Tautomerism unveils a self-inhibition mechanism of crystallization
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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Feb 02, 2023
- Source ID
- 10.1038/s41467-023-35924-3
Entities
People
- Alastair Florence
- Christian Kisielowski
- Cristian A. Morales-rivera
- Francisco Hernandez
- Giannis Mpourmpakis
- Hector A. Calderon
- Huaping Mo
- Jeffrey D Rimer
- Qing Tu
- Sungil Hong
- Taimin Yang
- Vijay K. Srirambhatla
- Vraj P. Chauhan
- Weiwei Tang
- Xi Geng
- Xiang Kang
- Xiaodong Zou
Organizations
- Knut and Alice Wallenberg Foundation
- National Natural Science Foundation of China
- National Science Foundation
- Office of Naval Research
- Robert A. Welch Foundation
- Swedish Research Council
- United States Department of Energy