Temperature sensitivity of a hydrogel network containing different LCST oligomers grafted to the hydrogel backbone

Abstract Hydrogels (HGs) containing two different lower critical solution temperature (LCST) oligomers grafted to the same HG backbone were synthesized using macromonomers of the LCST oligomers. Carboxy-terminated oligo(N-iso-propylacrylamide) (oNIPAAm) oligo(N-vinylcaprolactam) (oVCL) and a random co-oligomer of NIPAAm and acrylamide (AAm) (o[NIPAAm-co-AAm]) were selected as the LCST oligomers. The macromonomers were synthesized by reaction of the terminal carboxy groups with glycidyl metha-crylate. Using AAm as the base monomer for the HG macromonomers of the carboxy-terminated oNIPAAm and oVCL were copolymerized with AAm and a cross–linker and the HG was obtained. Despite the lack of temperature-sensitivity of the PAAm HG the grafted HG showed two volume phase transitions corresponding to the LCSTs of the grafted side chains of oNIPAAm and oVCL.

[1]  L. Goldstein,et al.  Application of a thermally-reversible polymer-antibody conjugate in a novel membrane-based immunoassay. , 1990, Biochemical and biophysical research communications.

[2]  Allan S. Huffman,et al.  Thermally reversible hydrogels: II. Delivery and selective removal of substances from aqueous solutions , 1986 .

[3]  Toyoichi Tanaka,et al.  Phase transition of submicron gel beads , 1987 .

[4]  T. Okano,et al.  Comb-type grafted hydrogels with rapid deswelling response to temperature changes , 1995, Nature.

[5]  S. Itô Phase Transition of Aqueous Solution of Poly (N-alkylacrylamide) Derivatives-Effects of Side Chain Structure- , 1989 .

[6]  B Mattiasson,et al.  Thermoreactive water-soluble polymers, nonionic surfactants, and hydrogels as reagents in biotechnology. , 1993, Enzyme and microbial technology.

[7]  J. Feijen,et al.  Heparin release from thermosensitive hydrogels , 1992 .

[8]  Y. Bae,et al.  pH/temperature-sensitive polymers for macromolecular drug loading and release , 1994 .

[9]  A. Hoffman,et al.  Phase-separation immunoassays. , 1987, Clinical chemistry.

[10]  L. Dong,et al.  Controlled release of amylase from a thermal and pH-sensitive, macroporous hydrogel , 1992 .

[11]  A. Hoffman,et al.  Graft copolymers that exhibit temperature-induced phase transitions over a wide range of pH , 1995, Nature.

[12]  T. Okano,et al.  Thermo-sensitive polymers as on-off switches for drug release , 1987 .

[13]  H. G. Schild Poly(N-isopropylacrylamide): experiment, theory and application , 1992 .

[14]  Teruo Okano,et al.  Insulin permeation through thermo-sensitive hydrogels , 1989 .

[15]  T. Park,et al.  Synthesis and characterization of a soluble, temperature-sensitive polymer-conjugated enzyme. , 1993, Journal of biomaterials science. Polymer edition.

[16]  Shozaburo Saito,et al.  Phase Transition of N-Substituted Acrylamide Gels , 1990 .

[17]  L. Dong,et al.  Thermally reversible hydrogels: III. Immobilization of enzymes for feedback reaction control , 1986 .

[18]  Allan S. Hoffman,et al.  Applications of thermally reversible polymers and hydrogels in therapeutics and diagnostics , 1987 .

[19]  Nikolaos A. Peppas,et al.  Pulsatile local delivery of thrombolytic and antithrombotic agents using poly(N-isopropylacrylamide-co-methacrylic acid) hydrogels , 1996 .

[20]  A. Hoffman,et al.  Synthesis of carboxylated poly(NIPAAm) oligomers and their application to form thermo-reversible polymer-enzyme conjugates. , 1994, Journal of biomaterials science. Polymer edition.

[21]  T. Park,et al.  Immobilized Biocatalysts in Reversible Hydrogels a , 1990 .

[22]  T. Soós,et al.  Poly-N-vinylamides, complexation and conformational changes in aqueous solution , 1983 .

[23]  Chuan Yi Tang,et al.  A 2.|E|-Bit Distributed Algorithm for the Directed Euler Trail Problem , 1993, Inf. Process. Lett..

[24]  T. Okano,et al.  Temperature-responsive bioconjugates. 1. Synthesis of temperature-responsive oligomers with reactive end groups and their coupling to biomolecules. , 1993, Bioconjugate chemistry.

[25]  K. Ishihara,et al.  Synthesis of graft copolymers having phospholipid polar group by macromonomer method and their properties in water , 1994 .

[26]  A. Hoffman,et al.  Synthesis and purification of thermally sensitive oligomer-enzyme conjugates of poly(N-isopropylacrylamide)-trypsin. , 1996, Bioconjugate chemistry.

[27]  A S Hoffman,et al.  Immobilization and characterization of beta-galactosidase in thermally reversible hydrogel beads. , 1989, Journal of biomedical materials research.

[28]  T. Okano,et al.  Stimuli sensitive polymers for drug delivery systems , 1990 .

[29]  R. Yoshida,et al.  Surface-modulated skin layers of thermal responsive hydrogels as on-off switches: I. Drug release. , 1991, Journal of biomaterials science. Polymer edition.

[30]  T. Okano,et al.  Temperature-responsive poly(N-isopropylacrylamide) as a modulator for alteration of hydrophilic/hydrophobic surface properties to control activation/inactivation of platelets , 1995 .

[31]  T. Okano,et al.  A novel recovery system for cultured cells using plasma-treated polystyrene dishes grafted with poly(N-isopropylacrylamide). , 1993, Journal of biomedical materials research.

[32]  A S Hoffman,et al.  Immobilization of Arthrobacter simplex in a thermally reversible hydrogel: Effect of temperature cycling on steroid conversion , 1990, Biotechnology and bioengineering.

[33]  Allan S. Hoffman,et al.  Effect of temperature on the release rate of biomolecules from thermally reversible hydrogels , 1987 .

[34]  T. Okano,et al.  Effect of molecular architecture of poly(N-isopropylacrylamide)-trypsin conjugates on their solution and enzymatic properties. , 1996, Bioconjugate chemistry.

[35]  T. Okano,et al.  Temperature-responsive bioconjugates. 3. Antibody-poly (N-isopropylacrylamide) conjugates for temperature-modulated precipitations and affinity bioseparations. , 1994, Bioconjugate chemistry.

[36]  T. Okano,et al.  Temperature-responsive bioconjugates. 2. Molecular design for temperature-modulated bioseparations. , 1993, Bioconjugate chemistry.

[37]  Teruo Okano,et al.  Thermally on-off switching polymers for drug permeation and release , 1990 .

[38]  L. Dong,et al.  Synthesis and application of thermally reversible heterogels for drug delivery , 1990 .

[39]  T. Okano,et al.  Swelling controlled zero order and sigmoidal drug release from thermo-responsive poly(N-isopropylacrylamide-co-butyl methacrylate) hydrogel. , 1993, Journal of biomaterials science. Polymer edition.