Synthesis and property of temperature and pH sensitive xanthan-MA/PNIPAAm hydrogels

Abstract

A novel class of xanthan-maleic anhydride (Xan-MA)/poly(N-isopropylacrylamide) hybrid hydrogels was designed and synthesized by solution polymerization. The xanthan-based precursor (Xan-MA) was prepared by substituting the hydroxyl groups in Xan by MA. This Xan-MA precursor was then polymerized with a known temperature sensitive precursor (N-isopropylacrylamide, NIPAAm) to form hybrid hydrogels with a series range of composition ratio of Xan-MA to NIPAAm precursors. These smart hydrogels were characterized by Fourier transform infrared spectroscopy for structural determination, differential scanning calorimertry for thermal property. And maximum swelling ratio, swelling kinetics and temperature response kinetics were studied. The data obtained clearly show that these smart hydrogels are responsive to the external changes of temperature as well as pH value. The magnitudes of smart and hydrogel properties of these hybrid hydrogels depend on the feed composition ratio of the two precursors. With the increase of the content of Xan-MA the maximum swelling ratio, reswelling ratio and thermo-sensitivities increase, and the feed composition ratio of Xan-MA/NIPAAm increases the maximum swelling ratio augment from 13.88 to 23.21. From XMN0, XMN1, XMN3 to XMN5, the lower critical solution temperatures (LCSTs) are 33.02, 36.15, 40.28 and 41.92 °, respectively. By changing the composition ratio of these two precursors, the LCST of the hybrid hydrogels could also be adjusted to be or near the body temperature for the potential applications in bioengineering and biotechnology fields.

Keywords

hydrogel / N-isopropylacrylamide / polysaccharide / temperature / pH

References

[1] Torres-LugoM., PeppasN. A.. Molecular design and in vitro studies of novel pH-sensitive hydrogels for the oral delivery of calcitonin [J]. Macromolecules, 1999, 32(20): 6646-6651

[2] HoffmanA. S.. Application of thermally reversible polymers and hydrogels in therapeutics and diagnostics [J]. Journal of Controlled Release, 1987, 6(1): 297-305

[3] SuzukiA., TanakaT.. Phase transition in polymer gels induced by visible-light [J]. Nature, 1990, 346: 345-347

[4] MiyataT., AsamiN., UragamiT.. A reversibly antigen-responsive hydrogel [J]. Nature, 1999, 399: 766-769

[5] StaytonP. S., ShimobjiT., LongC., ChilkotiA., ChenG., HarrisJ. M., HoffmanA. S.. Control of protein-ligand recognition using a stimuli-responsive polymer [J]. Nature, 1995, 378: 472-474

[6] PanY.-s., XiongD.-s., MaR.-yin.. Preparation and swelling behavior of polyvinyl alcohol physiological saline gel [J]. Journal of Central South University of Technology, 2006, 13(1): 27-31

[7] OsadaY., OkuzakiH., HoriH.. A polymer gel with electrically driven motility [J]. Nature, 1992, 355: 242-244

[8] LiuF., TaoG. L., ZhuoR. X.. Synthesis of thermal phase-separating reactive polymers and their applications in immobilized enzymes [J]. Polymer Journal, 1993, 25(6): 561-567

[9] HirokawaY., TanakaT.. Volume phase transition in a nonionic gel [J]. Journal of Chemical Physics, 1984, 81(12): 6379-6380

[10] HoffmanA. S.. Environmentally sensitive polymers and hydrogels smart biomaterials [J]. MRS Bulletin, 1991, 16(9): 42-46

[11] ZhangX. Z., YangY. Y., ChungT. S.. The influence of cold treatment on properties of temperature-sensitive poly (N-isopropylacrylamide) hydrogels [J]. Journal of Colloid and Interface Science, 2002, 246: 105-111

[12] HortonD., MolsO., WalasekZ., WernauW. C.. Structural and biosynthetic studies on xanthan by ¹³C-N.M.R. spectroscopy[J]. Carbohydrate Research, 1985, 141(2): 340-346

[13] HallL.D., YalpaniM.. Determination of the primary structure of polysaccharides and their derivatives by solid-state carbon-13 N.M.R. spectroscopy [J]. Carbohydrate Research, 1981, 91(2): C1-C4

[14] MilasM., RinaudoM.. Conformational investigation on the bacterial polysaccharide xanthan [J]. Carbohydrate Research, 1979, 76(1): 189-96

[15] WangL. F., ShenS. S., LuS. C.. Synthesis and characterization of chondroitin sulfate-methacrylate hydrogels [J]. Carbohydrate Polymers, 2003, 52(4): 389-396

[16] Martinez-RuvalcabaA., ChornetE., RodrigueD.. Viscoelastic properties of dispersed chitosan/xanthan hydrogels [J]. Carbohydrate Polymers, 2007, 67(4): 586-595

[17] LiuY. Y., FanX. D.. Preparation and characterization of a novel responsive hydrogel with β-cyclodextrin-based macromonomer [J]. Journal of Applied Polymer Science, 2003, 89(2): 361-367

[18] IijimaM., ShinozakiM., HatakeyamaT., TakahashiM., HatakeymaH.. AFM studies on gelation mechanism of xanthan gum hydrogels [J]. Carbohydrate Polymers, 2007, 68(4): 701-707

[19] HamcerencuM., DesbrieresJ., PopaM., KhoukhA., RiessG.. New unsaturated derivatives of xanthan gum: Synthesis and characterization [J]. Polymer, 2007, 48(7): 1921-1929

[20] KanekoY., YoshidaR., SakaiK., SakuraiY., OkanoT.. Temperature-responsive shrinking kinetics of poly (N-isopropylacrylamide) copolymer gels with hydrophilic and hydrophobic comonomers [J]. Journal of Membrane Science, 1995, 101: 13-22