Dynamic Spin-Controlled Enantioselective Catalytic Chiral Reactions

Metzger, Tzuriel S.; Siam, Reema; Kolodny, Yehoshua; Goren, Naama; Sukenik, Nir; Yochelis, Shira; Abu‐Reziq, Raed; Avnir, David; Paltiel, Yossi

doi:10.1021/acs.jpclett.1c01518

Cited by 26 publications

(29 citation statements)

References 32 publications

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“…This effect was observed in redox reactions that involve the transfer of spin-polarized electrons (8)(9)(10)(11). A magnetic catalyst has recently been used to make a product with asymmetric carbon when all the reactants are achiral (12).…”

Section: Introductionmentioning

confidence: 99%

Spin-induced asymmetry reaction—The formation of asymmetric carbon by electropolymerization

et al. 2022

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We describe the spin polarization–induced chirogenic electropolymerization of achiral 2-vinylpyridine, which forms a layer of enantioenhanced isotactic polymer on the electrode. The product formed is enantioenriched in asymmetric carbon polymer. To confirm the chirality of the polymer film formed on the electrode, we also measured its electron spin polarization properties as a function of its thickness. Two methods were used: First, spin polarization was measured by applying magnetic contact atomic force microscopy, and second, magnetoresistance was assessed in a sandwich-like four-point contact structure. We observed high spin-selective electron transmission, even for a layer thickness of 120 nm. A correlation exists between the change in the circular dichroism signal and the change in the spin polarization, as a function of thickness. The spin-filtering efficiency increases with temperature.

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Section: Introductionmentioning

confidence: 99%

Spin-induced asymmetry reaction—The formation of asymmetric carbon by electropolymerization

et al. 2022

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“…We can see a manifestation of this in the recent electrochemistry experiments with a magnetized electrode, where the electron spin direction enantioselectively affects the redox behavior of a chiral ferrocene derivative, Ugi’s amine, and camphorsulfonic acid ( 27 , 28 ). Similarly, it has been shown that chiral centers can be enantioselectively formed by a solid-state catalytic reaction on a magnetized hematite (Fe 2 O 3 ) surface due to enantioselective reaction kinetics by the CISS effect ( 29 ).…”

Section: Enantioselective Reduction Chemistrymentioning

confidence: 99%

On the origins of life’s homochirality: Inducing enantiomeric excess with spin-polarized electrons

Ozturk

Sasselov

2022

Proc. Natl. Acad. Sci. U.S.A.

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Life as we know it is homochiral, but the origins of biological homochirality on early Earth remain elusive. Shallow closed-basin lakes are a plausible prebiotic environment on early Earth, and most are expected to have significant sedimentary magnetite deposits. We hypothesize that ultraviolet (200- to 300-nm) irradiation of magnetite deposits could generate hydrated spin-polarized electrons sufficient to induce enantioselective prebiotic chemistry. Such electrons are potent reducing agents that drive reduction reactions where the spin polarization direction can enantioselectively alter the reaction kinetics. Our estimate of this chiral bias is based on the strong effective spin-orbit coupling observed in the chiral-induced spin selectivity (CISS) effect, as applied to energy differences in reduction reactions for different isomers. In the original CISS experiments, spin-selective electron transmission through a monolayer of double-strand DNA molecules is observed at room temperature—indicating a strong coupling between molecular chirality and electron spin. We propose that the chiral symmetry breaking due to the CISS effect, when applied to reduction chemistry, can induce enantioselective synthesis on the prebiotic Earth and thus facilitate the homochiral assembly of life’s building blocks.

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“…Demonstration of the CISS effect using chiral molecules and its use in a variety of applications, including in enantioselection, , water splitting, , molecular spintronics, and biorecognition, is remarkable and is one of the most sought-after areas of research among academicians across the globe. The presence of structural asymmetry in the form of chirality in various biomolecules, such as DNA, proteins, and amino acids, leads to this observable effect when electrons pass through these molecules with a predefined quantization (of spin) axis.…”

Section: Introductionmentioning

confidence: 99%

CISS-Based Label-Free Novel Electrochemical Impedimetric Detection of UVC-Induced DNA Damage

2022

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In this work, we demonstrate chiral-induced spin selectivity (CISS)-based label-free electrochemical impedimetric detection of radiation-induced DNA damage using the electrons’ spin as a novel tool of sensing. For this, self-assembled monolayers (SAMs) of short ds-DNA (of length 7.14 nm) are prepared on arrays of multilayer thin film devices comprising a gold overlay (500 μm diameter with 10 nm thickness) on a nickel thin film (100 nm) fabricated by the physical vapor deposition technique. Subsequently, the SAMs of ds-DNA are exposed to ultraviolet C (UVC) radiation for a prolonged period of 8 h to induce structural perturbations in DNA. The susceptibility of DNA to radiation-induced damage was probed by recording the spin-dependent electrochemical impedimetric spectra, wherein a continuous sinusoidal wave of the amplitude of 10 mV was superimposed on DC bias in the frequency range of 100–105 Hz, with simultaneous spin injection through the attached DNA. The inherent correlation between the charge-transfer resistance (R ct) and the spin selectivity of electrons through DNA was taken into account for the detection of DNA damage for the first time with a limit of detection achieved up to 10 picomolar concentrations of DNA. As the spin-polarized electrons directly probe the structural symmetry, it is robust against perturbation from electronic signals usually found in conventional electrochemical biosensors.

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Dynamic Spin-Controlled Enantioselective Catalytic Chiral Reactions

Cited by 26 publications

References 32 publications

Spin-induced asymmetry reaction—The formation of asymmetric carbon by electropolymerization

Spin-induced asymmetry reaction—The formation of asymmetric carbon by electropolymerization

On the origins of life’s homochirality: Inducing enantiomeric excess with spin-polarized electrons

CISS-Based Label-Free Novel Electrochemical Impedimetric Detection of UVC-Induced DNA Damage

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