Hsieh Wei-Hsien, Cheng Wen-Ting, Chen Ling-Chun, Lin Shan-Yang
Department of Biotechnology and Pharmaceutical Technology, Yuanpei University of Medical Technology, Hsin Chu 30015, Taiwan, China.
Asian J Pharm Sci. 2018 May;13(3):212-219. doi: 10.1016/j.ajps.2017.12.001. Epub 2017 Dec 8.
Three thermal analytical techniques such as differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) using five heating rates, and DSC-Fourier Transform Infrared (DSC-FTIR) microspectroscopy using one heating rate, were used to determine the thermal characteristics and the dehydration process of aspartame (APM) hemihydrate in the solid state. The intramolecular cyclization process of APM anhydrate was also examined. One exothermic and four endothermic peaks were observed in the DSC thermogram of APM hemihydrate, in which the exothermic peak was due to the crystallization of some amorphous APM caused by dehydration process from hemihydrate to anhydride. While four endothermic peaks were corresponded to the evaporation of absorbed water, the dehydration of hemihydrate, the diketopiperazines (DKP) formation via intramolecular cyclization, and the melting of DKP, respectively. The weight loss measured in TGA curve of APM hemihydrate was associated with these endothermic peaks in the DSC thermogram. According to the Flynn-Wall-Ozawa (FWO) model, the activation energy of dehydration process within 100-150 °C was about 218 ± 11 kJ/mol determined by TGA technique. Both the dehydration and DKP formation processes for solid-state APM hemihydrate were markedly evidenced from the thermal-responsive changes in several specific FTIR bands by a single-step DSC-FTIR microspectroscopy.
采用差示扫描量热法(DSC)、五种升温速率的热重分析(TGA)以及一种升温速率的DSC-傅里叶变换红外(DSC-FTIR)显微光谱这三种热分析技术,来测定阿斯巴甜(APM)半水合物在固态下的热特性和脱水过程。还研究了APM无水物的分子内环化过程。在APM半水合物的DSC热重曲线上观察到一个放热峰和四个吸热峰,其中放热峰是由于半水合物脱水形成无水物过程中一些无定形APM结晶所致。而四个吸热峰分别对应于吸附水的蒸发、半水合物的脱水、通过分子内环化形成二酮哌嗪(DKP)以及DKP的熔化。APM半水合物TGA曲线中测得的失重与DSC热重曲线上的这些吸热峰相关。根据Flynn-Wall-Ozawa(FWO)模型,通过TGA技术测定在100 - 150°C范围内脱水过程的活化能约为218±11 kJ/mol。通过单步DSC-FTIR显微光谱法,从几个特定FTIR波段的热响应变化中明显证实了固态APM半水合物的脱水和DKP形成过程。