Novel amphoteric cystine-based poly(amidoamine)s responsive to redox stimuli

被引:31
作者
Emilitri, Elisa
Ferruti, Paolo
Annunziata, Rita
Ranucci, Elisabetta
Rossi, Manuela
Falciola, Luigi
Mussini, Patrizia
Chiellini, Federica
Bartoli, Cristina
机构
[1] Ctr Interdisciplinare Mat & Interface Nanostruttu, Dipartimento Chim Organ & Ind, I-20133 Milan, Italy
[2] Ctr Interdisciplinare Mat & Interface Nanostruttu, Dipartimento Chim Fis & Elettrochim, I-20133 Milan, Italy
[3] Univ Pisa, Dipartimento Chim & Chim Ind, BIOLAB, UdR INSTM Consortium, I-56126 Pisa, Italy
关键词
BIOMEDICAL APPLICATIONS; POLYETHYLENE-GLYCOL; POLYMERS; CYSTEINE; POLY(AMIDO-AMINE)S; SPECTROSCOPY;
D O I
10.1021/ma062115e
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Novel poly(amidoamine)s (PAAs) containing disulfide linkages regularly arranged along the polymer chain, namely BP-CY and BAC-CY, were synthesized by stepwise polyaddition of L-cystine to 1,4-bis(acryloyl)piperazine (BP) and 2,2-bis(acrylamido)acetic acid (BAC), respectively. Even if L-cystine contains four acid hydrogens, no evidence of cross-linking was found. All products were characterized by H-1 and C-13 NMR spectroscopy, and their average molecular weight determined by size exclusion chromatography. The polymerization rates were investigated by means of H-1 NMR spectroscopy. In both cases, the experimental data were consistent with pseudo-second-order kinetics. The calculated kinetic constants were k(c,BP) = 8.10 x 10(-3) min(-1) L mol(-1) and k(c,BAC) = 1.41 x 10(-3) min(-1) L mol(-1) for the polyaddition of L-cystine to BP and BAC, respectively. A potentiometric study was carried out of BP-CY and BAC-CY speciation as a function of pH, and the electrochemical activity of their disulfide bonds as a function of pH was investigated by cyclic voltammetry on hanging drop mercury electrode, revealing many analogies with parent L-cystine. BP-CY and BAC-CY degraded in aqueous systems at a rate similar to that usually reported for PAAs. In the presence of reducing agents, however, they degraded completely in a few minutes. Preliminary biocompatibility in vitro tests showed that both BP-CY and BAC-CY are devoid of appreciable toxicity.
引用
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页码:4785 / 4793
页数:9
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