Enantioselective Separation on Naturally Chiral Metal Surfaces: <scp>d,l</scp>‐Aspartic Acid on Cu(3,1,17)R&amp;S Surfaces

Yun, Yongju; Gellman, Andrew J.

doi:10.1002/anie.201209025

Cited by 75 publications

(110 citation statements)

References 23 publications

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“…The first point to make is that the magnitudes of the enantiospecificities are all on the order of ∆∆ − E~1 S R des kJ mole −1 or ~0.3 RT at the temperature measured. To put this in perspective, an enantiospecificity of 1 kJ mole −1 corresponds to an enantiospecific difference of rate constants or equilibrium constants of ~35% at 300 K. This magnitude is consistent with other such measurements on naturally chiral metal surfaces: propylene oxide on Cu(6 4 3) R&S [16], lysine on Cu (3,1,17) R&S [20], and aspartic acid on Cu (3,1,17) R&S [21]. The greatest enantiospecific desorption energy measured to date is that of methyl lactate on Cu(6 4 3) R&S , ∆∆ ≈ E des 4 kJ mole −1 [30].…”

Section: Structure Sensitive Enantiospecific Adsorption On Cu(hkl) Randsupporting

confidence: 85%

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl)^R&S surfaces

Gellman

Huang

Koritnik

et al. 2016

J. Phys.: Condens. Matter

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The desorption kinetics of a chiral compound, R-3-methylcyclohexanone (R-3MCHO), have been measured on both enantiomers of seven chiral Cu(hkl) surfaces and on nine achiral Cu single crystal surfaces with surface structures that collectively span the various regions of the stereographic triangle. The naturally chiral surfaces have terrace-step-kink structures formed by all six possible combinations of the three low Miller index microfacets. The chirality of the kink sites is defined by the rotational orientation of the (1 1 1), (1 0 0) and (1 1 0) microfacets forming the kink. R-3MCHO adsorbs reversibly on these Cu surfaces and temperature programmed desorption has been used to measure its desorption energetics from the chiral kink sites. The desorption energies from the R- and S-kink sites are enantiospecific, [Formula: see text], on the chiral surfaces. The magnitude of the enantiospecificity is [Formula: see text] ≈ 1 kJ mol on all seven chiral surfaces. However, the values of [Formula: see text] are sensitive to elements of the surface structure other than just their sense of chirality as defined by the rotational orientation of the low Miller index microfacets forming the kinks; [Formula: see text] changes sign within the set of surfaces of a given chirality.

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Section: Structure Sensitive Enantiospecific Adsorption On Cu(hkl) Randsupporting

confidence: 85%

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl)^R&S surfaces

Gellman

Huang

Koritnik

et al. 2016

J. Phys.: Condens. Matter

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“…By using racemic mixtures of amino acids in which only one enantiomer was labeled by 13 C, a large contrast in rate constants of enantioselective binding was demonstrated on the chiral Cu surfaces. [115][116][117] 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 17 11 9S surface.…”

Section: Surface Chirality In Achiral Metal and Inorganicsmentioning

confidence: 99%

Chiral Surface and Geometry of Metal Nanocrystals

et al. 2019

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and their microscopic assembling and folding gradually give rise to chirality and left-right asymmetry from supramolecules to organelles, cells, and macroscopic organisms. Although the origin of homochirality is still unexplained and opens to arguments, investigating the chirality of matter and its origination is a central part of understanding asymmetric physical and chemical phenomena. The importance of chirality in chemistry lies in the asymmetric biochemical reactions with different physiological effect, which has paramount importance in biochemistry and pharmaceutical industry. [3,14,15] A mirror image of chiral objects can be determined into one of the left-handed or right-handed forms of geometry, called enantiomer or enantiomorph. Both enantiomers of a chiral object consist of identical chemical compositions but indeed are significantly different in their light-matter interaction, catalysis, and biological functions. The enantioselective signaling and enzymatic reaction are attributed to the homochirality of the living organism and its biological receptors, which are only composed of l-form amino acids and d-form sugars in nature. [7,14,15] Thalidomide is often referred to as a representative but also the most tragic example. The R-form of this drug is harmless to the body and was released as a painkiller for pregnant women, but its enantiomer causes severe malformation in the limbs of infants. [15,16] Since then, it has been a requirement for drugs to be characterized as a single enantiomer to be approved. 3D chirality is a unique characteristic of life, and the stereochemical aspect of molecular materials has come to fore of modern chemistry and biology. The optical property of chiral compounds, the so-called chiroptical effect, is highly effective for observing chirality in a nondestructive manner. [17] Chiroptical effects can be used for determination of the absolute configuration and enantiomeric excess of chiral molecules and as an optical probe for estimating the 3D structure of biomacromolecules such as proteins and DNA. [18] However, in most chiral organic molecules and biomolecules, chiroptical effects are typically very weak due to the much smaller size of molecules than the wavelength of exciting light. Integration of inorganic nanomaterials is one promising method for increasing the chiroptical signal of molecules; it focuses the light into nanoscale area to maximize the lightmatter interaction. [19-22] For example, a complex spatial profile Chirality is a basic property of nature and has great importance in photonics, biochemistry, medicine, and catalysis. This importance has led to the emergence of the chiral inorganic nanostructure field in the last two decades, providing opportunities to control the chirality of light and biochemical reactions. While the facile production of 3D nanostructures has remained a major challenge, recent advances in nanocrystal synthesis have provided a new pathway for efficient control of chirality at the nanoscale by transferring molecular chirality to the geo...

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“…Yun and Gellman demonstrated the impact of chiral surfaces on chiral amplification processes by reporting enantioselective separation of gas phase DL‐aspartic acid by equilibrium adsorption on naturally chiral metal Cu‐(3,1,17) R&S surfaces; the enantiospecific differences in adsorption energetic and reaction kinetics were considered to cause the enantiospecific interactions between chiral molecules and chiral surfaces.…”

Section: Auto‐amplification: Adsorption On An Achiral Surfacementioning

confidence: 99%

Enantioseparations in Achiral Environments and Chromatographic Systems

Martens

Bhushan

2016

Israel Journal of Chemistry

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Since the very first resolution of racemic tartaric acid by Pasteur, the importance of resolution and methodology has been on a path of continuous understanding and expansion. The science and chemistry of achieving such targets has changed a lot. The advent of chromatography changed the direction by involving synthetic, semisynthetic, or naturally occurring chiral materials for a direct approach to resolution, where rapid and reversible association occurs to form diastereomers with different stabilities and partition coefficients responsible for overall enantioseparation. It has now reached a stage where the separation of excess enantiomers from nonracemic mixtures has been achieved in a totally achiral environment, which does not appear to be in line with the prevalent concepts of basic stereochemistry. Caution should be exercised when enantiomerically enriched mixtures – obtained by enantioselective synthesis – are chromatographed for purification in preparative organic synthesis.

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Enantioselective Separation on Naturally Chiral Metal Surfaces: d,l‐Aspartic Acid on Cu(3,1,17)^R&S Surfaces

Cited by 75 publications

References 23 publications

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl)^R&S surfaces

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl)^R&S surfaces

Chiral Surface and Geometry of Metal Nanocrystals

Enantioseparations in Achiral Environments and Chromatographic Systems

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Enantioselective Separation on Naturally Chiral Metal Surfaces: d,l‐Aspartic Acid on Cu(3,1,17)R&S Surfaces

Cited by 75 publications

References 23 publications

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl) R&S surfaces

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl) R&S surfaces

Chiral Surface and Geometry of Metal Nanocrystals

Enantioseparations in Achiral Environments and Chromatographic Systems

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Enantioselective Separation on Naturally Chiral Metal Surfaces: d,l‐Aspartic Acid on Cu(3,1,17)^R&S Surfaces

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl)^R&S surfaces

Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl)^R&S surfaces