Tautomerism unveils a self-inhibition mechanism of crystallization
Tang, Weiwei and Yang, Taimin and Morales-Rivera, Cristian A. and Geng, Xi and Srirambhatla, Vijay K. and Kang, Xiang and Chauhan, Vraj P. and Hong, Sungil and Tu, Qing and Florence, Alastair J. and Mo, Huaping and Calderon, Hector A. and Kisielowski, Christian and Hernandez, Francisco C. Robles and Zou, Xiaodong and Mpourmpakis, Giannis and Rimer, Jeffrey D. (2023) Tautomerism unveils a self-inhibition mechanism of crystallization. Nature Communications, 14 (1). 561. ISSN 2041-1723 (https://doi.org/10.1038/s41467-023-35924-3)
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Abstract
Modifiers are commonly used in natural, biological, and synthetic crystallization to tailor the growth of diverse materials. Here, we identify tautomers as a new class of modifiers where the dynamic interconversion between solute and its corresponding tautomer(s) produces native crystal growth inhibitors. The macroscopic and microscopic effects imposed by inhibitor-crystal interactions reveal dual mechanisms of inhibition where tautomer occlusion within crystals that leads to natural bending, tunes elastic modulus, and selectively alters the rate of crystal dissolution. Our study focuses on ammonium urate crystallization and shows that the keto-enol form of urate, which exists as a minor tautomer, is a potent inhibitor that nearly suppresses crystal growth at select solution alkalinity and supersaturation. The generalizability of this phenomenon is demonstrated for two additional tautomers with relevance to biological systems and pharmaceuticals. These findings offer potential routes in crystal engineering to strategically control the mechanical or physicochemical properties of tautomeric materials.
ORCID iDs
Tang, Weiwei, Yang, Taimin, Morales-Rivera, Cristian A., Geng, Xi, Srirambhatla, Vijay K. ORCID: https://orcid.org/0000-0002-4492-7567, Kang, Xiang, Chauhan, Vraj P., Hong, Sungil, Tu, Qing, Florence, Alastair J. ORCID: https://orcid.org/0000-0002-9706-8364, Mo, Huaping, Calderon, Hector A., Kisielowski, Christian, Hernandez, Francisco C. Robles, Zou, Xiaodong, Mpourmpakis, Giannis and Rimer, Jeffrey D.;-
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Item type: Article ID code: 84066 Dates: DateEventDecember 2023Published2 February 2023Published Online9 January 2023Accepted14 November 2022SubmittedSubjects: Medicine > Pharmacy and materia medica > Pharmaceutical chemistry
Science > Chemistry
Technology > Chemical engineeringDepartment: Faculty of Science > Strathclyde Institute of Pharmacy and Biomedical Sciences Depositing user: Pure Administrator Date deposited: 07 Feb 2023 16:15 Last modified: 05 Dec 2024 01:21 URI: https://strathprints.strath.ac.uk/id/eprint/84066