Suppr超能文献

有机晶体特有的双重生长模式依赖于介观液体前驱体。

A dual growth mode unique for organic crystals relies on mesoscopic liquid precursors.

作者信息

Yerragunta Manasa, Tiwari Akash, Chakrabarti Rajshree, Rimer Jeffrey D, Kahr Bart, Vekilov Peter G

机构信息

William A. Brookshire Department of Chemical and Biomolecular Engineering, University of Houston, 4226 Martin Luther King Blvd., Houston, TX, 77204-4004, USA.

Welch Center for Advanced Bioactive Materials Crystallization, University of Houston, 4226 M.L. King Blvd., Houston, TX, 77204-4004, USA.

出版信息

Commun Chem. 2024 Aug 28;7(1):190. doi: 10.1038/s42004-024-01275-3.

Abstract

Organic solvents host the synthesis of high-value crystals used as pharmaceuticals and optical devices, among other applications. A knowledge gap persists on how replacing the hydrogen bonds and polar attraction that dominate aqueous environments with the weaker van der Waals forces affects the growth mechanism, including its defining feature, whether crystals grow classically or nonclassically. Here we demonstrate a rare dual growth mode of etioporphyrin I crystals, enabled by liquid precursors that associate with crystal surfaces to generate stacks of layers, which then grow laterally by incorporating solute molecules. Our findings reveal the precursors as mesoscopic solute-rich clusters, a unique phase favored by weak bonds such as those between organic solutes. The lateral spreading of the precursor-initiated stacks of layers crucially relies on abundant solute supply directly from the solution, bypassing diffusion along the crystal surface; the direct incorporation pathway may, again, be unique to organic solvents. Clusters that evolve to amorphous particles do not seamlessly integrate into crystal lattices. Crystals growing fast and mostly nonclassically at high supersaturations are not excessively strained. Our findings demonstrate that the weak interactions typical of organic systems promote nonclassical growth modes by supporting liquid precursors and enabling the spreading of multilayer stacks.

摘要

有机溶剂可用于合成用作药物和光学器件等的高价值晶体。在用较弱的范德华力取代主导水性环境的氢键和极性吸引力后,对于其如何影响生长机制,包括晶体是经典生长还是非经典生长这一决定性特征,仍存在知识空白。在此,我们展示了初卟啉I晶体罕见的双重生长模式,这是由与晶体表面缔合以形成层堆叠的液体前体实现的,这些层堆叠随后通过并入溶质分子进行横向生长。我们的研究结果表明,前体是介观富溶质簇,这是一种受有机溶质之间等弱键青睐的独特相。由前体引发的层堆叠的横向扩展关键依赖于直接从溶液中获取的丰富溶质供应,绕过了沿晶体表面的扩散;直接并入途径可能同样是有机溶剂所特有的。演变成无定形颗粒的簇不会无缝融入晶格。在高过饱和度下快速且大多非经典生长的晶体不会受到过度应变。我们的研究结果表明,有机体系典型的弱相互作用通过支持液体前体并使多层堆叠得以扩展来促进非经典生长模式。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5c96/11358147/29cf48268851/42004_2024_1275_Fig1_HTML.jpg

文献AI研究员

20分钟写一篇综述,助力文献阅读效率提升50倍。

立即体验

用中文搜PubMed

大模型驱动的PubMed中文搜索引擎

马上搜索

文档翻译

学术文献翻译模型,支持多种主流文档格式。

立即体验