Recent advances in de novo designed metallopeptides as tailored enzyme mimics

Current Opinion in Chemical Biology, Journal Year: 2025, Volume and Issue: 86, P. 102586 - 102586

Published: March 21, 2025

Language: Английский

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Electrocatalytic CO₂ reduction by a cobalt porphyrin mini-enzyme

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Cobalt-mimochrome VI*a (CoMC6*a), a synthetic mini-enzyme with cobalt porphyrin active site, is developed as biomolecular catalyst for electrocatalytic CO2 reduction in water. The catalytic turnover number reaches ∼14 000 CO production selectivity of 86 : 5 over H2 under the same conditions. Varying applied potential and pK proton donor was used to gain insight into basis selectivity. protected site CoMC6*a proposed enhance conditions that typically favor by related catalysts. activity change only marginally air, indicating excellent oxygen tolerance.

Language: Английский

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Cu-Albumin Artificial Enzymes with Peroxidase and Oxidase Activity for Stereoselective Oxidations

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 16344 - 16352

Published: Oct. 22, 2024

We herein report a design of artificial enzymes by incorporating synthetic copper complex into noncatalytic bovine serum albumin (Cu-BSA) to carry out stereoselective oxidation. This Cu-BSA catalyst with stably bound Cu as cofactor shows peroxidase-like activity catalyze epoxidation styrene high chiral selectivity (>99%) R-styrene epoxide. With the electrochemical conversion Cu2+ Cu+, also exhibits oxidase-like selectively reduce oxygen hydrogen peroxide (H2O2), which can be combined its peroxidase function drive oxidation C═C bonds using air. enzymatic system holds promise for chiral-selective transformations non-natural substances and highlights versatility proteins in enzymes.

Language: Английский

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Hybrid Metal Catalysts as Valuable Tools in Organic Synthesis: An Overview of the Recent Advances in Asymmetric C─C Bond Formation Reactions

Molecules, Journal Year: 2024, Volume and Issue: 29(21), P. 5090 - 5090

Published: Oct. 28, 2024

Carbon–carbon bond formation represents a key reaction in organic synthesis, resulting paramount importance for constructing the carbon backbone of molecules. However, traditional metal-based catalysis, despite its advantages, often struggles with issues related to efficiency, selectivity, and sustainability. On other hand, while biocatalysis offers superior selectivity due an extraordinary recognition process substrate, scope applicable reactions remains somewhat limited. In this context, Artificial Metalloenzymes (ArMs) Metallo Peptides (MPs) offer promising not fully explored solution, merging two fields transition metal catalysis biotransformations, by inserting catalytically active cofactor into customizable protein scaffold or coordinating ion directly short tunable amino acid (Aa) sequence, respectively. As result, these hybrid catalysts have gained attention as valuable tools challenging catalytic transformations, providing systems new-to-nature properties synthesis. This review overview recent advances development ArMs MPs, focusing on their application asymmetric carbon–carbon bond-forming reactions, such carbene insertion, Michael additions, Friedel–Crafts cross-coupling cyclopropanation, underscoring versatility synthesizing biologically relevant compounds.

Language: Английский

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Structure Determination of Zinc and Cadmium Dication Complexes with Intact and Deprotonated Histidyl Glycine and Glycyl Histidine Dipeptides

The Journal of Physical Chemistry B, Journal Year: 2024, Volume and Issue: 128(45), P. 11134 - 11143

Published: Nov. 1, 2024

Metalated intact and deprotonated histidyl glycine glycyl histidine dipeptides were investigated in the gas phase by using infrared multiple photon dissociation (IRMPD) spectroscopy with light from a free-electron laser (FEL). The M2+(GlyHis), M2+(HisGly), [M(GlyHis-H)]+, [M(HisGly-H)]+, where M = Zn Cd, probed to elucidate how His position along peptide chain ligand charge state might influence structures observed phase. Simulated annealing calculations performed determine energetically low-lying conformers isomers of these structures. Quantum chemical used optimize at B3LYP level theory 6-311+G(d,p) def2-TZVP basis sets for zinc cadmium complexes, respectively. IRMPD calculated linear absorption spectra compared evaluate which are present. Relative energies various species evaluated single-point energy B3LYP, B3LYP-GD3BJ, ωB97XD, MP2(full) levels 6-311+G(2d,2p) def2-TZVPP sets. For all species, both metals mirror each other, those that reproduce experimental spectrum determined be iminol ligands or iminol-like ligands. Additionally, when dipeptides, change is correlated group deprotonated.

Language: Английский

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