Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 25, Pages 8562-8569Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b03116
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Funding
- National Natural Science Foundation of China [21625105, 21571155]
- Fundamental Research Funds for the Central Universities of China [2012XZZX005]
- Excellent Doctoral Student Supporting Program of Zhejiang University
- U.S. Department of Energy by Lawrence Livermore National Laboratory [DE-AC52-07NA27344]
- Talent Program of Zhejiang University
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We herein show the chiral recognition and separation of aspartic acid (Asp) enantiomers by achiral brushite due to the asymmetries of their dynamical steps in its nonequilibrium states. Growing brushite has a higher adsorption affinity to d-Asp, while l-Asp is predominant on the dissolving brushite surface. Microstructural characterization reveals that chiral selection is mainly attributed to brushite [101] steps, which exhibit two different configurations during crystal growth and dissolution, respectively, with each preferring a distinct enantiomer due to this asymmetry. Because these transition step configurations have different stabilities, they subsequently result in asymmetric adsorption. By varying free energy barriers through solution thermodynamic driving force (i.e., supersaturation), the dominant nonequilibrium intermediate states can be switched and chiral selection regulated. This finding highlights that the dynamic steps can be vital for chiral selection, which may provide a potential pathway for chirality generation through the dynamic nature.
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