Decoding the Biomimetic Mineralization of Metal-Organic Frameworks in Water

Shang Wei Lin, Phuc Khanh Lam, Chin Teng Wu, Kuan Hsuan Su, Chi Fang Sung, Sen Ruo Huang, Je Wei Chang, Orion Shih, Yi Qi Yeh, Trung Hieu Vo, Heng Kwong Tsao, Haw Ting Hsieh, U. Ser Jeng, Fa Kuen Shieh, Hsiao Ching Yang

研究成果: 雜誌貢獻期刊論文同行評審

3 引文 斯高帕斯(Scopus)

摘要

This study unveils the “green” metal-organic framework (MOF) structuring mechanism by decoding proton transfer in water during ZIF-8 synthesis. Combining in situ small- to wide-angle X-ray scattering, multiscale simulations, and quantum calculations, we reveal that the ZIF-8 early-stage nucleation and crystallization process in aqueous solution unfolds in three distinct stages. In stage I, imidazole ligands replace water in zinc-water cages, triggering an “acidity flip” that promotes proton transfer. This leads to the assembly of structures from single zinc ions to 3D amorphous cluster nuclei. In stage II, amorphous nuclei undergo a critical transformation, evolving into crystalline nuclei and subsequently forming mesoscale-ordered structures and crystallites. The process proceeds until the amorphous precursors are completely consumed, with the transformation kinetics governed by an energy barrier that determines the rate-limiting step. In stage III, stable crystallite nanoparticles form in solution, characterized by a temperature-dependent thermal equilibrium of molecular interactions at the crystal-solution interface. Beyond these core advancements, we explore the influence of encapsulated pepsin and nonencapsulated lysozyme on ZIF-8 formation, finding that their amino acid proton transfer capacity and concentration influence the resulting biomolecule-MOF composite’s shape and encapsulation efficiency. The findings contribute to understanding the molecular mechanisms behind biomimetic mineralization and have potential implications for engineering proteins within amorphous MOF nuclei as protein embryo growth sites.

原文???core.languages.en_GB???
頁(從 - 到)25170-25182
頁數13
期刊ACS Nano
18
發行號36
DOIs
出版狀態已出版 - 10 9月 2024

指紋

深入研究「Decoding the Biomimetic Mineralization of Metal-Organic Frameworks in Water」主題。共同形成了獨特的指紋。

引用此