文献类型：期刊文献

英文题名：Prediction of the phase diagram of liquid-liquid phase separation during crystallization via a molecular mechanism study

作者：Liu, Yanbo[1];Ouyang, Jinbo[4];Wei, Xuemei[3];Yu, Guoqi[3];Shen, Hualiang[3];Shen, Runpu[3];Zhang, Xin[1];Tang, Weiwei[1];Chen, Mingyang[1,2,5];Li, Kangli[1,2,5];Gong, Junbo[1,2]

机构：[1]Tianjin Univ, Sch Chem Engn & Technol, State Key Lab Chem Engn, Tianjin 300072, Peoples R China;[2]Zhejiang Inst Tianjin Univ, Shaoxing 312300, Zhejiang, Peoples R China;[3]Shaoxing Univ, Zhejiang Engn Res Ctr Fat soluble Vitamin, Shaoxing 312000, Zhejiang, Peoples R China;[4]East China Univ Technol, Jiangxi Prov Key Lab Polymer Micro Nano Mfg & Devi, Nanchang 330013, Peoples R China;[5]Tianjin Univ, Sch Chem Engn & Technol, Tianjin 300072, Peoples R China

年份：2023

卷号：387

外文期刊名：JOURNAL OF MOLECULAR LIQUIDS

收录：SCI-EXPANDED(收录号：WOS:001052907800001)、、EI(收录号：20233214490471)、Scopus(收录号：2-s2.0-85166471787)、WOS

基金：This work was financially supported by Opening Project of Zhejiang Engineering Research Center of Fat-soluble Vitamin (202204), Key Research and Development Project of Hebei 22372601D, Academic and Technical Leader Training Program for Major Disciplines in Jiangxi Province 20212BCJ23001, and Kangli Li thanks the Shaoxing People's Government for a supporting her post-doctoral research.

语种：英文

外文关键词：Oiling-out; Crystallization; Liquid-liquid phase separation; Phase diagram; Molecular cluster

外文摘要：Oiling-out is a unique liquid-liquid phase separation phenomenon in solution crystallization. The unknown microscopic mechanism of oiling-out makes it difficult to control and significantly reduces the separation efficiency. In this work, an adsorption-desorption mechanism of temperature-driven molecular clustering is proposed based on the configuration search and the transformation process monitoring of dimers. This mechanism indicates that the stable and sufficient solute dimers in the solvent is the key condition for inducing oiling-out, accompanied by the transformation among various dimer configurations. Based on this mechanism, a prediction method of oiling-out phase diagram has been established through configurational stability analysis and determination of the total energy-temperature curve. This prediction method has been successfully applied to five systems: pyraclostrobin, vanillin, ethyl vanillin, citric acid, and benzoic acid. Importantly, the purity of pyraclostrobin is increased from 42.76% to 99.32% with the assistance of the oiling-out phase diagram. These findings not only provide advanced insights into understanding and controlling oiling-out during crystallization, but also highlight the role that oiling-out plays in the molecular assembly process of crystal nucleation.