Bioengineering Functional Copolymers. IX. Synthesis and Characterization of Stimuli-Responsive Poly N-isopropylacrylamide-co-N-vinyl-2-pyrrolidone and Its Cu II Complexes

Radical copolymerization of N-isopropylacrylamide NIPA with N-vinyl-2-pyrrolidone VP were carried out with 2,2’azobisisobutyronitrile AIBN as an intiator in N,N’-dimethylformamide solution at 65oC under nitrogen atmosphere.Cu II –copolymer macrocomplexes were prepared by incorporation of copolymers with copper sulfate in aqueoussolution at 40oC. Structure and composition of the obtained copolymers, and the formation of coordinated Cu II complexes between amide VP unit and Cu II ions were studied by FTIR spectroscopy, DSC and TGA-DTG methods,as well as by the electrical conductivity measurements. Compositon of the copolymers synthesized in a wide rangeof monomer feed ratios were determined by FTIR and1H 13C NMR–DEPT-135 spectroscopy. The monomer reactivityratios were determined by Fineman-Ross, Kelen-Tüdös and non-linear regression methods. It was observed thatstudied monomer pair has some tendency to alternation in the chosen monomer feed ratios due to formation ofintermolecular interaction through H-bonding and N→O=C coordination. The copolymers predominantly showamorphous structure while their Cu II –macrocomplexes exhibit crystalline phase. The conductive properties of thesynthesized Cu II –poly VP-co-NIPA complexes was also discussed.The synthesized poly NIPA-co-VP s showtemperature sensitiveness Ts and higher glass-transition temperature Tg and thermal stability, polyelectrolyte andstimuli-responsive temperature- and pH-sensitive behavior, and can be attributed to the class of bioengineeringfunctional copolymers useful for application in various gene- and bioengineering processes, drug delivery systems,and biomacromolecule conjugations

___

  • Ding, X. B.; Sun, Z. H.; Zhang, W. C.; Peng, Y. X.; Wan, G. X. J. Appl. Polym. Sci. 2000, 77, 2915-2920.
  • Ringsdorf, H.; Venzmer. J.; Vinnik, F. M. Macromolecules 1991, 24, 1678-1686.
  • Umeno, D.; Maeda, M. Anal. Sci. 1997, 13, 553-556.
  • Dinçer, S.; Köseli, V.; Kesim, H.; Rzaev, Z. M. O.; Pişkin, E. Eur. Polym. J. 2002, 38, 2143- 2152.
  • Kesim, H.; Rzaev, Z. M. O, Dinçer, S.; Pişkin, E. Polymer 2003, 44, 2897-909.
  • Köseli, V.; Rzaev, Z. M. O.; Pişkin, E. J. Polym. Sci. A-1: Polym. Chem. 2003, 41, 1580-1593.
  • Otake, K.; Inomata, H.; Konno, M.; Saita, S. Macromolecules 1990, 23, 83-88.
  • Hirotsu, S. Macromolecules 1992, 25, 4445- 4447.
  • Dong, C.; Hoffmann, A. S. J. Control. Rel. 1990, 13, 21-31.
  • Chilkoti, A.; Chen, G.; Stayton, P. S.; Hoffman, A. S. Bioconjugate Chem, 1994, 5, 504-507.
  • Chen, G.; Hoffman, A. S. Macromol. Rapid Commun. 1995, 16, 175-182.
  • Tuncel, A.; Demirgöz, D.; Patir, S.; Pişkin, E. J. Appl. Polym. Sci. 2002, 84, 2060-2071.
  • Bokias, G.; Hourdert, D. Macromolecules 2000, 33, 2929-2935.
  • Bokias, G; Hourdert, D. Polymer 2001, 42, 6329-6337.
  • Dinçer, S.; Tuncel, A.; Pişkin, E. Macromol. Chem. Phys. 2002, 203, 1460-1465.
  • Türk, M.; Dinçer, S.; Yulug, G. I.; Pişkin, E. J. Control. Release 2004, 96:2 325-340.
  • Bulmuş, V.; Patır, S.; Tuncel, A.; Pişkin, E. J. Control. Release 2001, 76, 265-274.
  • Mark, H. F.; Bikales, N. M.; Overberger, C. G.; Menges, G., Eds.; Encyclopedia of Polymer Science and Engineering, Wiley-Interscience: New York, 1989; Vol. 17. 1989, p 198.
  • Kirsh, Yu. K.Water Soluble Poly-N-vinylamides. Synthesis and Physicochemical Properties, Wiley: Chichester, 1998; p 233.
  • Huglin, M. B.; Khairou, K. S. Eur. Polym. J. 1988, 24, 239-243.
  • Brar, A. S.; Kumar, R. Polym. Int. 2002, 51, 519-529.
  • Gatica, N.; Gargallo, L.; Radic, D. Polym. Int. 1998, 45, 285-290.
  • Gatica, N.; Gargallo, L.; Radic, D. Eur. Polym. J. 2002, 38, 1371-1375.
  • Veron, L.; Revol, M.; Mandransd, B.; Delair, T. J. Appl. Polym. Sci. 2001, 81, 3327-3337.
  • Georgiev, G.; Konstantinov, C.; Kabaivanov, V. Macromolecules 1992, 25, 6302-6308.
  • Ng, L.-T.; Jönsson, S.; Swami, S.; Lindgren, K. Polym. Int. 2002, 51, 1398-403.
  • Reddy, B,.; Arshady, R.; George, M. Eur. Polym. J. 1985, 21, 511-602.
  • Radic, D.; Gargallo, L. Macromolecules 1997, 30, 817-825.
  • Bauduin, G.; Boutevin, B.; Belbachir, M.; Meghabar, R. Macromolecules 1995, 28, 1750- 1753.
  • Senel, S.; Isik-Uruksoy, B.; Çiçek, H.; Tuncel, A. J. Appl. Polym. Sci. 1997, 64, 1775-1784.
  • Anufrieva, E. V.; Gromova, R. A.; Kirsh, Yu. E.; Yanul, N. A.; Krakovyak, M. G.; Lushchik, V. B.; Pautov, V. D.; Sheveleva, T. V. Eur. Polym. J. 2001, 37, 323-328.
  • Eeckman, F.; Moes, A. J.; Amighi, K. Eur. Polym. J. 2004, 40, 873-881.
  • Rivas, B. L.; G. V. Seguel, G. V. Polyhedron 1999, 18, 2511. 43. Salomone, J. C. Polymeric Material Encyclopedia, CRC Press: London, 1996, Vol.6, p.4102.
  • Bulman, R. A. Struct Bonding 1987, 67, 91.
  • Bryce-Smith, D. Chem Soc Rev 1973, 15, 93 .
  • Albert, A. Selective Toxicity; Chapman & Hall: London, 1973.
  • Lauffer, R. B. Chem Rev 1987, 87, 901.
  • Sahni, S. K.; Reedijik, J. Coord Chem Rev 1984, 1, 59.
  • Michalska, Z. M.; Strzelec, K.; Sobczak, J. W. J Mol Catalysis A, Chem 2000, 156, 91.
  • Berslow, R.; Belvedere, S.; Gershell, L.; Leung, D. Pure Appl Chem 2000, 72, 333.
  • Pekel, N.; ahiner, N.; Güven, O.; Rzaev, Z. M. O. Eur. Polym. J. 2001, 37, 2443-2451.
  • Brandrup, J.; Immergut, E. H. Polymer handbook, 3nd ed.; John Wiley & Sons: New York, 1989; p II-274.
  • Robinson, B. V.; Sallivan, F. M.; Borzelleca, J. F.; Schwartz, S. L. Poly(vinyl pyrrolidone). Levis Publishers: Michigan, 1990; p 209.
  • Fineman, M.; Ross, S. D. J. Polym. Sci. 1950, 5, 259-265.
  • Kelen, T.; Tüdös, F. J. Macromol. Sci. Chem. A: 1975, 9, 1-27.
  • Dube, M.; Amin Sanayei, R.; Penlidis, A.; O’Driscoll, K. F.; Reilly, P. M. J. Polym. Sci. Part A-2: Polym. Chem. 1991, 29, 703-708.
  • Odian, G. Principles of Polymerization, 3nd ed.; John Wiley & Sons Inc.: New York, 1991; p 480. 58. Molineux, P. Water Soluble Synthetic Polymers; Properties and Behavior; CRC Press: Boca Raton, FL, 1983; Vol. 1, p 146.
  • Salamova, Ü.; Masimov, A. A.; Rzaev, Z. M. O. Polymer 1996, 37, 2415-2421.
  • Durand, A.; Hourdet, D. Polymer 2000, 41, 545-557.