Synthesis of temperature-responsive heterobifunctional block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide)

被引:96
作者
You, Ye-Zi [1 ]
Oupicky, David [1 ]
机构
[1] Wayne State Univ, Dept Pharmaceut Sci, Detroit, MI 48202 USA
关键词
D O I
10.1021/bm060635b
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Heterobifunctional block copolymers of poly( ethylene glycol) ( PEG) and poly(N-isopropylacrylamide) ( PNIPAM) were synthesized by reversible addition-fragmentation chain transfer ( RAFT) polymerization of NIPAM using a macromolecular trithiocarbonate PEG-based chain transfer agent. The polymerization showed all the expected features of living radical polymerization and allowed the synthesis of copolymers with different lengths of the PNIPAM block. The synthesized block copolymers contained a carboxylic acid group from L-lysine at the focal point and a trithiocarbonate group at the terminus of the PNIPAM block. The trithiocarbonate functionality was converted into a thiol group and used for conjugation of biotin to the end of the PNIPAM block. The copolymers exhibited temperature-dependent association behavior in aqueous solution with a phase transition of approximately 32 degrees C. The described heterobifunctional block copolymers show promise for surface modifications with the potential for stimulus-controlled surface presentation of ligands attached to the terminus of the PNIPAM block.
引用
收藏
页码:98 / 105
页数:8
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共 43 条
[1]   pH-controlled association of PEG-containing terpolymers of N-isopropylacrylamide and 1-vinylimidazole [J].
Bisht, HS ;
Wan, L ;
Mao, GZ ;
Oupicky, D .
POLYMER, 2005, 46 (19) :7945-7952
[2]   Living free-radical polymerization by reversible addition-fragmentation chain transfer: The RAFT process [J].
Chiefari, J ;
Chong, YK ;
Ercole, F ;
Krstina, J ;
Jeffery, J ;
Le, TPT ;
Mayadunne, RTA ;
Meijs, GF ;
Moad, CL ;
Moad, G ;
Rizzardo, E ;
Thang, SH .
MACROMOLECULES, 1998, 31 (16) :5559-5562
[3]   A more versatile route to block copolymers and other polymers of complex architecture by living radical polymerization: The RAFT process [J].
Chong, YK ;
Le, TPT ;
Moad, G ;
Rizzardo, E ;
Thang, SH .
MACROMOLECULES, 1999, 32 (06) :2071-2074
[4]   Facile, controlled, room-temperature RAFT polymerization of N-isopropylacrylamide [J].
Convertine, AJ ;
Ayres, N ;
Scales, CW ;
Lowe, AB ;
McCormick, CL .
BIOMACROMOLECULES, 2004, 5 (04) :1177-1180
[5]   KINETICS AND MECHANISM OF POLYTHIOAMIDATION IN SOLUTION .1. REACTION OF MONO(DITHIOESTER)S AND BIS(DITHIOESTER)S WITH EXCESS AMINE [J].
DELETRE, M ;
LEVESQUE, G .
MACROMOLECULES, 1990, 23 (22) :4733-4741
[6]   N,N'-DISUCCINIMIDYL CARBONATE - A USEFUL REAGENT FOR ALKOXYCARBONYLATION OF AMINES [J].
GHOSH, AK ;
DUONG, TT ;
MCKEE, SP ;
THOMPSON, WJ .
TETRAHEDRON LETTERS, 1992, 33 (20) :2781-2784
[7]   Functionalized (X-PEO)2-(PS-Y)2 star block copolymers at the interfaces:: Role of terminal groups in surface behavior and morphology [J].
Gunawidjaja, R ;
Peleshanko, S ;
Tsukruk, VV .
MACROMOLECULES, 2005, 38 (21) :8765-8774
[8]   Synthesis and characterization of well-defined diblock and triblock copolymers of poly(N-isopropylacrylamide) and poly(ethylene oxide) [J].
Hong, CY ;
You, YZ ;
Pan, CY .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2004, 42 (19) :4873-4881
[9]   The coil-to-globule-to-brush transition of linear thermally sensitive poly(N-isopropylacrylamide) chains grafted on a spherical microgel [J].
Hu, TJ ;
You, YZ ;
Pan, CY ;
Wu, C .
JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (26) :6659-6662
[10]   pH-sensitive gating by conformational change of a polypeptide brush grafted onto a porous polymer membrane [J].
Ito, Y ;
Ochiai, Y ;
Park, YS ;
Imanishi, Y .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (07) :1619-1623