Explosive enantiospecific decomposition of aspartic acid on Cu surfaces

Mhatre, Bharat S.; Dutta, Soham; Reinicker, Aaron; Karagoz, Burcu; Gellman, Andrew J.

doi:10.1039/c6cc06887a

Cited by 24 publications

(95 citation statements)

References 36 publications

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“…Differently from studies from Gellman's group, 24,25 we hypothesize that the NH 2 amine group is not interacting with the surface. In fact, since no contribution from the NH 2 group is visible in corresponding infrared data, we deduce that, at low coverage, its plane is parallel, or almost parallel, to the surface.…”

Section: Resultscontrasting

confidence: 78%

“…More recently, Gellman and co-workers have studied ASP films evaporated (in racemic mixture or as pure D or L enantiomers) in UHV conditions, to characterize the enantiomer nature of ASP molecules on chiral and achiral copper surfaces. 21,22,23,24,25 All these studies have in common the conclusion that ASP chemical form after adsorption on a surface depends on the film coverage. However, this form is different according to the substrate.…”

Section: Asp C 4 H 7 No 4 (mentioning

confidence: 99%

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Deciphering the Adsorption Mechanisms of RGD Subunits: l-Aspartic Acid on Cu(110)

et al. 2017

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In this work we present a detailed surface science characterization of L-Aspartic acid adsorption on a Cu(110) surface. Aspartic acid is one of the main components of the tri-peptide RGD (arginine-glycine-aspartic acid). We replaced the traditional sublimation method to obtain molecular films by dosing aspartic acid directly from an aqueous solution through an Electrospray Ionization (ESI) device. X-ray Photoelectron Spectroscopy (XPS) and Polarization Modulation Reflection Absorption Infra Red Spectroscopy (PM-RAIRS) evidenced different

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Section: Resultscontrasting

confidence: 78%

Section: Asp C 4 H 7 No 4 (mentioning

confidence: 99%

Deciphering the Adsorption Mechanisms of RGD Subunits: l-Aspartic Acid on Cu(110)

et al. 2017

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“…Aspartic acid adsorption on Cu(100), Cu(110) and Cu(111) revealed that on all three surfaces, Asp was adsorbed as a zwitterion ( -O2CCH(NH3 + )CH2CO2H) in the multilayer but as a doubly deprotonated anion ( -O2CCH(NH2)CH2CO2 -) in the monolayer. 29,42 Furthermore, Cu(111) is relevant as it is the structure of the terrace on the chiral Cu(643) R&S surfaces.…”

Section: Xps Of D-pro/cu(111)mentioning

confidence: 99%

“…The N 1s spectra (Figure 2, center panel) reveal a peak at 402.0 eV (blue dashed curve) in the multilayer that is assigned to the >NH2 + group 29 and is absent in the monolayer spectrum. Conversely, there is a peak at 399.5 eV in the monolayer spectrum (red curve) assigned to the >NH group 29 that is present but much less intense in the multilayer spectrum. This indicates that in the D-Pro multilayer, the imine group is protonated while in the monolayer, it is not.…”

Section: Xps Of D-pro/cu(111)mentioning

confidence: 99%

“…Naturally chiral surfaces have been used in the recent past to study enantiospecific phenomena such as adsorption energetics, reaction kinetics, adsorbate orientation, enantiomer separations, and enantiomer aggregation. [25][26][27][28][29][30] The rigidity of Pro has been employed in metal-catalyzed diastereoselective hydrogenation reactions to produce enantiopure hydrogenated products. [31][32][33][34] In these reaction schemes, Pro is used as a chiral auxiliary which forms an intermediate compound with the organic reactant.…”

Section: Introductionmentioning

confidence: 99%

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Enantiospecific equilibrium adsorption and chemistry of d‐/l‐proline mixtures on chiral and achiral Cu surfaces

Dutta

Gellman

2019

Chirality

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A fundamental understanding of the enantiospecific interactions between chiral adsorbates and understanding of their interactions with chiral surfaces is key to unlocking the origins of enantiospecific surface chemistry. Herein, the adsorption and decomposition of the amino acid proline (Pro) has been studied on the achiral Cu(110), Cu(111) surfaces and on the chiral Cu(643) R&S surfaces. Isotopically labelled 1-13 C-L-Pro has been used to probe the Pro decomposition mechanism and to allow mass spectrometric discrimination of D-Pro and 1-13 C-L-Pro when adsorbed as mixtures. On the Cu(111) surface, Xray photoelectron spectroscopy reveals that Pro adsorbs as an anionic species in the monolayer. On the chiral Cu(643) R&S surface, adsorbed Pro enantiomers decompose with non-enantiospecific kinetics. However, the decomposition kinetics were found to be different on the terraces versus the kinked steps. Exposure of the chiral Cu(643) R&S surfaces to a racemic gas phase mixture of D-Pro and 1-13 C-L-Pro resulted in the adsorption of a racemic mixture; i.e. adsorption is not enantiospecific. However, exposure to non-racemic mixtures of D-Pro and 1-13 C-L-Pro resulted in amplification of enantiomeric excess on the surface, indicative of homochiral aggregation of adsorbed Pro. During coadsorption, this amplification is observed even at very low coverages, quite distinct from the behaviour of other amino acids, which begin to exhibit homochiral aggregation only after reaching monolayer coverages. The equilibrium adsorption of D-Pro and 1-13 C-L-Pro mixtures on achiral Cu(110) did not display any aggregation, consistent with prior STM observations of DL-Pro/Cu(110). This demonstrates convergence between findings from equilibrium adsorption methods and STM experiments and corroborates formation of a 2D random solid solution.

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Near‐Enantiopure Trimerization of 9‐Ethynylphenanthrene on a Chiral Metal Surface

et al. 2020

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Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on‐surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9‐ethynylphenanthrene (9‐EP) upon annealing to 500 K on the chiral Pd3‐terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9‐EP propellers. The observed behavior strongly contrasts the reaction of 9‐EP on the chiral Pd1‐terminated PdGa{111} surfaces, where 9‐EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level.

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Explosive enantiospecific decomposition of aspartic acid on Cu surfaces

Cited by 24 publications

References 36 publications

Deciphering the Adsorption Mechanisms of RGD Subunits: l-Aspartic Acid on Cu(110)

Deciphering the Adsorption Mechanisms of RGD Subunits: l-Aspartic Acid on Cu(110)

Enantiospecific equilibrium adsorption and chemistry of d‐/l‐proline mixtures on chiral and achiral Cu surfaces

Near‐Enantiopure Trimerization of 9‐Ethynylphenanthrene on a Chiral Metal Surface

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