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甘氨酸相变的研磨方法

Grinding Method for Phase Transformation of Glycine.

作者信息

Kang Jeongki, Kim Jinsoo, Kim Woo-Sik

机构信息

Functional Crystallization Center, Department of Chemical Engineering (Integrated Engineering Program), Kyung Hee University, Yong-in, Gyeonggi-do 17104, South Korea.

Process Research Department, Research & Development Division, Yuhan Corporation, Yong-in, Gyeonggi-do 17084, South Korea.

出版信息

ACS Omega. 2023 May 4;8(19):17116-17121. doi: 10.1021/acsomega.3c01435. eCollection 2023 May 16.

Abstract

Glycine had three polymorphs, two metastable phases (α-glycine, β-glycine) and one stable phase (γ-glycine). However, the phase transformation of glycine from α-phase to γ-phase was well known as the kinetically unfavorable process. In this study, a simple and effective grinding method for phase transformation of glycine from α-phase to γ-phase is proposed. In an aqueous solution, α-glycine and γ-glycine had bulk solubilities of 180 and ∼172 g/L, respectively. According to the Ostwald-Freundlich equation, however, as the crystal size of α-glycine was reduced to ∼0.6 μm by grinding, the saturated concentration of α-glycine increased from 180 to 191 g/L. As long as the solution concentration exceeds a critical point (σ = 0.1), it can be possible to suddenly induce the nucleation of γ-glycine by grinding the α-glycine crystal in the solution. Subsequently, the complete transformation of α-phase to γ-phase was achieved without additives. Similarly, the grinding method was effective for producing the γ-glycine crystal in the cooling crystallization whereas the α-glycine crystal was always produced in the cooling crystallization without grinding. This study showed that physical grinding can effectively facilitate phase transformation by triggering the nucleation of stable polymorph.

摘要

甘氨酸有三种多晶型物,两种亚稳相(α-甘氨酸、β-甘氨酸)和一种稳定相(γ-甘氨酸)。然而,甘氨酸从α相到γ相的相变是众所周知的动力学不利过程。在本研究中,提出了一种将甘氨酸从α相转变为γ相的简单有效的研磨方法。在水溶液中,α-甘氨酸和γ-甘氨酸的本体溶解度分别为180和172 g/L。然而,根据奥斯特瓦尔德-弗伦德里希方程,通过研磨将α-甘氨酸的晶体尺寸减小至0.6μm时,α-甘氨酸的饱和浓度从180 g/L增加到191 g/L。只要溶液浓度超过临界点(σ = 0.1),通过在溶液中研磨α-甘氨酸晶体就有可能突然诱导γ-甘氨酸的成核。随后,在无添加剂的情况下实现了从α相到γ相的完全转变。同样,研磨方法在冷却结晶中对于生成γ-甘氨酸晶体是有效的,而在未研磨的冷却结晶中总是生成α-甘氨酸晶体。本研究表明,物理研磨可以通过触发稳定多晶型物的成核有效地促进相变。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ea8e/10193568/c0a02ab0ec07/ao3c01435_0002.jpg

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