Blasi Paolo, D'Souza Susan S, Selmin Francesca, DeLuca Patrick P
Dipartimento di Chimica e Tecnologia del Farmaco, Università degli Studi di Perugia, Via del Liceo, 1-06123 Perugia, Italy.
J Control Release. 2005 Nov 2;108(1):1-9. doi: 10.1016/j.jconrel.2005.07.009. Epub 2005 Aug 10.
The purpose of this research was to evaluate the effect and nature of hydration on the glass transition temperature (Tg) of poly(D,L-lactide-co-glycolide) and investigate the physical state of water within the polymer during hygrothermal aging. The polymer was incubated in water at 23, 30, 37 and 55 degrees C, while the vapor sorption studies were carried out at 37 degrees C using saturated salt solutions. The water content and the thermal behavior of PLGA-water system were assessed by Karl Fischer titration and modulated differential scanning calorimetry, respectively, the hygrothermal aging was monitored by gel permeation chromatography. Water depressed reversibly the Tg by about 15 degrees C regardless of the incubation conditions. The Tg then remained constant at approximately 30 degrees C for five days, except when degradation occurred. A broad ice melting peak was detected around 0 degrees C. In the sorption studies, a linear correlation (r2 0.9837) between the Tg and the moisture content was observed in the range of 0.3-2.6% w/w, but there was no discernible endothermic event associated with the melting of ice. Data were found to fit reasonably well to the Gordon-Taylor/Kelley-Bueche equation. There were no differences between bulk and vapor water aging. It is proposed that the water responsible for plasticizing the polymer was non-freezable (bound) water and the small fraction of such water which was absorbed at high relative humidity caused polymer degradation in the same manner as bulk water.
本研究的目的是评估水合作用对聚(D,L-丙交酯-共-乙交酯)玻璃化转变温度(Tg)的影响及性质,并研究在湿热老化过程中聚合物内部水的物理状态。将聚合物分别在23、30、37和55摄氏度的水中孵育,同时在37摄氏度下使用饱和盐溶液进行蒸汽吸附研究。通过卡尔费休滴定法和调制差示扫描量热法分别评估PLGA-水体系的含水量和热行为,通过凝胶渗透色谱法监测湿热老化。无论孵育条件如何,水均可使Tg可逆地降低约15摄氏度。然后,Tg在约30摄氏度下保持恒定五天,除非发生降解。在0摄氏度左右检测到一个宽的冰融化峰。在吸附研究中,在0.3-2.6% w/w范围内观察到Tg与水分含量之间存在线性相关性(r2 = 0.9837),但没有与冰融化相关的明显吸热事件。发现数据与Gordon-Taylor/Kelley-Bueche方程拟合得相当好。本体水老化和蒸汽水老化之间没有差异。有人提出,使聚合物增塑的水是不可冻结的(结合)水,并且在高相对湿度下吸收的一小部分这种水以与本体水相同的方式导致聚合物降解。