title: Stimuli-responsive zwitterionic block copolypeptides: poly(N-isopropylacrylamide)-block-poly(lysine-co-glutamic acid).
abstract: Synthesis of novel zwitterionic block copolypeptides, poly(N-isopropylacrylamide)-block-poly(L-glutamic acid-co-L-lysine) [PNiPAM(n)(PLG(x)-co-PLLys(y))m , where n is the number-average degree of polymerization (DP(n)) of PNiPAM block, x and y are the mole fraction of glutamic acid and lysine residues, respectively, and m is the total DP(n) of the peptide block], and their stimuli-responsiveness to temperature and pH variation in aqueous solutions are described. Initiated with the amino-terminated poly(N-isopropylacrylamide) (PNiPAM(n)-NH2), ring-opening polymerization (ROP) of a mixture of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA), and Boc-L-lysine N-carboxyanhydride (BLLys-NCA) afforded the block copolypeptides PNiPAM(n)(PBLG(x)-co-PBLLys(y))m, with a poly(N-isopropylacrylamide) block together with a random copolypeptide block, which was then deprotected with HBr/trifluoroacetic acid into the double hydrophilic block copolypeptides, PNiPAM(n)(PLG(x)-co-PLLys(y))m. Their block ratios and lengths, as well as the amino acid residue ratios in the random copolypeptide block are varied (n = 360, x = 0.4-0.5, y = 0.4-0.6, and m = 220-252). The secondary structures of the copolypeptides in aqueous solution at different pH conditions were examined. Phase transitions in aqueous solutions induced by both pH and temperature variation were investigated by (1)H NMR spectroscopy. The transitions induced by temperature were also explored by turbidity measurements using UV/vis spectroscopy for their lower critical aggregation temperature (LCAT) determination. Furthermore, these aggregation processes were followed by dynamic light scattering measurements.
authors.affiliation: School of Materials Science and Engineering, Zhengzhou University, Daxue Beilu 75, Zhengzhou 450052, China.
authors.forename: Jingguo
authors.initials: J
authors.lastname: Li
authors.forename: Tao
authors.initials: T
authors.lastname: Wang
authors.forename: Dalin
authors.initials: D
authors.lastname: Wu
authors.forename: Xiuqiang
authors.initials: X
authors.lastname: Zhang
authors.forename: Jiatao
authors.initials: J
authors.lastname: Yan
authors.forename: Song
authors.initials: S
authors.lastname: Du
authors.forename: Yifei
authors.initials: Y
authors.lastname: Guo
authors.forename: Jintao
authors.initials: J
authors.lastname: Wang
authors.forename: Afang
authors.initials: A
authors.lastname: Zhang