title: Superenantioselective chiral surface explosions.
abstract: Chiral inorganic materials predated life on Earth, and their enantiospecific surface chemistry may have played a role in the origins of biomolecular homochirality. However, enantiospecific differences in the interaction energies of chiral molecules with chiral surfaces are small and typically lead to modest enantioselectivities in adsorption, catalysis, and chemistry on chiral surfaces. To yield high enantioselectivities, small energy differences must be amplified by reaction mechanisms such as autocatalytic surface explosions which have nonlinear kinetics. Herein, we report the first observations of superenantiospecificity resulting from an autocatalytic surface explosion reaction of a chiral molecule on a naturally chiral surface. R,R- and S,S-tartaric acid decompose via a vacancy-mediated surface explosion mechanism on Cu single crystal surfaces. When coupled with surface chirality, this leads to decomposition rates that exhibit extraordinarily high enantiospecificity. On the enantiomorphs of naturally chiral Cu(643)(R&S), Cu(17,5,1)(R&S), Cu(531)(R&S) and Cu(651)(R&S) single crystal surfaces, R,R- and S,S-tartaric acid exhibit enantiospecific decomposition rates that differ by as much as 2 orders of magnitude, despite the fact that the effective rates constants for decomposition differ by less than a factor of 2.
authors.affiliation: Department of Chemical Engineering, Carnegie Mellon University , 5000 Forbes Avenue, Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Gellman
authors.forename: Ye
authors.initials: Y
authors.lastname: Huang
authors.forename: Xu
authors.initials: X
authors.lastname: Feng
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Pushkarev
authors.forename: Brian
authors.initials: B
authors.lastname: Holsclaw
authors.forename: Bharat S
authors.initials: BS
authors.lastname: Mhatre
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D013237:Stereoisomerism; D013499:Surface Properties; D013644:Tartrates / Q000737:chemistry*
chemical_list: D013644:Tartrates; D002245:Carbon Dioxide; D003300:Copper; C029768:tartaric acid