Sibik Juraj, Sargent Michael J, Franklin Miriam, Zeitler J Axel
Department of Chemical Engineering and Biotechnology, University of Cambridge , New Museums Site, Pembroke Street, Cambridge CB2 3RA, United Kingdom.
Mol Pharm. 2014 Apr 7;11(4):1326-34. doi: 10.1021/mp400768m. Epub 2014 Mar 13.
For the case of paracetamol, we show how terahertz time-domain spectroscopy can be used to characterize the solid and liquid phase dynamics. Heating of supercooled amorphous paracetamol from 295 K in a covered sample under vacuum leads to its crystallization at 330 K. First, form III is formed followed by the transformation of form III to form II at 375 K, to form I at 405 K, and finally melting is observed around 455 K. We discuss the difference between the featureless spectra of the supercooled liquid and its liquid melt. Lastly, we studied the onset of crystallization from the supercooled liquid in detail and quantified its kinetics based on the Avrami-Erofeev model. We determined an effective rate constant of k = 0.056 min(-1) with a corresponding onset of crystallization at T = 329.5 K for a heating rate of 0.4 K min(-1).
对于扑热息痛的情况,我们展示了太赫兹时域光谱如何用于表征固相和液相动力学。在真空中覆盖样品的条件下,将过冷无定形扑热息痛从295K加热,会导致其在330K结晶。首先形成III型,随后在375K时III型转变为II型,在405K时转变为I型,最后在455K左右观察到熔化。我们讨论了过冷液体与其液体熔体的无特征光谱之间的差异。最后,我们详细研究了过冷液体的结晶起始,并基于阿弗拉米-埃罗费耶夫模型对其动力学进行了量化。对于0.4K min⁻¹的加热速率,我们确定有效速率常数k = 0.056 min⁻¹,相应的结晶起始温度为T = 329.5K。