Biao Jin, Ying Chen, Harley Pyles, Marcel D. Baer, Benjamin A. Legg, Zheming Wang, Nancy M. Washton, Karl T. Mueller, David Baker, Gregory K. Schenter, Christopher J. Mundy, James J. De Yoreo
{"title":"生物碳酸钙致密液相的形成、化学演变和凝固","authors":"Biao Jin, Ying Chen, Harley Pyles, Marcel D. Baer, Benjamin A. Legg, Zheming Wang, Nancy M. Washton, Karl T. Mueller, David Baker, Gregory K. Schenter, Christopher J. Mundy, James J. De Yoreo","doi":"10.1038/s41563-024-02025-5","DOIUrl":null,"url":null,"abstract":"<p>Metal carbonates, which are ubiquitous in the near-surface mineral record, are a major product of biomineralizing organisms and serve as important targets for capturing anthropogenic CO<sub>2</sub> emissions. However, pathways of carbonate mineralization typically diverge from classical predictions due to the involvement of disordered precursors, such as the dense liquid phase (DLP), yet little is known about DLP formation or solidification processes. Using in situ methods we report that a highly hydrated bicarbonate DLP forms via liquid–liquid phase separation and transforms into hollow hydrated amorphous CaCO<sub>3</sub> particles. Acidic proteins and polymers extend DLP lifetimes while leaving the pathway and chemistry unchanged. Molecular simulations suggest that the DLP forms via direct condensation of solvated Ca²<sup>+</sup><span>⋅</span>(HCO<sub>3</sub><sup>−</sup>)<sub>2</sub> complexes that react due to proximity effects in the confined DLP droplets. Our findings provide insight into CaCO<sub>3</sub> nucleation that is mediated by liquid–liquid phase separation, advancing the ability to direct carbonate mineralization and elucidating an often-proposed complex pathway of biomineralization.</p>","PeriodicalId":19058,"journal":{"name":"Nature Materials","volume":"13 1","pages":""},"PeriodicalIF":37.2000,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Formation, chemical evolution and solidification of the dense liquid phase of calcium (bi)carbonate\",\"authors\":\"Biao Jin, Ying Chen, Harley Pyles, Marcel D. Baer, Benjamin A. Legg, Zheming Wang, Nancy M. Washton, Karl T. Mueller, David Baker, Gregory K. Schenter, Christopher J. Mundy, James J. De Yoreo\",\"doi\":\"10.1038/s41563-024-02025-5\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Metal carbonates, which are ubiquitous in the near-surface mineral record, are a major product of biomineralizing organisms and serve as important targets for capturing anthropogenic CO<sub>2</sub> emissions. However, pathways of carbonate mineralization typically diverge from classical predictions due to the involvement of disordered precursors, such as the dense liquid phase (DLP), yet little is known about DLP formation or solidification processes. Using in situ methods we report that a highly hydrated bicarbonate DLP forms via liquid–liquid phase separation and transforms into hollow hydrated amorphous CaCO<sub>3</sub> particles. Acidic proteins and polymers extend DLP lifetimes while leaving the pathway and chemistry unchanged. Molecular simulations suggest that the DLP forms via direct condensation of solvated Ca²<sup>+</sup><span>⋅</span>(HCO<sub>3</sub><sup>−</sup>)<sub>2</sub> complexes that react due to proximity effects in the confined DLP droplets. Our findings provide insight into CaCO<sub>3</sub> nucleation that is mediated by liquid–liquid phase separation, advancing the ability to direct carbonate mineralization and elucidating an often-proposed complex pathway of biomineralization.</p>\",\"PeriodicalId\":19058,\"journal\":{\"name\":\"Nature Materials\",\"volume\":\"13 1\",\"pages\":\"\"},\"PeriodicalIF\":37.2000,\"publicationDate\":\"2024-10-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nature Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1038/s41563-024-02025-5\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nature Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1038/s41563-024-02025-5","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Formation, chemical evolution and solidification of the dense liquid phase of calcium (bi)carbonate
Metal carbonates, which are ubiquitous in the near-surface mineral record, are a major product of biomineralizing organisms and serve as important targets for capturing anthropogenic CO2 emissions. However, pathways of carbonate mineralization typically diverge from classical predictions due to the involvement of disordered precursors, such as the dense liquid phase (DLP), yet little is known about DLP formation or solidification processes. Using in situ methods we report that a highly hydrated bicarbonate DLP forms via liquid–liquid phase separation and transforms into hollow hydrated amorphous CaCO3 particles. Acidic proteins and polymers extend DLP lifetimes while leaving the pathway and chemistry unchanged. Molecular simulations suggest that the DLP forms via direct condensation of solvated Ca²+⋅(HCO3−)2 complexes that react due to proximity effects in the confined DLP droplets. Our findings provide insight into CaCO3 nucleation that is mediated by liquid–liquid phase separation, advancing the ability to direct carbonate mineralization and elucidating an often-proposed complex pathway of biomineralization.
期刊介绍:
Nature Materials is a monthly multi-disciplinary journal aimed at bringing together cutting-edge research across the entire spectrum of materials science and engineering. It covers all applied and fundamental aspects of the synthesis/processing, structure/composition, properties, and performance of materials. The journal recognizes that materials research has an increasing impact on classical disciplines such as physics, chemistry, and biology.
Additionally, Nature Materials provides a forum for the development of a common identity among materials scientists and encourages interdisciplinary collaboration. It takes an integrated and balanced approach to all areas of materials research, fostering the exchange of ideas between scientists involved in different disciplines.
Nature Materials is an invaluable resource for scientists in academia and industry who are active in discovering and developing materials and materials-related concepts. It offers engaging and informative papers of exceptional significance and quality, with the aim of influencing the development of society in the future.