Enantiospecific Adsorption and Decomposition of Cysteine Enantiomers on the Chiral Cu{421}^R Surface

Abstract

A detailed understanding of the bonding and molecular geometry characteristics of amino acids on chiral surfaces is vital toward discovering new pathways in chiral chemistry. Saturated layers of d- and l-cysteine amino acids were chemisorbed onto a chiral Cu{421}R surface. Although very little difference was observed in the molecular orientation of the two enantiomers as observed with near-edge X-ray absorption fine structure, a large variation in the sulfur bond scission energy was measured using a high-resolution X-ray photoelectron spectroscopy thermal annealing sequence. As a result of this scission process, enantiomers of cysteine molecules completely dissociate into alaninate at temperatures separated by as much as 16 K or 0.06 eV which is one of the largest stereo effects observed on chiral metal surfaces.

l-Methionine-Zr complex supported on magnetic ZnFe2O4 as a novel, green, and efficient heterogeneous magnetic nanocatalyst for the synthesis of 1H-tetrazole and polyhydroquinoline derivatives

“…64 New peaks for N 1s and S 2s are observed from about 442 and 135 eV, respectively. 65 As expected, much smaller shifts are observed in the C 1s spectra as no carbon atoms are directly bonded to the Zr surface. 63 As a result, l -methionine-Zr has been successfully immobilized on the surface of the ZnFe 2 O 4 MNPs.…”

Chiral Surface and Geometry of Metal Nanocrystals

“…www.advmat.de www.advancedsciencenews.com favorable states are greatly dependent on the absolute configuration of both the molecule and kinked sites. [108,109,[118][119][120][121][122][123][124][125][126][127] In addition to theoretical approaches, molecular geometry can be probed by infrared (IR) absorption spectroscopy because vibrational modes in IR range can identify functional groups and their relative orientations to the binding site. The Gellman group observed differentiated IR peaks from R-3-methylcyclohexanone molecules on Cu(643) R and Cu(643) S surfaces, which suggests that the molecular orientation is enantioselective.…”

“…Enantioselective interaction at the molecular level, including molecular orientations on chiral high‐Miller‐index surfaces and their equilibrium chemical states, was investigated by theoretical prediction and spectroscopic analysis. Various attempts based on DFT and Monte Carlo simulations have predicted that the adsorption geometries of molecules at energetically favorable states are greatly dependent on the absolute configuration of both the molecule and kinked sites . In addition to theoretical approaches, molecular geometry can be probed by infrared (IR) absorption spectroscopy because vibrational modes in IR range can identify functional groups and their relative orientations to the binding site.…”

Dynamic Diastereomerism on Chiral Surfaces

“…The adsorption of amino acids has become an active area of research within the field of surface chirality, due to the close connection with biochemically and pharmaceutically important molecules . Studying amino acid adsorption on chiral surfaces has revealed various phenomena, including diastereomeric differences in local adsorption geometry, long-range order, and decomposition kinetics. − Alanine, in particular, as the smallest chiral amino acid, has attracted a lot of interest, and it has been studied with a variety of experimental and computational techniques. ,− …”