Enzyme engineering by molecular modelling and site-directed mutagenesis can be remarkably efficient. Directed enzyme evolution appears as a more general strategy for the isolation of catalysts as it can be applied to most chemical reactions in aqueous solutions. Selections, as opposed to screening, allow the simultaneous analysis of protein properties for sets of up to about 10(14) different proteins. These approaches for the parallel processing of molecular information 'Is the protein a catalyst?' are reviewed here in the case of selections based on the formation of a specific reaction product. Several questions are addressed about in vivo and in vitro selections for catalysis reported in the literature. Can the selection system be extended to other types of enzymes? Does the selection control regio- and stereo-selectivity? Does the selection allow the isolation of enzymes with an efficient turnover? How should substrates be substituted or mimicked for the design of efficient selections while minimising the number of chemical synthesis steps? Engineering sections provide also some clues to design selections or to circumvent selection biases. A special emphasis is put on the comparison of in vivo and in vitro selections for catalysis.
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http://dx.doi.org/10.1016/j.jbiotec.2004.03.032 | DOI Listing |
Nat Commun
December 2024
Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, China.
The emergence of single-atom catalysts offers exciting prospects for the green production of hydrogen peroxide; however, their optimal local structure and the underlying structure-activity relationships remain unclear. Here we show trace Fe, up to 278 mg/kg and derived from microbial protein, serve as precursors to synthesize a variety of Fe single-atom catalysts containing FeNO (1 ≤ x ≤ 4) moieties through controlled pyrolysis. These moieties resemble the structural features of nonheme Fe-dependent enzymes while being effectively confined on a microbe-derived, electrically conductive carbon support, enabling high-current density electrolysis.
View Article and Find Full Text PDFNat Commun
December 2024
Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, Hangzhou, China.
Natural enzymes feature distinctive second spheres near their active sites, leading to exquisite catalytic reactivity. However, incumbent synthetic strategies offer limited versatility in functionalizing the second spheres of heterogeneous catalysts. Here, we prepare an enzyme-mimetic single Co-N atom catalyst with an elaborately configured pendant amine group in the second sphere via 1,3-dipolar cycloaddition, which switches the oxygen reduction reaction selectivity from the 4e to the 2e pathway under acidic conditions.
View Article and Find Full Text PDFCurr Opin Chem Biol
December 2024
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210, USA; Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA. Electronic address:
Enzymes catalyze molecular reactions with remarkable efficiency and selectivity under mild conditions. Photoactivated enzymes make use of a light-absorbing chromophore to drive chemical transformations, ideally using sunlight as an energy source. The direct attachment of a chromophore to native enzymes is advantageous, as information on the underlying catalytic mechanisms can be obtained.
View Article and Find Full Text PDFJACS Au
December 2024
State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024, China.
Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields of pharmaceuticals, dyes, pesticides, functional materials, fertilizers, and explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge of fumes and waste acids, poor functional group tolerance, and tremendous purification difficulty, renders mild, efficient, and environmentally friendly nitration a formidable challenge. Herein, we develop a visible-light-driven biocompatible arene C-H nitration strategy with good efficiency and regioselectivity, marvelous substrate applicability and functional group tolerance, and wide application in scale-up synthesis, total synthesis, and late-stage functionalization.
View Article and Find Full Text PDFACS Cent Sci
December 2024
Department of Chemistry, Shanghai Stomatological Hospital & School of Stomatology, State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, P. R. China.
An efficient regiospecific co-assembly (RSCA) strategy is developed for general synthesis of mesoporous metal oxides with pore walls precisely decorated by highly dispersed noble metal nanocrystals with customized parameters (diameter and composition). It features the rational utilization of the specific interactions between hydrophilic molecular precursors, hydrophobic noble metal nanocrystals, and amphiphilic block copolymers, to achieve regiospecific co-assembly as confirmed by molecular dynamics simulations. Through this RSCA strategy, we achieved a controllable synthesis of a variety of functional mesoporous metal oxide composites (e.
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