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Materials Letters 62 (2008) 215 218 www.elsevier.com/locate/matlet

Effect of heat treatment of starch on the properties of the starch hydrogels

Kunal Pal a , A.K. Banthia b,, D.K. Majumdar c
c

School of Nutrition, Ryerson University, Toronto, ON, Canada M5B 2K3 Materials Science Centre, Indian Institute of Technology, Kharagpur-721302, India Delhi Institute Of Pharmaceutical Sciences & Research, Formerly College of Pharmacy, University of Delhi, Pushp Vihar, New Delhi-110017, India
b

Received 6 June 2005; accepted 27 April 2007 Available online 17 May 2007

Abstract Development of hydrogels prepared by crosslinking of corn starch and polyvinyl alcohol with glutaraldehyde was attempted. The membranes were characterized by FTIR spectroscopy and XRD. The mechanical properties of the hydrogels were characterized by tensile tests. Diffusion studies of salicylic acid and gatifloxacin through the membranes were also evaluated. FTIR spectroscopy indicated absence of carbonyl group absorption band of glutaraldehyde and presence of hydroxyl group in the hydrogel membranes. XRD studies indicated that the crystallinity of the membranes was mainly due to PVA. The membranes had sufficient strength to be used for biomedical applications. Diffusion studies indicated diffusion of both anionic and cationic drugs through the hydrogel membranes. 2007 Elsevier B.V. All rights reserved.
Keywords: Hydrogels; Corn starch; Polyvinyl alcohol; Crosslinking

1. Introduction The first thing that comes to our mind when we hear the term hydrogel is three dimensional crosslinked hydrophilic polymer network capable of absorbing and holding water within the interstitial space of the polymer and does not release water under ordinary pressure. The water holding capability of the hydrogels could be accounted to the hydrophilic groups of the polymer network. Polysaccharides are being recently used for the development of hydrogels due to its unique advantages viz. non-toxicity, biocompatibility, biodegradability and abundance in nature [1,2]. The main disadvantage of polysaccharides is their easy solubility in water which limits its ability to form stable hydrogel. Currently the academic and industrial interest is towards the chemical modification of the polysaccharides into crosslinked polymer gel network. The applications of hydrogels include artificial skin, contact lenses, blood contact materials and incontrolled release applications for delivery of enzymes, hormones, contraceptives, anticoagulant, etc. Various biodegradable polymers viz. poly(lactic acid) (PLA), poly(glycolic acid) (PGA) and their copolymers have long been used in drug delivery systems.
Corresponding author. E-mail address: ajitbanthia2000@yahoo.co.in (A.K. Banthia). 0167-577X/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2007.04.113

However, only a few attempts have been reported in trying to use starch-based polymers in these type of applications; despite being well known that they are biodegradable materials they have been proposed in several works to be used as biomaterials [35]. Chemical modification of starch via graft copolymerization of vinyl monomers onto it has been studied widely in recent years. But only a few studies on starch polymer blend hydrogels have been reported. In this work PVA/starch blend hydrogels will be prepared by chemical Crosslinking technique (Fig. 1), and in the meantime the efforts will be made to characterize the hydrogel. Diffusion of molecules in polymer gels has been the subject of several studies. In the present study an effort was made to study the effect of change in processing condition of hydrogel synthesis on the diffusion coefficient of salicylic acid and gatifloxacin, used as model drugs. 2. Experimental 2.1. Materials Corn starch (CS), salicylic acid (SA), ethanol and glutaraldehyde (GA) were obtained from Loba-Chemie Indoaustranal Co., Mumbai, India. Polyvinyl alcohol (PVA), mol. wt. 125,000, was obtained from s.d. fine-chem. limited, Mumbai, India.

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were subjected to Attenuated Total Reflectance (ATR) spectroscopy in the range of 4000400 cm 1. FTIR spectrophotometer (NEXUS-870, Thermo Nicolet Corporation) was used for the study. The raw materials and the membranes were subjected to Xray diffraction (XRD-PW 1700, Philips, USA) using CuK radiation generated at 40 kV and 40 mA; the range of diffraction angle was 10.0070.00 2. The tensile strengths of the membranes were determined in the Hounsfield H10KS tensile testing machine. The following test conditions were maintained: a) Cross-head speed: 50 mm/min b) Temperature: 18 C and c) Relative humidity: 60. 2.4. Measurement of diffusion coefficient Hydrochloric acid 35% pure was obtained from Merck Limited, Mumbai, India. Double distilled water was used throughout the study. Gatifloxacin (GF) was obtained as a gift from Ranbaxy India limited, Gurgaon. GA reagent was prepared by mixing 0.5 ml of GA in a solution mixture of 10 ml ethanol and 0.05 ml hydrochloric acid. 2.2. Preparation of hydrogels The method of preparation of RT1 and HT1 has been described elsewhere [6]. The method of development of RT1 and HT1 has been described below in a precise manner. Fifty ml of 10% aqueous PVA solution was taken in a beaker. To the PVA solution 50 ml of 5% starch suspension in water was added with constant stirring to get a homogeneous mixture. To this mixture GA reagent (10.55 ml) was added with constant stirring. Care was taken to eliminate entrapment of air bubbles during mixing and the mixture was used immediately to obtain a membrane by the conventional solution casting method. The membrane was dried at room temperature. The membrane so obtained was designated as RT1. In another experiment, 2.5 g of starch suspension in 50 ml water was boiled with constant stirring to get dispersion. Fifty ml of heattreated starch dispersion was mixed with 50 ml of 10% aqueous PVA solution. To this mixture GA reagent (10.55 ml) was added with constant stirring. Then the above mixture was used to obtain a membrane as described in the above paragraph. The membrane so obtained was transparent and was designated as HT1. Similarly, RT2 and HT2 membranes were also developed having PVA:CS ratio of 1:1 i.e. 50 ml of 10% (w/v) CS suspension (heat-treated or non-heat-treated) and 50 ml of 10% (w/v) PVA solutions were used to develop the membranes. All of the membranes were washed thoroughly with water to wash off the hydrochloric acid and GA, if any. Then the membranes were dried at room temperature. 2.3. Characterization The raw materials were subjected to FTIR spectroscopy in the range of 4000400 cm 1 as KBr pellets and the membranes A two-compartment diffusion apparatus was used to measure the diffusion coefficient. The cell consisted of two chambers separated by a film ( 0.2-mm thick) of the hydrogel. The first chamber contained 5 ml of a known concentration of SA/GF in water (donor). The other chamber consisted 100 ml of filtered deionized water/Ringer's solution (receptor). The lower chamber was kept on stirring at 100 4 rpm. The diffusion studies were carried out at room temperature (30 C). A pipette was used to draw 0.1 ml sample from donor and 1.0 ml from receptor periodically and was replaced by equivalent amount of deionized water/Ringer's solution. The samples were analyzed by UV spectroscopy at 294 nm for SA and at 291 nm for GF. The diffusion coefficient, D, was calculated from these results [7].
3. Results and discussion 3.1. FTIR characterization In the present study more stress was given on the hydroxyl group determination, as it is present in both the raw materials and is responsible for water holding capacity of the hydrogel. The FTIR spectrum of CS (Fig. 2) showed a peak at 3387 cm 1 indicating the presence of intermolecular hydrogen bonded hydroxyl group having polymeric

Fig. 1. Schematic representation of crosslinking reaction.

Fig. 2. FTIR spectra of CS and hydrogel membranes.

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association. The FTIR spectrum of CS also showed peaks at 2930 cm 1 (CH stretching) and 1372 cm 1 (CH bending) indicating the presence of hydrocarbon chromophore in CS. The spectrum of PVA showed peak at 3423 cm 1 indicating the presence of intramolecularly hydrogen bonded hydroxyl groups in single bridge compounds [8]. The spectrum of PVA indicated peaks at 2942 cm 1 (CH stretching) and 1327 cm 1 (CH bending) indicating the presence of hydrocarbon chromophore in PVA [8]. The spectrum of the RT1 hydrogel (Fig. 2) showed peaks at 3550 cm 1, 3379 cm 1 and 3578 cm 1 indicating the presence of intermolecular hydrogen bonded hydroxyl group having polymeric association (3550 cm 1 and 3379 cm 1) and intramolecularly hydrogen bonded hydroxyl groups in single bridge compounds (3578 cm 1). This indicated the presence of free hydroxyl groups of both the raw materials in the hydrogel membrane. In addition to the above peaks the hydrogel also showed peaks at 2948 cm 1 and 1319 cm 1 indicating the presence of hydrocarbon chromophore. The spectrum of the RT2 hydrogel (Fig. 2) showed peaks at 3559 cm 1, 3382 cm 1 and 3582 cm 1 indicating the presence of intermolecular hydrogen bonded hydroxyl group having polymeric association (3559 cm 1 and 3382 cm 1) and intramolecularly hydrogen bonded hydroxyl groups in single bridge compounds (3582 cm 1). This indicated the presence of free hydroxyl groups of both the raw materials in the hydrogel membrane. In addition to the above peaks the hydrogel also showed peaks at 2949 cm 1 and 1326 cm 1 indicating the presence of hydrocarbon chromophore. The spectrum of the HT1 hydrogel (Fig. 2) showed peaks at 3552 cm 1, 3200 cm 1 and 3575 cm 1 indicating the presence of intermolecular hydrogen bonded hydroxyl group having polymeric association (3552 cm 1 and 3200 cm 1) and intramolecularly hydrogen bonded hydroxyl groups in single bridge compounds (3575 cm 1). This gives us the indication of the presence of free hydroxyl groups of both the

Table 1 Diffusion coefficients of SA and gatifloxacin through starch hydrogels Diffusion coefficient (cm2/s) SA (distilled water) RT1 RT2 HT1 HT2 4.11 10 6 1.22 10 6 5.55 10 6 2.18 10 6 SA (Ringer's solution) 3.84 10 6 5.27 10 6 Gatifloxacin (Ringer's solution) 2.80 10 6 3.53 10 6

raw materials in the hydrogel membrane. In addition to the above peaks the hydrogel also showed peaks at 2948 cm 1 and 1325 cm 1 indicating the presence of hydrocarbon chromophore. The spectrum of the HT2 hydrogel (Fig. 2) showed peaks at 3531 cm 1, 3227 cm 1 and 3574 cm 1 indicating the presence of intermolecular hydrogen bonded hydroxyl group having polymeric association (3531 cm 1 and 3227 cm 1) and intramolecularly hydrogen bonded hydroxyl groups in single bridge compounds (3574 cm 1). This gives us the indication of the presence of free hydroxyl groups of both the raw materials in the hydrogel membrane. In addition to the above peaks the hydrogel also showed peaks at 2946 cm 1 and 1326 cm 1 indicating the presence of hydrocarbon chromophore. In all the hydrogels there are no peaks in the range of 1740 1720 cm 1 indicating the absence of aldehydic group of GA. 3.2. XRD characterization XRD patterns of raw materials and hydrogel membranes are shown in (Fig. 3). It could be observed that CS had peaks at 15, 17, 18, 23 and 26.5 2 where the peak at 18 2 was most intense while PVA had peaks [8] at 19.5, 22.5, and 28.6 2 and the peak at 22.5 2 was most intense. In the case of RT1 and RT2 there was only one peak at 19.25 2 and 19.41 2, respectively, indicating that the crystallinity of the membrane was mainly due to PVA. Similarly, in the case of HT1 and HT2 there was only one peak at 19.42 and 19.41 2, respectively, indicating that the crystallinity of the membranes was contributed by PVA. From the XRD patterns the % crystallinity of PVA, CS, RT1, RT2, HT1 and HT2 was found to be 5.27, 8.24, 3.97, 9.99, 4.96 and 7.00 respectively. The % crystallinity suggested that the hydrogen bonding in RT1 and HT1 was lower than that of the hydrogen bonding in RT2 and HT2. This indicated that as the proportion of CS increases the crystallinity of the hydrogel increases due to the increased hydrogen bonding within the hydrogel structure. 3.3. Tensile strength of the membranes In order to evaluate the mechanical properties of the hydrogel membranes, the tensile strength and the % elongation of the membranes were measured. The tensile strengths of dry RT1, HT1, RT2 and HT2 hydrogel membranes were found to be 35.92 1.87 MPa, 41.01 5.30 MPa, 33.74 1.14 MPa and 51.98 4.98 MPa which were comparable to the failure strength of skin (34 MPa) [9]. The tensile strengths of RT1 and RT2 were almost comparable. But the tensile strength of HT2 was higher than HT1. In general, it could be observed that HT hydrogels were having higher tensile strengths than that of RT hydrogels. The % elongation results indicated that the % elongations of RT hydrogels were more than that of HT hydrogels. The % elongations of RT1, RT2, HT1 and HT2 were found to be 118, 20, 27 and 4, respectively (approx.). So, the membrane developed could be used as wound dressings that can give a cushioning effect to the wound, drug delivery matrix for controlled release etc.

Fig. 3. XRD diffractogram of CS and hydrogel membranes.

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3.4. Measurement of the diffusion coefficient The comparison of the diffusion coefficients indicated that the presence of ions in the receptor fluid, i.e. when the receptor fluid contained Ringer's solution, effects the diffusion of SA through the starch hydrogels. Also, as the molecular weight of the drug increases (MW of SA is 138.12 g/mol and MW of GF is 375.394 g/mol) the diffusion of the drug decreases as is evident from the diffusion coefficient of SA and gatifloxacin. It can also be observed that as the %age of starch was increased in the hydrogel the diffusion of SA decreased indicating that starch played an important role in decreasing the mobility of the SA (Table 1). Hence the %age of starch could be varied so as to obtain a controlled drug delivery system.

also grateful to his lab-technician and lab-mates (Mr. N. Mallick, Mr. A. H. Bhat, Mr. Arfat Anis, Mr. Dibakar Behara, Dr. S. Ghosh, Ms. H. Satpathee, Ms. S. Mondal, Ms. D. Mukherjee and Ms. R. Bana) for their constant encouragement and support during the completion of the work. References
[1] M.G. Cascone, N. Barbani, C. Cristallini, P. Giusti, G. Ciardelli, L. Lazzeri, Bioartificial polymeric materials based on polysaccharides, Journal of Biomaterials Science, Polymer Ed. 12 (3) (2001) 267281. [2] J. Chen, S. Jo, K. Park, Polysaccharide hydrogels for protein drug delivery, Carbohydrate Polymers 28 (1995) 6976. [3] S. Pereira, A.M. Cunha, R.L. Reis, B. Vazquez, J. San Roman, New starchbased thermoplastic hydrogels for use as bone cements or drug delivery carriers, Journal of Material Science, Materials in Medicine 9 (1998) 825833. [4] S. Kiatkamjornwong, W. Chomsaksakul, M. Sonsuk, Radiation modification of water absorption of cassava starch by acrylic acid/acrylamide, Radiation Physics and Chemistry 59 (2000) 413427. [5] K. Hashim, K.Z. Dahlan, N.M. Noordin, Hydrogel of sago starch/watersoluble polymers by electron beam irradiation technique, International Symposium on Radiation Technology in Emerging Industrial Applications, International Atomic Energy Agency(IAEA)-SM-365, 2000, pp. 7980. [6] K. Pal, A.K. Banthia, D.K. Majumdar, Characterizations of the prepared corn-starch based hydrogel membranes, Journal of Applied Biomaterials and Biomechanics 4 (2006) 3844. [7] K. Pal, A.K. Banthia, D.K. Majumdar, Preparation and characterization of polyvinyl alcoholgelatin hydrogel membranes for biomedical applications, AAPS PharmSciTech 8 (1) (2007) E1E5. [8] K. Pal, A.K. Banthia, D.K. Majumdar, Polyvinyl alcoholgelatin patches of salicylic acid: preparation, characterization and drug release studies, first published online on 27th January, 2006 in Journal of Biomaterials Application. [9] S.V. Bhat, Biomaterials, Narosa Publishing House, New Delhi, India, 2002, p. 106.

4. Conclusion The hydrogels developed by the heat-treated starch were transparent and that of the non-heat-treated starch were white in color. FTIR studies indicated the presence of free hydroxyl group in the hydrogel membranes. XRD studies indicated that the crystallinity of the hydrogel membranes was mainly due to PVA. The mechanical tests indicated that the membranes had sufficient strength and elongation properties for biomedical applications. The diffusion studies indicated that both anionic (SA) and cationic drugs (GF) could easily diffuse through the starch hydrogels. In short, the prepared hydrogel membrane could be used as artificial skin and at the same time various nutrients/healing factors and medicaments can be delivered to the site of action by the process of diffusion. Acknowledgements The authors are thankful to Indian Institute of Technology, Kharagpur, India for funding the research. The first author is