Chiral Metal Nanoparticles for Asymmetric Catalysis

Yasukawa, Tomohiro; Kobayashi, Shū

doi:10.1007/3418_2020_39

Cited by 8 publications

(6 citation statements)

References 132 publications

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“…4 However, considering the economic and environmental benefits, special attention is paid to the preparation of easily separable and recoverable heterogeneous catalysts. 5 The immobilization of organocatalysts could be accomplished by attaching to various inert supports such as silica gel, 6 polyethylene glycol, 7 Fe 3 O 4 , 8 ionic liquids, 9 etc. Nevertheless, heterogeneous catalysts often suffer from decreased catalytic activity and/or enantioselectivity.…”

Section: Introductionmentioning

confidence: 99%

A highly stereoselective and recyclable microgel-supported bifunctional sulfonamide organocatalyst for asymmetric alcoholysis of meso-cyclic anhydrides: a thermo-responsive “organic nanoreactor”

Xiong

Zhu

et al. 2022

New J. Chem.

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Section: Introductionmentioning

confidence: 99%

A highly stereoselective and recyclable microgel-supported bifunctional sulfonamide organocatalyst for asymmetric alcoholysis of meso-cyclic anhydrides: a thermo-responsive “organic nanoreactor”

Xiong

Zhu

et al. 2022

New J. Chem.

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“…The interaction between chiral nanostructures and natural chiral objects enhances the CD signal of the latter ones, making them observable in a wide range of the spectrum. Chiral nanoparticles are widely used in rapidly developing fields such as chiral sensing [ 10 , 11 ], biomolecular recognition [ 12 ], cell imaging [ 13 ], cytotoxicity control [ 14 ], design of circularly polarized light sources, asymmetric catalysis [ 15 ], and circular polarized luminescence (CPL) [ 16 ]. A variety of potential applications motivated the development of different ways of inducing chirality and synthesis chiral nanoparticles, especially in plasmonics, since plasmonic materials can effectively enhance weak signals due to their strong light–matter interaction [ 17 ].…”

Section: Introductionmentioning

confidence: 99%

Laser-Induced Chirality of Plasmonic Nanoparticles Embedded in Porous Matrix

Sapunova,

Yandybaeva,

Zakoldaev

et al. 2023

Nanomaterials

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Chiral plasmonic nanostructures have emerged as promising objects for numerous applications in nanophotonics, optoelectronics, biosensing, chemistry, and pharmacy. Here, we propose a novel method to induce strong chirality in achiral ensembles of gold nanoparticles via irradiation with circularly-polarized light of a picosecond Nd:YAG laser. Embedding of gold nanoparticles into a nanoporous silicate matrix leads to the formation of a racemic mixture of metal nanoparticles of different chirality that is enhanced by highly asymmetric dielectric environment of the nanoporous matrix. Then, illumination with intense circularly-polarized light selectively modifies the particles with the chirality defined by the handedness of the laser light, while their “enantiomers” survive the laser action almost unaffected. This novel modification of the spectral hole burning technique leads to the formation of an ensemble of plasmonic metal nanoparticles that demonstrates circular dichroism up to 100 mdeg. An unforeseen peculiarity of the chiral nanostructures obtained in this way is that 2D and 3D nanostructures contribute almost equally to the observed circular dichroism signals. Thus, the circular dichroism is neither even nor odd under reversal of direction of light propagation. These findings will help guide the development of a passive optical modulator and nanoplatform for enhanced chiral sensing and catalysis.

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“…Activity and selectivity in heterogeneous catalysis can be modulated through binding organic molecules to metal surfaces. − The modes of action include steric hindrance leading to the imposition of specific adsorption geometries, electron transfer modification of the electronic structure of the catalyst material, and direct attractive noncovalent bonding to reactant functional groups. Through the formation of a molecular environment on the catalyst surface, the approach mimics ligand-control in homogeneous catalysis .…”

Section: Introductionmentioning

confidence: 99%

Ligand-Assisted Carbonyl Bond Activation in Single Diastereomeric Complexes on Platinum

et al. 2022

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It is a significant challenge to relate ligand-assisted bond activation on metal surfaces to specific adsorption and intermolecular binding structures. To address this objective, we studied carbonyl bond activation in single chirality transfer complexes formed by methyl 3,3,3-trifluoropyruvate (i.e., MTFP) and (R)-1-(1-naphthyl)ethylamine (i.e., (R)-NEA) on a Pt(111) surface. The experiments combined reflectance absorbance infrared spectroscopy (RAIRS), scanning tunneling microscopy (STM), and density functional theory (DFT) methods. While STM measurements, in combination with DFT calculations, permit the study of single surface complexes, RAIRS is an ensemble technique that yields a composite spectrum resulting from an often heterogeneous distribution of molecular structures on the sampled surface. We show that the intrinsic thermal behavior of the MTFP/(R)-NEA/Pt(111) system facilitates meaningful comparison between single complex measurements by STM and ensemble measurements by RAIRS in that the vibrational signal can be attributed to a small number of complexation configurations, one of which has a high relative abundance. We take advantage of mode mixing in a ν(CF3) + ν(CO)keto vibration to detect a spectroscopic signature for complexation-induced carbonyl bond activation. A red-shift of the band correlates with DFT-predicted lengthening of the bridge-bonded carbonyl group. While the intensity of the shifted band is in the majority due to the most abundant complexation configuration, minority states produce line broadening. In addition to providing insight on rate-enhancement in enantioselective reactions on catalysts bearing chiral auxiliaries, the study contributes to the development of ligand control of reactivity and selectivity in heterogeneous catalysis.

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Chiral Metal Nanoparticles for Asymmetric Catalysis

Cited by 8 publications

References 132 publications

A highly stereoselective and recyclable microgel-supported bifunctional sulfonamide organocatalyst for asymmetric alcoholysis of meso-cyclic anhydrides: a thermo-responsive “organic nanoreactor”

A highly stereoselective and recyclable microgel-supported bifunctional sulfonamide organocatalyst for asymmetric alcoholysis of meso-cyclic anhydrides: a thermo-responsive “organic nanoreactor”

Laser-Induced Chirality of Plasmonic Nanoparticles Embedded in Porous Matrix

Ligand-Assisted Carbonyl Bond Activation in Single Diastereomeric Complexes on Platinum

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