.1.2.1.3. Mesquite seed gum (MSG). Algarrobo (Prosopis spp) trees are leguminous plants wildly distributed in arid and semi-arid zones over the world. Prosopis genus (mesquites and algarrobos) is leguminous plant, which belongs to the Mimosoideae family (Polhill, 1994). Prosopis species are known with the common name of mesquite in North America and Algarrobo in Peru (Cruz Alcedo, 1999). Prosopis

Fig. 1. The primary structure of fenugreek gum (Doyle et al., 2009).

H. Mirhosseini, B.T. Amid / Food Research International 46 (2012) 387–398 Table 6 Composition of fenugreek seed and fenugreek seed galactomannan. Brummer et al. (2003). Fenugreek seed (%, w/w) Lipid Protein Galactomannan Total ethanol soluble sugars Individual ethanol soluble sugars Galactose Sucrose Raffinose Stachyose Moisture Ash

7.24 ± 0.42 34.10 ± 0.84 22.57 ± 2.8 8.06 ± 0.62 0.25 ± 0.01 0.70 ± 0.06 0.50 ± 0.08 2.84 ± 0.51 7.49 ± 0.53 3.38 ± 0.04

Fenugreek seed galactomannan (%, w/w) Protein Fraction A Fraction B G/M Ratioa

Fraction A Fraction B

2.36 ± 0.04 0.57 ± 0.03 1.00/1.02 1.00/1.05

Chemical name

Relative abundance (%)

Deduced linkage (%)

1,5-di-O-acetyl-(1-deuterio)-2,3,4,6tetra-O-methyl hexitol 1,4,5-tri-O-acetyl-(1-deuterio)-2,3,6tetra-O-methyl hexitol 1,4,5,6-tetra-O-acetyl-(1deuterio)-2,3di-O-methyl hexitol 1,5,6-tri-O-acetyl-(deuterio)-2,3,4tri-O-methyl hexitol

42

t-Galp

12.7

4-Manp

45.2

4,6-Manp



t-6-Manp

All measurements on a dry weight basis. a Trace.

flexuosa or mesquite fruit is a drupaceous lomentum, (i.e.) a pod with an articulated endocarp that forms indehiscent coriaceous segments. It contains the high content of sugars and proteins; therefore, it can be considered as a valuable fodder (Ibańez & Ferrero, 2003). Furthermore, Prosopis pallida cotyledon contains 65% protein, which represents 31% of the seed weight (Cruz, Del Re, & Amado, 1987). Table 7 shows the amino acid profile of Prosopis cotyledon proteins. As shown in Table 7, the amount of essential amino acids is extremely high in the chemical structure of P. pallida seed cotyledon; while

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cysteine and methionine are the main limiting amino acids in its chemical structure (Cruz et al., 1987). The mesquite fruit can be used as a source of mucilage, chemically classified as a galactomannan (Cruz et al., 1987). Mucilaginous endosperm is characteristic of the seeds of leguminous plants and contains the hydrocolloid classified as a galactomannan in Prosopis spp. (Burkart, 1952). A fully water-soluble gum is extracted from the “endocarp capsule” of the seed coating of Prosopis africana (Achi & Okolo, 2004). The extracted gum from P. flexuosa DC seeds had a particular composition, which resembled other commercial gums from the leguminous family, but it contained a high content (66.1–72.5%, w/w) of total polysaccharide. Two different types of polysaccharide mucilage have been extracted from the seed endosperm of mesquite: a bark-exuded gum and a galactomannan fraction (storage polysaccharide), which accounts for almost 30% (w/w) of the seed (Estévez et al., 2004; Goycoolea, Calderón de la Barca, Balderrama, & Valenzuela, 1997; Goycoolea, Milas, & Rinaudo, 2001). Mesquite seed gum (MSG) appears to have a ‘core’ of ß-D-galactose units, comprising α (l-+3)-linked backbone chain with (l-6)-linked branching units, along with L-arabinose (pyranose and furanose ring forms), L-rhamnose, ß-D-glucuronate and 4-0-methyl-/I-D-glucuronate (Anderson & Farquhar, 1982; Churms, Merrifield, & Stephen, 1981; Cruz Alcedo, 1999). As shown in Fig. 2, the major fragment of MSG is composed of galactose and mannose with the molar ratio of 1.00:2.78 and molecular weight of 62,500 Da (Vernon-Carter et al., 2000). The rhamnose in the backbone of MSG is linked through α-(1→ 3) glycoside linkage (Fig. 2). Ibańez and Ferrero (2003) showed that mannose (M) and galactose (G) were as the major monosaccharides of MSG with M/G ratio of 2.1. They found that the percentage of protein remained to be high even after the extraction (between 10 and 20% (w/w)) — “especially while the mucilage was being separated from the flour and not from the whole seeds” (Ibańez & Ferrero, 2003). However, the purification process led to reduce the protein content. Ibańez and Ferrero (2003) reported that there was a difficulty to dissolve the extracted mucilage in the cold water, showing a tendency to form dispersion system with pseudoplastic and non-thixotropic rheological behavior. Achi and Okolo (2004) extracted P. africana gum through the dehulling Achi method. They found that the endocarp gum contained a high amount of galactose and mannose as well as a low amount of protein and fat content. They reported that the purified gum from P. africana contained 2.4% fat, 1.04% protein, 21.5% crude fiber and 10% gelation content. The researcher also found that galactose and

Table 7 Amino acid profile of Prosopis pallida seed cotyledon. Cruz Alcedo (1999) and Cruz et al. (1987). Amono acids (g/100 g protein) WHO/FAO pattern Aspartic acid Threonine Serine Glutamic acid Proline Glycine Alanine Cysteine Methionine Met + Cys Valine Isoleucine Leucine Tyrosine Phenylalanine Tyr + Phe Lysine Histidine Arginine Tryptophan

8.30 2.42 4.87 21.31 7.49 4.59 4.34 1.31 0.88 2.19 4.56 3.09 7.51 1.84 4.29 6.13 4.09 3.10 14.63 1.37

4

3.5 4 7

6 5.5

1

Fig. 2. Structural feature of mesquite gum (Vernon-Carter and Sherman, 1980).

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mannose were the major monosaccharides in P. africana gum. Mesquite seed gum (MSG) or Prosopis gum has been reported to have similar composition, properties and applications to gum Arabic (Anderson & Weiping, 1989; Goycoolea et al., 1997). It has been widely used as a wheat flour substitute in dough for bread making and confectionery products. It is also used as a microencapsulating agent, flavor and color emulsifier, colloid protector, emulsion coating agent, binder in tablet dosage forms and suspending agent at par (Cruz Alcedo, 1999). 2.1.2.1.4. Carob bean gum (CBG) or locust bean gum (LBG). Carob tree (C. siliqua L.) is grown in Mediterranean regions. Carob bean gum (CBG) (or locust bean gum, LBG) is a heteropolysaccharide galactomannan extracted by mashing the seed endosperm of the fruit pod of the carob tree (C. siliqua L.) (Dakia et al., 2008). The final powder has a yellowish to whitish colour. The carob seed consists of the husk (30–33%), endosperm (42–46%) and germ (23–25%) (Neukom, 1988). LBG is a long chain polysaccharide made of monosaccharide units (i.e. galactose and mannose) (Kawamura, 2008). As shown in Fig. 3, CBG or LBG is a linear polysaccharide including the ß-(l-4)-mannane backbone chain associated with single D-galactopyranosyl residues (as side chain) via α-(l-6) linkages (Da Silva & Gonçalves, 1990; Daas Piet, Schols Henk, & De Jongh Harmen, 2000). The average M/G ratio of LBG is approximately 3.5 which is higher than guar gum (GG) with the average ratio of ~1.8 (Dea & Morrison, 1975). Samil (2007) studied the chemical composition and molecular structure of high quality refined locust bean gum (rLBG) and low quality crude locust bean gum (cLBG). The researcher found that rheological properties of LBG significantly depended on its chemical and molecular structure. As reported by Samil (2007), M/G ratio of cLBG and rLBG varied from 3.1 to 3.9. Nevertheless, the cLBG contained a considerable amount of arabinose (Samil, 2007). As reported by Samil (2007), cLBG also contained higher amount of protein, fat and ash than those of rLBG, which influenced its functional properties. The molecular size and structure (M/G ratio, galactose distribution in the mannose linear chain) of galactomannan influence the viscosity, solubility mechanism and ability to self-associate (intra-chain and inter-chain interactions). A higher M/G ratio leads to higher thickening properties (Lazaridou et al., 2000). Dakia et al. (2008) also demonstrated that the degree of galactose substitution affected the water solubility and rheological properties of LBG (Dakia et al., 2008). LBG shows the low solubility at the ambient temperature; therefore, the heat is required to achieve the maximum solubilisation and reach the highest water holding capacity (WHC) (Gainsford, Harding, Mitchell, & Bradley, 1986; Maier, Anderson, Karl, Magnuson, & Whistler, 1993). CBG or LBG can be regarded as the first galactomannan biopolymer which is applicable to food products. It has been mainly used as a thickener and stabilizer in frozen desserts, ice cream, and cream cheese. It can be also used in other industrial products such as paper, textile, pharmaceutical and cosmetic products (Dakia et al., 2008). 2.1.2.1.5. Cassia seed gum (CSG). Cassia plants are considered as “non-conventional” resources for plant seed gums. The nonconventional Cassia seed gums (CSGs) have a specific molecular structure that resembles other industrial gums such as guar gum and LBG (Fig. 4A, B). These biodegradable/biocompatible polymers are

extensively used as a viscous enhancing agent and water binder in the cosmetic, pharmaceutical and other industrial products such as paper, textile, adhesive, inks, paint, explosive, and smoking products (Singh, Srivastava, & Tiwari, 2009b; Whistler, 1973). CSGs are galactomannans classified based on their M/G ratio and molecular weights varying from species to species (Kirtikar & Basu, 1935; Saldanaha & Nicolson, 1976). CSGs are extracted from the seed endosperm of Cassia tora and Cassia obtusifolia, which belong to the leguminosae family (Mahungu & Meyland, 2008). They can be also isolated from other Cassia species such as Cassia occidentalis Linn. (Anonymous, 1992), Cassia javahikai (Saldanaha & Nicolson, 1976; Singh et al., 2009b) and Cassia pleurocarpa (Singh, Sethi, & Tiwari, 2009a). C. tora and C. obtusifolia are the sources of CSGs which grow wildly in subtropical regions of the world. They are annual ruderal plants that ripen after approximately 100 days (Mahungu & Meyland, 2008). C. occidentalis Linn. (Kasondi) is also a common herbaceous annual weed cultivated in India up to 1500 m in altitude (Anonymous, 1992). C. occidentalis Linn. seeds are a rich source of galactomannan (~30% endosperm) (Kapoor, Khan & Farroqi, 1991). Another Cassia variety is C. javahikai, which is a decorative plant initially grown in India (Saldanaha & Nicolson, 1976; Singh et al., 2009b). C. javahikai seed is a rich source of seed gum composing of galactose and mannose in the molar ratio of 1.02:3.20 (Azero, Lopes, & Andrade, 1997). The chemical structure of CSG is composed of a large content (75%) of high molecular weight polysaccharide (~200,000–300,000). The major monosaccharide compositions of CSG included mannose (77.2–78.9%), galactose (14.7–15.7%), and glucose (6.3–7.1%) (Mahungu & Meyland, 2008). CSG has a linear backbone of 1,4-ß-Dmannopyranose units, and 1,6 linked D-galactopyranose units with random distribution of α-(1/6) linked D-galactopyranose units as side chain (M/G:3.1) (Mahungu & Meyland, 2008). The researchers reported that CSG had the similar molecular and chemical structure to carob bean gum (CBG), Tara gum (TG) and guar gum (GG) (Mahungu & Meyland, 2008). Fig. 4 (A, B) shows the molecular structure of plant seed gum from C. javahikai and C. pleurocarpa (Singh, Singh, & Maurya, 2010; Singh et al., 2009a). Singh et al. (2010) studied the effect of extraction condition on the chemical structure of Cassia javanica seed gum. They found that the C. javanica seed gum extracted under alkaline condition contained 62.0% carbohydrates, 8.3% ash and 8.4% protein. Singh et al. (2010) reported that arabinose (31.9%), galactose (29.2%) and rhamnose (29.5%) were the major monosaccharide compositions of CSG. The chemical structure of Cassia javanica seed gum also contained 6.4% uronic acid and little amounts of glucose, xylose and mannose (Singh et al., 2010). C. pleurocarpa is a bush-like plant including branched green leaves and bright colored flowers, wildly grown in the northern Australia (Dale, Gibbs, & Behncken, 1984). The seed endosperm of C. pleurocarpa is also a source of non-ionic water soluble galactomannan composed of D-galactose and D-mannose in the molar ratio of 1.00:2.01 (Singh et al., 2009a). The galactomannan isolated from seed endosperm of C. pleurocarpa is a heteropolysaccharide with a linear backbone chain of β(1→ 4) linked D-mannopyranosyl units linked to D-galactopyranosyl side chains via α(1→ 6) linkages (Fig. 4B) (Singh et al., 2009a).

Fig. 3. Structural feature of locust bean (carob bean) gum structure (Kawamura, 2008).

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Fig. 4. Molecular structure of the repeating units of Cassia javahikai (A) and Cassia pleurocarpa (B) galactomannan (Singh et al., 2009a,b).

The galactomannan from C. pleurocarpa can be used for the drug delivery, tissue engineering fields and some other biomedical applications due to the unique gelling ability, water retention capacity and viscous-enhancing property (Singh et al., 2009a). 2.1.2.1.6. Basil seed gum (BSG). Basil (Ocimum basilicum L.) is a member of genus Ocimum, which encompasses a broad range of species, herbs and shrubs – between 50 and 150 – globally distributed in the tropical regions of Asia, Africa and Central and South America (Paton, Harley, & Harley, 1999; Simon, Morales, Phippen, Vieira, & Hao, 1999). The genus Ocimum is considered as a pharmaceutical plant because it is widely used as a culinary herb for traditional medicine. It is also a well-known source of flavoring agent and essential oil with antioxidative and antimicrobial activities (Javanmardi, Stushnoff, Locke, & Vivanco, 2003; Naghibi, Mosaddegh, Motamed, & Ghorbani, 2005). Basil seed (O. basilicum L.) has reasonable content of gum with outstanding functional properties which is comparable with some other commercial gums (Razavi et al., 2009). Basil seed gum (BSG) is a polysaccharide extracted from basil (O. basilicum L.) seed by using either cold water extraction or alcohol precipitation (Anjaneyalu & Channe Gowda, 1979; Tharanathan & Anjaneyalu, 1975). It is comprised of two major fractions: (i) an acidstable core glucomannan (43%) with G/M ratio of 10:2, and (ii) a (Achi & Okolo, 2004; Amin, Ahmad, Yin Yin, Yahaya, & Ibrahim, 2007; Amin & Arshad, 2009)-linked xylan (24.29%) including acidic side chains at C-2 and C-3 of the xylosyl residues in the acid-soluble portion. It also contains a minor fragment of glucan (2.31%) as a degraded cellulose material with DP equal to 80 (Anjaneyalu & Channe Gowda, 1979; Razavi et al., 2009; Tharanathan & Anjaneyalu, 1975). Razavi et al. (2009) studied the physicochemical and mechanical properties of Iranian basil seeds. They found that the extraction conditions significantly influenced the apparent viscosity and protein

content of BSG. As reported by Razavi et al. (2009), the extraction temperature and pH were the most important extraction variables affecting the quantity and quality of BSG. As reported in Table 8, the major difference between the chemical composition of Iranian Basil seed and Indian basil seed was related to their protein, lipid and carbohydrate contents (Mathews, Singhal, & Kulkarni, 1993; Razavi et al., 2009). The researchers reported that Iranian Basil seed contained a lower content of carbohydrate and moisture, but higher amount of protein and lipid fractions as compared to Indian basil seed (Table 8). As shown in Table 8, carbohydrate (~47–50%), lipid (~22–25%) and protein (~18–20%) were the major consituents present in the Iranian Basil seed. As reported by Razavi et al. (2009), Iranian basil seed had higher amount of lipid and protein fractions as compared to Indian basil seed; while it showed lower carbohydrate concentration than Indian basil seed. 2.1.2.2. Non-galactomannan 2.1.2.2.1. Flaxseed gum (FSG). Flax is one the major Canadian crops cultivated mainly for the extraction of industrial linseed oil. The flaxseed (Linum usitatissimum) meal is the main waste material remaining after the oil extraction. It is one of the main sources of the plant-based lignan precursor secoisolariciresinol diglucoside (SDG) containing 75–800 times more than that of other foods (Mazur, 1998). The chemical structure of SDG is shown in Fig. 5. Lignans are phenolic compounds formed by the union of monomeric units hydroxyl- and hydroxy-methoxy derivatives of cinnamic and benzoic acids (Budavari, 1996). Flaxseed has been mainly interested due to its abundant polyunsaturated fatty acid (i.e. α-linolenic acid). In addition, it also contains dietary fiber and lignan constituents, which is potentially used to reduce the risk of cardiovascular disease in human (Dodin et al., 2008). Flaxseed also contains proteins

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Table 8 Chemical composition of Iranian and Indian basil seeds, crude and pure BSGa (%). Mathews et al. (1993) and Razavi et al. (2009). Component

Moisture Proteinb Lipidb Ashb Carbohydrate (by difference)b a b

Iranian basil seeds Qom

Kerman

Yazd

Mashhad

Isfahan

5.07 ± 0.15 20.16 ± 0.92 23.12 ± 0.97 5.38 ± 0.10 47.27 ± 0.64

5.11 ± 0.16 19.44 ± 0.67 23.70 ± 1.01 5.54 ± 0.10 47.21 ± 0.73

5.02 ± 0.17 17.94 ± 0.62 24.45 ± 0.91 5.41 ± 0.11 48.38 ± 0.81

5.32 ± 0.16 19.75 ± 0.76 22.54 ± 0.74 5.34 ± 0.13 48.05 ± 0.32

5.51 ± 0.16 18.37 ± 0.63 21.97 ± 0.71 5.04 ± 0.11 50.11 ± 0.86

Indian basil seed

BSG (from Isfahan seeds) Cude

Pure

9.63 ± 0.14 14.76 ± 1.52 13.8 ± 0.29 7.7 ± 0.2 63.8 ± 2.01

7.39 ± 0.18 2.01 ± 0.11 11.55 ± 0.29 5.89 ± 0.14 74.19 ± 0.61

5.79 ± 0.12 1.56 ± 0.08 9.71 ± 0.25 3.32 ± 0.17 79.62 ± 0.86

Values are mean ± SD of three determinations. On a dry weight basis.

comprising of high amounts of arginine, lysine and branch-chain amino acids (Hall, Tulbek, & Xu, 2006). Therefore, it can be potentially used as value-added by products in the food industry. Mucilaginous compounds can be isolated from flaxseed (L. usitatissimum L.) a substantial source of the plant gum (Mazza & Biliaderis, 1989). Flaxseed gum (FSG) is comprised of two different polysaccharide fractions: a neutral fraction (arabinoxylans) plus an acidic fraction (Cui & Mazza, 1996). Cui and Mazza (1996) compared the main monosaccharide composition of different varieties of FSG with other commercial gums i.e. gum Arabic, guar and xanthan gum. Table 9 shows the major difference between the chemical composition of various flaxseed gums and several commercial gums (i.e. gum Arabic, guar and xanthan gum). As shown in Table 9, D-xylose, L-arabinose, L-rhamnose, L-galactose, and D-galacturonic acid were the major constituent monosaccharide and uronic acid present in the chemical structure of FSG obtained by acid-catalyzed hydrolysis (Cui & Mazza, 1996; Mazza & Biliaderis, 1989; Warrand et al., 2005). FSG has an abundant water holding capacity (WHC) with similar rheological properties as guar gum (Fedeniuk & Biliaderis, 1994). Cui, Kenaschuk, and Mazza (1996) studied the effect of chemical composition of various brown and yellow flaxseed cultivars on their rheological behaviors. They indicated that those flaxseed gums containing higher amounts of arabinoxylans (neutral polysaccharide) showed more shear thinning (pseudoplastic) flow behavior and ‘weak gel’-like properties; while those flaxseed gums containing higher content of acidic monosaccharides s(e.g. galacturonic acid) exhibited weaker rheological properties (i.e. viscoelastic fluid). As reported by Cui et al. (1996), FGs obtained from yellow Flaxseed showed stronger rheological properties than those extracted from the brown cultivars. They found that the yellow flaxseed cultivars contained a significantly lower content of rhamnose (12.8–14.4%) and galacturonic acid (13.8–16.2%), but much higher content of neutral polysaccharide (e.g. xylose, 39.0–48.7%). This observation is consistent with their ‘weak gel-like/rheological properties (Cui et al., 1996). 2.1.2.2.2. Tamarind kernel seed gum (TKSG). Tamarind kernel powder (TKP) is derived from Tamarindus seeds indica belonging to

Leguminosae family. It is the most important tree grown in South East Asia and widely indigenous to India, Bangladesh, Myanmar, Sri Lanka, Malaysia, and Thailand (Anonymous, 1976; El-Siddig et al., 2006). The chemical structure of TKP was reported to contain protein (12.7–15.4%), oil (3–7.5%), crude fiber (7–8.4%), carbohydrates (61–72.2%) and ash (2.45–3.3%) in the chemical structure of TKP (Table 10) (Jones & Jordan, 1978). Tamarind kernel polysaccharide (TKP) or Tamarind seed gum (TSG) is a galactoxyloglucan derivative isolated from the seed kernel of Tamarindus indica. TSG has a backbone chain of β-D-1-glucopyrynosyl units linked to a side chain of D-xylopyranosyl unit (Gerard, 1980). It is rich in a high molecular weight polysaccharide (~65–72%) with the molecular weight of 720–880 kDa (Freitas et al., 2005; Kumar & Bhattacharya, 2008). However, different molecular weight ranging from 2.5 × 105 to 6.5 × 105 Da was reported in the previous study (Zhang, Xu, Zhang, & Du, 2008). TSG is an extremely branched carbohydrate polymer composed of three monosaccharide units i.e. “glucose, galactose and xylose in the molar ratio of ~ 3:2:1” (Freitas et al., 2005; Patel et al., 2008). An approximately 80% of glucose remains are replaced by xylose residues (1–6 linked), which themselves replaced in part by p-1-2 galactose residues (Fig. 6) (Goyal, Kumar, & Sharma, 2007; Zhang et al., 2008). TSP is a promising polymer mainly used as stabilizer, thickener, gelling agent, and binder in food and pharmaceutical industries. TSP can simply swell in water and form the mucilaginous solution after heating up. TSP solution has the proper resistance against acid and thermal process. It can form a gel which is mainly used as a thickening and stabilizing agent in the food industry (Zhang et al., 2008). TSP is also known as a novel drug delivery system and bioadhesive agent in pharmaceutical products with non-carcinogenicity, Table 9 Comparison of flaxseed gum obtained from different varieties with various commercial gums. Cui and Mazza (1996). Flaxseed gums Norman Loss on drying (105 °C; %)a Total ash (550 °C; %) Nitrogen (Kjeldahl, %) Uronic acid (%) Relative neutral Rhamnose Fucose Arabinose Xylose Galactose Glucose Mannose a

Fig. 5. Structure of secoisolariciresinol diglucoside (SDG; 2,3-bis[(4-hydroxy-3methoxyphenyl)methyl]-1,4-butane-diglucoside) (Budavari, 1996; Mazur, 1998).

b c

Omega

Commercial gums Foster

84495

Arabic

6.5

3.7

14.4

11.5

12.8

8.6

10.2

7.4

8.2

8.4

3.3

1.2

11.9

1.5

1.50

2.69

2.95

2.42

0.34

25.1 23.9 21.0b sugar composition (%) 21.2 27.2 25.6 5.0 7.1 5.8 13.5 9.2 11.0 37.4 28.2 21.1 20.0 24.4 28.4 2.1 3.6 8.2 0.0 0.0 0.0

Guar

1.31

Xanthan

0.86

15.7

15.0c

0.0

21.5

12.8 3.0 18.1 42.5 18.4 3.7 0.0

34.0 0.0 24.0 0.0 45.0 0.0 0.0

0.0 0.0 0.0 0.0 33.0 0.0 67.0

0.0 0.0 0.0 0.0 0.0 50.7 49.3

On a dry weight bade. Galacturonic acid for flaxseed gum. Content of glucuronic acid, from Anderson and Morrison (1990).

H. Mirhosseini, B.T. Amid / Food Research International 46 (2012) 387–398 Table 10 Representative composition of crude tamarind kernel powder. US patent, 4074043. Non-polysaccharide components Protein Moisture Fat Fiber Ash Tannin Free sugars Mechanical impurities Impurities

About 45–55% 17–19% 8–10% 7–8% 3–5% 2–4% 2–3% 2–3% 0–5%

biocompatibility, high drug holding capacity, and high thermal stability (Gupta, Puri, Gupta, Jain, & Rao, 2010). 2.1.2.2.3. Durian seed gum (DSG). Durian (Durio zibethinus Murray) is the most popular seasonal fruit in South East Asia countries, particularly Malaysia, Indonesia, Thailand, and Philippines (Booncherm & Siriphanich, 1991; Brown, 1997). Durian is a large, spiky fruit, native to the tropical rain forests — known as “the king fruit”. It is a climacteric fruit of several tree species which belongs to the genus “Durio” and “Malvaceae” family (Lim, 1990; United States Department of Agriculture, USDA, 2008). Durian has very large seed, which relies upon being discarded after consuming the fruit. It makes a huge volume of waste in the food and beverage industry. As reported by Amiza, Aziz, Ong, Wong, and Pang (2004), the durian seed flour is very nutritious containing high fiber content. It is used by incorporating into various traditional food products including cake, cookies, soup, tempura, tempoyak (fermented durian) and lempuk (durian cake). It has been also used as a dietary fiber, thickening agent and replacer for wheat flour (Tabatabaee Amid, & Mirhosseini (2011); Amiza et al., 2004; Che Man, Irwandi, Yusof, Jinap, & Sugisawa, 1997). A large amount of slime will come out after cutting a fresh durian seed. This might be due to the presence of hydrocolloid and starch in the durian seed (Amiza et al., 2004). As reported by Amin et al. (2007), durian seed gum (DSG) contained the monosaccharide such as rhamnose, glucose and D-galactose in the

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ratio of 3:9:1. They also found that galactomannan was not available in DSG. Amin et al. (2007) also demonstrated that the ash content of DSG was higher compared to the other commercial gums. They reported that the extraction yield of durian seed gum (DSG) was low as compared to other seeds such as Ipomoea seed (2.8%), turpethum seed (2.3%) and Abutilon indicum seed (3.0%). Amin and Arshad (2009) reported that whole durian seed (WDS) flour was comprised of carbohydrate (73.9%), crude fiber (10.1%), water (6.5%), and protein (6.0%). It also contained the low amount of ash (3.1%) and fat (0.4%). They found that the de-hulled durian seed (DDS) floor contained higher amount of carbohydrate (76.8%), moisture (6.6%), protein (7.6%), ash (3.8%), but lower content of crude fiber (4.8%) and a similar amount of fat (0.4%) as compared to WDS. They also reported that the total contents of dietary fiber of WDS and DDS were 52.9% and 7.7%, respectively. The ash content of DSG was higher than that of gum Arabic (1.2%) and xanthan gum (1.5%), but lower than that of guar gum (11.9%) (Amin et al., 2007; Cui & Mazza, 1996). As shown by previous researchers (Amin et al., 2007; Cui & Mazza, 1996), DSG contained higher calcium content than guar and xanthan gum; while it had a lower amount of calcium than gum Arabic (Table 11). Moreover, the researchers reported that DSG was rich with natrium content, which was not comparable to other examined gums such as gum Arabic, guar and xanthan gum. As reported in previous studies (Amin et al., 2007; Cui & Mazza, 1996), DSG contained a high content of zinc and manganese in comparison with gum Arabic, guar and xanthan gum; while it showed incomparably lower quantity of lead and copper than that of gum Arabic, guar and xanthan gum (Table 11). 2.1.2.2.4. Karaya gum (KG). Karaya gum (KG) is a commercially extracted polysaccharide from Sterculia urens, which is notable tree cultivated in India. S. urens belongs to the Sterculiaceae family, which usually grows in dry and rocky forests regions (Galla & Dubasi, 2010; The Wealth of India, 1952). The seed of S. urens is composed of 56% kernels containing 35% protein, 26% oil and 28% carbohydrates (The Wealth of India, 1952). KG is a partially acetylated complex polysaccharide gum involving high molecular weight strcuture. The chemical structure of KG is composed of 55–60% of neutral monosaccharide residues (namely galactose and rhamnose), 8% acetyl groups and

Fig. 6. The molecular structure of Tamarind gum (Zhang et al., 2008).

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Table 11 Mineral content of durian seed gum compared to other commercial gums.

Table 12 Chemical composition of gum from karaya seed meal.

Mineral

Durian seed guma Arabic gumb Guar gumb Xanthan gumb

Parameters, %

Whole seed meal

Dehulled–defatted seed meal

Calcium (ppm) Natrium (ppm) Zinc (ppm) Aluminum (ppm) Manganese (ppm) Pottasium (ppm) Ferum (ppm) Lead (ppm) Copper (ppm) Cobalt (ppm) Nickel (ppm) Cadmium Magnesium

3169 221.3 107.7 18.5 15.3 10.9 2.8 1.6 1.5 – – nd nd

Moisture Total ash Fat Protein (N × 6.25) Crude fiber Carbohydrates (by difference) Energy kcal/100 g

7.32 ± 0.07a 3.40 ± 0.03a 29.02 ± 0.14 20.47 ± 0.14a 8.24 ± 0.09a 31.55 ± 0.26a 469.00 ± 0.31a

5.16 ± 0.05b 4.06 ± 0.05b ND 40.74 ± 0.18b 3.58 ± 0.08b 46.46 ± 0.25 348.00 ± 0.19b

7222 nd b4.0 nd 9.5 nd nd b4.0 b4.0 nd nd b0.5 2400

1258 nd 12.1 nd 4.6 nd nd b4.0 5.4 nd nd b0.5 760

1458 nd 9.0 nd 6.0 nd nd 12.0 9 nd nd 0.7 1340

nd—not determined. a Reported by Amin et al. (2007). b Reported by Cui and Mazza (1996).

37–40% uronic acid residues (galacturonic and glucuronic acid) (Davidson, 1980; Ibrahim, Abo-Shosha, Allam, & El-Zairy, 2010; Stephen & Churns, 1995). Vinod et al. (2010) also reported the presence of the aspartic acid (64.2 ± 2.44 lg/g), proline (30.5± 1.86 lg/g), glutamic acid (34.2 ± 1.44 lg/g), threonine (25.2 ± 1.06 lg/g) and glycine (4.8± 0.45 lg/g) and leucine (3.9 ± 0.28 lg/g) in the chemical structure of KG. Vinod et al. (2010) also reported the presence of saturated and unsaturated fatty acids such as stearic acid (C18:0, 25.5 ± 1.64), palmitic acid (C16:0, 18.5 ± 0.95), palmitoleic acid (C16:1, 13.2 ± 0.95), lauric acid (C16:0, 12.8 ± 0.62) and oleic acid (C18:1, 4.2 ± 0.21) in the chemical structure of KG. They explained that the emulsifying property of KG might be due to the presence of fatty acids in the gum structure. KG has been used in pharmaceutical, leather, bakery and dairy products due to specific functional characteristics such as suitable water holding capacity (WHC), oil holding capacity (OHC), foam capacity and stability, thickening properties, emulsification capacity and bulk density (Anderson, McNab, Anderson, Braown, & Pringuer, 1982; Ibrahim, Abo-Shosha, Allam, & El-Zairy, 2010; Galla & Dubasi, 2010). It can be also utilized as a thickener in textile printing (Davidson, 1980) and drug release controlling agent (Munday & Cox, 2000). The following structure belongs to the backbone structure of KG (Fig. 7). Galla and Dubasi (2010) studied the chemical and functional characterization of KG from whole seed and dehulled–defatted S. urens L. seed meal (Table 12). They found that the karaya seed consisted of 60.5% kernels and 39.5% hull. The researchers also reported that the protein content of seed ranged from 20.4% in whole seed meal to 40.7% in dehulled–defatted seed meal. Galla and Dubasi (2010) also reported that the other components such as carbohydrate content also increased in the dehulled defatted meal by removing the hull and fat. However, the de-hulling process of seed led to reduce the crude fiber and ash content as compared to whole seed meal. They

ND: not determined. a, b different letters within the same row indicate significant differences at p b 0.05. Values are means of triplicate with ± standard deviation.

reported that dehulled–defatted karaya seed meal was richer in protein and polyphenol content as compared to the whole seed meal. The considerable concentration of minerals such as Ca 2 +, Fe 2 +, K + and P 3 + were also available in dehulled–defatted seed meal (Galla & Dubasi, 2010). Galla and Dubasi (2010) reported that the protein solubility increased by increasing pH from the acidic pH to alkaline pH. They also found that the increase of salt concentration level led to enhance the protein solubility at isoelectric point.

3. Summary The present review study summarized the chemical composition and molecular structure of plant-based gums. As mentioned earlier, natural plant-based gums are mainly extracted from the endosperm of plant seeds (guar gum (GG)), plant exudates (e.g. tragacanth) and tree or shrub exudates (e.g. karaya gum (KG)). The present study indicates the presence of galactose, arabinose, rhamnose, uronic acids, galactoronic acid, protein, Ca and Mg as major structure constituents as well as glucose, xylose, mannose, protein and fat as minor constituents of plant gum exudates. The present work demonstrated the major differences among plant-based gums in terms of M/G ratio, distribution of galactose residues along with the mannan backbone, molecular weight and molecular distribution. The future challenge is to expand the better understanding about the relationship between the molecular structure, functionality and mechanical properties of seed gum. Since, plant-based gums are mainly used for various applications (as dietary fiber, hydrogels, films, bioadhesives, thickener, stabilizers, emulsifiers and drug delivery agents), a further study is required to investigate the effect of extraction, purification, drying and further processing conditions on the chemical composition, molecular structure and functional properties of plant-based gums.

Acknowledgment We would like to gratefully appreciate for financial support of this work by the Ministry of Science, Technology and Innovation of Malaysia through Science Fund (05-01-04-SF1059).

Fig. 7. The molecular structure of the karaya gum (Ibrahim et al., 2010).

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