Moon Hye Kyoung, Choi Yong Seok, Lee Jin-Kook, Ha Chang-Sik, Lee Won-Ki, Gardella Joseph A
Department of Polymer Science and Engineering, Pusan National University, Busan 609-735, Korea.
Langmuir. 2009 Apr 21;25(8):4478-83. doi: 10.1021/la8032435.
In this study, two biodegradable polymers, poly(trimethylene carbonate) (PTMC) and poly(L-lactide) (PLLA) along with a series of PTMC/PLLA blends, were used as spreading materials to form LB monolayers at the air/water interface to study hydrolytic reaction kinetics of the monolayers with the Langmuir film balance technique. The pi-A isotherms of each homopolymer and their blends showed that blends of PTMC and PLLA were miscible on the neutral subphase (pH 7.4), whereas there was evidence of phase separation on the basic subphase (pH 10.7). The hydrolysis behavior of each homopolymer was investigated at these two different pH conditions. The PTMC monolayer showed faster hydrolysis on the neutral subphase (pH 7.4) than on the basic subphase (pH 10.7). However, in the case of the PLLA monolayer, the hydrolysis on the basic subphase is faster than that on the neutral subphase. On the basis of this result, hydrolysis mechanisms of PTMC and PLLA, considering a general hydrolysis mechanism and their stereo structures, are proposed. The hydrolysis rates of blends of PTMC and PLLA were much faster than that of each homopolymer on the basic subphase (pH 10.7). This result, which can be explained by a "dilution effect", was supported by the structure based mechanism proposed here.
在本研究中,两种可生物降解聚合物,聚碳酸三亚甲基酯(PTMC)和聚(L-丙交酯)(PLLA)以及一系列PTMC/PLLA共混物,被用作铺展材料以在空气/水界面形成LB单分子层,从而用Langmuir膜天平技术研究单分子层的水解反应动力学。每种均聚物及其共混物的π-A等温线表明,PTMC和PLLA的共混物在中性亚相(pH 7.4)上是可混溶的,而在碱性亚相(pH 10.7)上有相分离的迹象。在这两种不同的pH条件下研究了每种均聚物的水解行为。PTMC单分子层在中性亚相(pH 7.4)上的水解比在碱性亚相(pH 10.7)上更快。然而,对于PLLA单分子层,碱性亚相上的水解比中性亚相上的更快。基于这一结果,考虑到一般水解机理及其立体结构,提出了PTMC和PLLA的水解机理。在碱性亚相(pH 10.7)上,PTMC和PLLA共混物的水解速率比每种均聚物的水解速率快得多。这一结果可以用“稀释效应”来解释,此处提出的基于结构的机理支持了这一结果。