International Research Journal of Plant Science (ISSN: 2141-5447) Vol. 2(3) pp. 078-086, March, 2011 Available online http://www.interesjournals.org/IRJPS Copyright © 2011 International Research Journals Full length Research Paper Swelling behaviour of konkoli (maesopsis eminii) galactomannan hydrogels. Nkafamiya II, Barminas JT, Aliyu BA and Osemeahon SA. Federal University of Technology, Yola Adamawa State Nigeria Accepted 21 March, 2011 To utilize konkoli (maesopsis eminii) seeds (KS), a medicinal natural polysaccharide, for development of a novel hydrogels for use in drug delivery, we prepared hydrogels by varying the concentrations of both the KS and borax (BX) using different ratios. This paper discusses the swelling responses of the hydrogels in different mediums [distilled water (DW), pH2.2 and pH7.4]. Percentage swelling (PS) has been observed to be increasing with increase in the concentration of KS and keeping the concentration of BX constant. On varying the concentration of BX and keeping the one of KS constant, it was observed that PS increases with decrease in concentration of BX. By changing the swelling medium from DW to pH2.2 and pH7.4, the PS increases abruptly, this indicates the smart behaviour of the hydrogels. For all the mediums, maximum PS was observed in pH7.4. These observations indicate that these hydrogels are pH sensitive and have potentials for use in colon specific drug delivery. Key words: Konkoli, hydrogel, swelling, pH. INTRODUCTION Hydrogels are hydrophilic, three – dimensional networks that possess the ability to swell in aqueous media without dissolution in response to changes in their external environment (Cauich- Rodriguez et al, 2001 and Baljit et al., 2007a). For drug delivery, among hydrophilic polymers, natural polysaccharides are the choice material due to their nontoxicity and acceptance by regulatory authorities (Sumthi and Ray, 2002). For example, hydrogel from tamarind has been used for drug release due to non-carcinogenicity, mucoadhesivity, biocompatibility, high drug holding capacity and high thermal stability (Sumathi and Ray, 2002). These polymeric networks are increasingly being used in variety of biomedical applications because of their similarities to living tissue. Like living tissue, they have a soft rubbery nature and allow the permeation of low molecular weight species (Sumathi and Ray, 2002: Tommansina et al, 2007). Hydrogels usually exhibit different degrees of swelling depending on their composition and molecular structure. In addition, there is a growing interest in the group of hydrogels that are responsive to changes in their *Corresponding author Email: iliyankafamiya@yahoo.com environment such as pH, temperature, or ionic strength. Hydrogels show significant variation in swelling as a result of external changes such as pH and temperature have been investigated for a wide range of application namely controlled release, pH-specific membrane separation, purification of pharmaceutical products, solution separation and solvent recovery (CauichRodriguez et al., 2001). The volume phase transition as a response to different stimuli makes these materials interesting objects of scientific observations and useful materials for use in advanced technologies (Baljit et al., 2007a). These hydrogels are mostly obtained from seeds of indigenous leguminous plants. These plants can be both cultivated or found in the wild. In this study, the hydrogels used are obtained from konkoli (Maesopsis eminii) a wild plant. Konkoli seed gum (KSG) is a galactomannan obtained from the seed of konkoli plant scientifically identified as maesopsis eminii, commonly called musizi in Tanzania (Hall, 1995; Joker, 2000; Rugalema et al, 1994), but locally it is known as ‘konkoli’ in North Eastern Nigeria. KSG is widely used as thickeners in soup and traditional baked food products in Nigeria, primarily because of its high viscosity, binding and swelling propensity (Barminas and Eromosele, 2002; Osemeahon et al., 2008).This plant is a large Africa tropical forest tree introduce to Nkafamiya et al. 079 various parts of the tropics for timber production or as a shade tree (Barminas, 2004). In Nigeria, this plant grows in the wild in the east, south and middle belt of the country (Aliyu, 2002; Osemeahon, 2003; Osemeahon et al, 2008). It’s shoots greenish flowers around April and may and bears fruits which get matured around August and September as they become publish black containing a very hard seed. The seed are normally removed from the dry fruits and ground into fine powder and may be constituted in hot or cold water and used in the preparation of soups and other traditional baked foods (Osemeahon, 2003; Osemeahon et al., 2008) Recently there is a marked thrust on research activities related to the use of natural polysaccharides for the development of hydrogels as colon specific drug delivery devices. These include chemically or physically crosslinked polysaccharides, such as carboxymethyl cellulose (Bajpai and Mishra, 2004; Baljit et al., 2007a), starch (Bajpai and Saxena, 2004), Chitin (Mahdavinia et al., 2004), dextran (Chiu et al., 1999; Kim and Oh, 2005), guar gum (Gilko et al., 1998; Prasad et al., 1998; Xiuyu et al., 2006) and psylluim (Baljit et al., 2007a). The rational for the development of a polysaccharide-based delivery system for colon is the presence of large amount of polysaccharidases in the human colon, as the colon is inhabited by a large number and variety of bacteria, which secrete many enzymes (Baljit et al., 2007a) Interests have been generated by many researches on hydrogels from konkoli and up to now no scientific information is currently present on its use in drug delivery. This study was therefore undertaken to find a novel hydrogel in addition to the existing once for the use in drug delivery as the drug delivery systems achieve more effective therapies while eliminating the potential of both under and over dosing, maintenance of drug levels with a desired range, and the need for fewer administration of drug. MATERIAL AND METHODS solutions and stirred with a glass rod to form a gel (that is 6.5g/2.6g konkoli/borax ration). The gel was then cast on a clean glass surface and dried over a period of 48 hours. Using the same procedure, different hydrogels were formed using different konkoli/borax ratios as indicated in Table 1(varying both the concentrations of galactomannan and borax). The different hydrogels formed were then designated with symbols with respect to galactomannan/ borax as indicted. Swelling measurement behaviour of hydrogels. The modified “Tea bag” method by Osemeahon et al., (2003) was employed. A transparent polyethylene bag was employed here and instead of hanging the bag to drain off, a micro-syringe was used to suck- away excess solution. The method entailed weighing 0.1 g of each of the samples into a weighed polyethylene bag and reweighed again. 10ml of distilled water was added to the polyethylene bag with the sample inside and hermetically sealed. The bag with its content was then left undisturbed at room temperature (270C) and at different time intervals, excess solution was carefully sucked out after a specified time is reached. The bag with the wet was reweighed again. The percentage absorption (water uptake) was calculated using the relation: Absorption/water uptake (%) = (w2 – w1/wo) x 100 Where: w2 = weight of the wet bag plus sample w1 = weight of the dry bag plus sample W o = weight of the original sample The swelling measurements for each system were repeated five times. The mean of the result were presented in all the figures. Preparation of buffer solution This was done according to standard method described by Baljit et al., 2007b. That is pH7.2 was prepared by taking 50 mL of 0.2M KCl and 7.8 mL of 0.2N HCl in volumetric flask to make volume 200mL with distilled water. 0.2 M KCl solution was prepared by dissolving 14.911 g of KCl in distilled water to make volume 1000mL with distilled water. Buffer solution of pH7.4 was prepared by taking 50mL of 0.2M KH2 PO4 and 39.1 mL of 0.2N NaOH in volumetric flask to make volume 200mL with distilled water. 0.2M KH2 PO4 was prepared by dissolving 27.218g of KH2PO4 in distilled water to make volume 1000mL with distilled water. pH2.2 and pH7.4 were chosen because there are the pH of gastrointestinal tract and the large intestine (Baljit et al., 2007b; Orienti et al., 2001) and this study also intended to know the swelling of these hydrogels in these parts. Materials Konkoli seeds (Maesopsis eminii) were obtained from Bayalse Local Government Area of Taraba State. The seeds were cleaned to remove dirt, sun-dried for three days and finally ground in an electric mill (National Food Drinder, Model MK308, Japan). Borax, KCI, HCl, KH2PO4 and NaOH were obtained from British Drug House (BDH). The chemicals were of analytical grade and were used as provided. Fourier transform infrared spectroscopy (FTIR) FTIR was carried out to study the modified nature of the hydrogel obtained from konkoli seeds. The FTIR spectra’s were recorded in KBr pellets on Perkin-Elmer (FTIR 8400S Shimadzu). Statistical analysis Methods Preparation of Hydrogel Systems 25ml portion of distilled water was transferred into 250ml glass beaker and mixed thoroughly with 6.5 g konkoli powder to form a very viscous solution. Then 2.6 g of borax was added to these Statistical analysis was performed by one- way analysis of variance, and differences between means were tested using Ducan’s multiple range tests. P-values of < 0.05 were considered to be significant following Steel and Torric procedures (1980) and Rui et al., (2007). 080 Int. Res. J. Plant Sci. Table 1. Blend ratio of galactomannan-borax system K/borax (w/v) 6.5g/2.6g 5.2g/2.6g 3.9g/2.6g 2.6g/2.6g 6.5g/3.25g 6.5g/4.33g RESULTS AND DISCUSSION Results Discussion Fourier transform infrared spectroscopy (FTIR) FTIR spectra of polymeric networks were recorded to study the modification of the konkoli hydrogel (Fig. 1a, and b). The absorption band at 3435.34 cm-1 can be ascribed to –OH stretching which indicated association in the polymeric networks. FTIR absorption bands due to C = O stretching of amide has been witnessed at 1654.01 -1 -1 cm in modified hydrogel. 1358.90 cm peak due to NH -1 and CH in plane bending, 823.63 cm peak due to NH and CH out of plane bending of amide and 1016.52 cm-1 peak due to C – O stretching of carboxylic acid has been observed apart form usual peaks in konkoli hydrogel. Swelling behaviour of hydrogels The chemical structure of the polymer affects the swelling ratio of the hydrogels which is directly related to loading of drug to the polymers and release of drug from the polymeric matrix. The chemical structure depended upon composition of the polymeric matrix i.e the crosslinking ratio. The higher the crosslinking ratio, the more crosslinking agent is incorporated in the hydrogels structure. Highly crosslinking hydrogels have a tighter structure, and will swell less compared to the same hydrogels with lower crosslinking ratios. Crosslinking hinders the mobility of the polymer chain, hence lowering the swelling ratio. Swelling of environmentally-sensitive hydrogels can be affected by specific stimuli. In the hydrogels systems, absorption of water from the environment changes the system and thus the drug release kinetics (Baljit et al., 2007a). Figure 2 presents the swelling behaviour of hydrogels on increasing the concentration of KG and keeping the Ratio 2.5:1 2:1 1.5:1 1:1 2:1 1.2:1 Symbol BG1 BG2 BG3 BG4 BG5 BG6 concentration of the BX constant. The result shows that the swelling ratio increases with increase in time and also increase with increase in the concentration KG ratio. This is because on keeping the concentration of borax (i.e crosslinking agent) constant and increasing the concentration of KG, the structure becomes less tight and absorbs more water. All the hydrogels absorbs water but hydrogel formulated with 6.5/2.6 (w/w) galactomanna/borax ratio absorbed more water between 5-9 hours. The order of water uptake is KG4< KG3 <KG2 <KG1 with significant differences in swelling values (P < 0.05). The hydrogels absorbed water in an increasing order from 1-5 hours but decreased at 6 hour and then increases from 7-9 hour except KG1 which decreases at 7 hour and again increases from 8-9 hour. This is due to the fact that the structures (KG2, KG3, KG4) have less KG concentration than KG1. Among all the hydrogels the one formulated with 6.5/2.6 (w/w) gives better results since it absorbed more water and start losing its network structure at 7 hour instead at 6 hour compared to the other hydrogels. With this result it is clearly indicated that KG1 would give better water uptake followed by KG2. Figure 3: shows the result for increasing concentration of BX and keeping the one of KSG constant. From this Figure KG5 absorbed more water than KG6 (P < 0.05). This is due to the fact that KG6 has more concentration of the crosslinking agent thereby leading to tight structure and swell less. KG5 start losing its network structure at 7 hour and KG6 at the 6 hour, which indicates that KG5 is better in terms of swelling and possible drug delivery. Effect of pH on swelling of hydrogels Figures 4-9 presence the effect of pH on swelling of hydrogels prepared with different concentrations of KG with significant differences in swelling values (P < 0.05). The swelling for KG1, KG2, KG3, and KG4 (Varying concentration of KG and keeping the concentration of borax constant) are given in Figures 4-7 respectively. In all the figures, it was observed that PS increases with change of the swelling medium from distilled water to pH7.2 and pH7.4. It has been also observed from all the figures that PS of pH7.4 was more compared to the pH2.2 and the distilled water. This is due to the fact that Nkafamiya et al. 081 A B Figure 1 (a) FTIR of konkoli hydrogel (b) FTIR spectra of modified konkoli hydrogel 1000 KG1 900 KG2 PercentageSw elling 800 KG3 700 KG4 600 500 400 300 200 100 0 0 2 4 6 Time (hrs) Figure 2. Effect of increasing KG on swelling (% Distilled water) 8 10 082 Int. Res. J. Plant Sci. 900 800 KG5 KG6 Percentage Swelling 700 600 500 400 300 200 100 0 0 2 4 6 8 10 Time (Hrs) Figure 3. Effect of increasing Borax on swelling (% Distilled water) 1000 900 Percentage swelling 800 DW pH2.2 700 pH7.4 600 500 400 300 200 100 0 0 2 4 6 8 10 Time (hour) Figure 4 : Effect of pH on Swelling behaviour KG1 Figure 4. Effect of PH on swelling behavior KG1 at lower pH values the –CONH2 groups do not ionizes and keep the network at its collapse state. At high pH value it gets partially ionizes, and the charged –COO groups repel each other, leading to increase in swelling of the polymer. These observations indicate that these hydrogels are pH sensitive and hence have potential for use in colon specific drug delivery devices. Similar observation was reported by Balijt and coworkers during syntheses, characterization and swelling response of pH sensitive psyllium and polyacrylamide based hydrogels for the use in drug delivery (I) (Baljit et al., 2007a). Baljit and coworkers again reported the same during the release dynamic of salicylic acid and tetracycline hydrochloride from the psyllium and polyacrylamide Nkafamiya et al. 083 900 800 DW Percentage Swelling 700 pH2.2 600 pH7.4 500 400 300 200 100 0 0 2 4 6 8 10 Time (hours) Figure 5. Effect PH on swelling of KG2 900 800 Percentage Swelling 700 600 500 400 DW 300 pH2.2 pH7.4 200 100 0 0 2 4 6 8 10 Time (Hours) Figure 6. Effect of swelling on KG3 based hydrogel (II) (Baljit et al., 2007b). Also, it is reported that the swelling of microgels, prepared with grafting of poly (AAm) onto guar gum, increases when the pH of the medium changes from acid to alkaline because of the saponification of the –CONH2 to the – COOH group (Soppimath et al., 2001). For varying concentration of borax and keeping the concentration of KG constant, are presented in Figures 89. Maximum PS was also observed in the medium of pH7.4. From the forgone discussion, these hydrogels have potentials to compete with other hydrogels reported 084 Int. Res. J. Plant Sci. 800 700 P e r c e n t a g e S w e llin g 600 500 DW 400 pH2.2 pH7.4 300 200 100 0 0 2 4 6 8 10 Time (hours) Figure 7. Effect of swelling on KG4 by Sumathi and Ray (2002), Balijt et al., (2007a) and Tommasina et al., (2007). CONCLUSION The swelling of the hydrogels is affected by concentration of polymer in the polymeric networks and nature of the swelling medium (pH). The swelling of the hydrogels increases by changing the swelling medium from DW to pH7.2 and pH7.4. This indicates the intelligent nature of polymers. Therefore KS when modified with BX, result in the formation of the pH sensitive hydrogels and have potential to use as colon specific drug delivery devices in addition to the existing once. 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