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空间限制对多晶和非晶形成的形成和稳定性的影响

The influence of space restriction on the formation and stability of polymorphic and amorphous forms
课程网址: http://videolectures.net/slonano07_godec_isr/  
主讲教师: Aljaž Godec
开课单位: 斯洛文尼亚国家化学研究所
开课时间: 2008-02-12
课程语种: 英语
中文简介:
从经典成核理论可知,只有形成关键核才能发生结晶。因此,必须有足够的空间来形成这种核。在目前的工作中,我们确定了在限制条件下从过饱和溶液中出现结晶相必须满足的理论标准(例如,由于将药物溶液截留到多孔基质中)。确定在限制条件下从无定形或亚稳态多晶相发生结晶的类似标准。从理论上证明,空间约束可以引起溶液或多晶型选择的玻璃化1。以这种方式形成的亚稳相可以通过空间限制有效地防止结晶成热力学上更稳定的产物。理论标准用硝苯地平实验测试,所述硝苯地平包埋在纳米多孔二氧化硅干凝胶基质中,平均孔径为2.5nm。热分析和X射线粉末衍射的结果表明,在干凝胶孔内形成的无定形硝苯地平在其化学稳定的温度区间内被保护免于结晶。通过差示扫描量热法和BET分析的组合,我们估计了可以在干凝胶中稳定的硝苯地平的总量。此外,通过计算显示,捕获到具有一定孔径的低温纳米多孔基质中允许选择性形成磺胺噻唑多晶型物。如果孔半径等于1.7nm,则从甲苯溶液中选择性地形成IV形式。如果孔半径小于1,4nm,则形成非晶相。
课程简介: It is known from the classical nucleation theory that crystallization can only occur if critical nuclei are formed. Thus, there has to be enough space available for the formation of such nuclei. In the present work, we determined theoretical criteria that have to be satisfied for the occurence of a crystalline phase from a supersaturated solution in confinement conditions (e. g. resulting from entrapment of a drug solution into a porous matrix). Similar criteria were determined for the occurence of crystallization from amorphous or metastable polymorphic phases in confinement conditions. It was shown theoretically that spati al constraint can cause vitrification from solution or polymorph selection1. Metastable phases, which are formed in this manner, can be effectively protected against crystallization into thermodynamically more stable products through space restriction. The theoretical criteria were tested experimentally with nifedipine entrapped into a nanoporous silica xerogel matrix with an average pore diameter of 2,5 nm. The results of thermal analysis and X-ray powder diffraction have shown that the amorphous nifedipine, formed inside the xerogel pores, is protected against crystallization in the temperature interval in which it is chemically stable. With a combination of differential scanning calorymetry and BET analysis we estimated the total amount of nifedipine that can be stabilized in the xerogel. Also, it was shown through calculations, that entrapment into a hypotetical nanoporous matrix with a certain pore size allows selective formation of sulfathiazole polymorphs. If the pore radius is equal to 1,7 nm, then form IV is formed selectively from a toluene solution. If the pore radius is less than 1,4 nm, an amorphous phase is formed.
关 键 词: 纳米技术; 结晶; 热分析
课程来源: 视频讲座网
最后编审: 2020-05-31:吴雨秋(课程编辑志愿者)
阅读次数: 45