New poly(amidoamine)s containing disulfide linkages in their main chain
New poly(amidoamine)s containing disulfide linkages in their main chain
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DOI：
10.1002/pola.20599
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发表时间：
2005-04-01
影响因子：
--
通讯作者：
Ferruti, P
中科院分区：
文献类型：
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作者：
Emilitri, E;Ranucci, E;Ferruti, P
通过2-甲基哌嗪与N,N'-双(丙烯酰)胱胺(BACy1)或N,N'-双(丙烯酰)-(L)胱氨酸(BACy2)逐步加聚合成了新型聚(酰胺基胺)(PAA)，其含有沿主链规则排列的二硫键。两种双丙烯酰胺又都是通过丙烯酰氯与相应的胺反应获得的。所有产物均采用 H-1 和 C-13 NMR 光谱进行表征，并通过尺寸排阻色谱法测定聚合物的平均分子量。两种 PAA 表现出不同的溶解度特性。特别是，源自 BACy1 的 PAA-Cy1 微溶于水，而源自 BACy2 的 PAA-Cy2 极易溶于水介质。用1H NMR 光谱研究聚合速率。在这两种情况下，实验数据都符合伪二级动力学。计算得出BACy1和BACy2的加聚反应动力学常数分别为5.96 X 10(-3)和5.90 X 10(-2) min(-1) L mol(-1)。观察到的 PAA-Cy2 在 pH 7.4 三（羟甲基）氨基甲烷 (TRIS) 缓冲液中的水解降解率与传统两性 PAA（即重复单元中含有羧基的 PAA）相当。在 2-巯基乙醇存在下与两种 PAA 进行的降解实验表明，其重复单元中包含的二硫基在硫醇存在下易于还原裂解。 (c) 2005 年 Wiley 期刊公司。
Novel poly(amidoamine)s (PAAs) containing disulfide linkages regularly arranged along their backbones were synthesized by the stepwise polyaddition of 2-methylpiperazine to N,N'-bis(acryloyl)cystamine (BACy1) or N,N'-bis(acryloyl)-(L)cystine (BACy2). Both bisacrylamides had, in turn, been obtained by the reaction of acryloyl chloride with the corresponding amines. All the products were characterized with H-1 and C-13 NMR spectroscopy, and the average molecular weights of the polymers were determined by size exclusion chromatography. Both PAAs showed different solubility properties. In particular, PAA-Cy1, derived from BACy1, was sparingly soluble in water, whereas PAA-Cy2, derived from BACy2, was very soluble in aqueous media. The polymerization rates were investigated with 1H NMR spectroscopy. In both cases, the experimental data were consistent with pseudo-second-order kinetics. The calcu lated kinetic constants were 5.96 X 10(-3) and 5.90 X 10(-2) min(-1) L mol(-1) for the polyaddition of BACy1 and BACy2, respectively. The observed hydrolytic degradation rate of PAA-Cy2 in a pH 7.4 tris(hydroxymethyl)aminomethane (TRIS) buffer was comparable to that of conventional amphoteric PAAs, that is, PAAs containing carboxyl groups in their repeating unit. Degradation experiments carried out in the presence of 2-mercaptoethanol with both PAAs demonstrated that the disulfide groups contained in its repeating units were susceptible to reductive cleavage in the presence of thiols. (c) 2005 Wiley Periodicals, Inc.