Laccases are multicopper oxidases which oxidize a wide variety of aromatic compounds with the concomitant reduction of oxygen to water as by-product. Due to their high stability and biochemical versatility, laccases are key enzymes to be used as eco-friendly biocatalyst in biotechnological applications. The presence of copper paramagnetic species in the catalytic site paired with the substrate radical species produced in the catalytic cycle makes laccases particularly attractive to be studied by spectroscopic approaches. In this review, the potentiality of a combined multifrequency electron paramagnetic spectroscopy /computational approach to gain information on the nature of the catalytic site and radical species is presented. The knowledge at molecular level of the enzyme oxidative process can be of great help to model new enzymes with increased efficiency and robustness.
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http://dx.doi.org/10.1007/s00018-014-1825-7 | DOI Listing |
J Org Chem
January 2025
Faculty of Science, Kunming University of Science and Technology, Jingming South Road 727, Chenggong District, Kunming 650500, P. R. China.
A novel silver-catalyzed cascade radical isonitrile insertion and defluorinative cyclization have been developed to synthesize CFH- and phosphinoyl-containing quinolines from -isocyanyl α-trifluoromethylstyrenes. The reaction proceeded under redox-neutral conditions and allowed the construction of a highly attractive quinoline ring system, with the simultaneous formation of the CFH group and introduction of various phosphinoyl groups in a single transformation, showing operational simplicity, a wide substrate scope, good tolerance for functional groups, and remarkable atom-/stepeconomy. Mechanistic studies indicated that the reaction is likely to involve the participation of P-centered radicals and key carbanion intermediates.
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, and Discipline of Intelligent Instrument and Equipment, Xiamen University, Xiamen 361005, P. R. China.
ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes and capacity to offer novel reactivity and selectivity, represents an emerging field in organic chemistry that addresses the growing demands for environmental sustainability and synthetic efficiency. This synergistic approach permits access to a wider range of redox potentials, facilitates redox transformations under gentler electrode potentials, and decreases the use of external harsh redox reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we and others reported the first examples of modern molecular photoelectrocatalysis.
View Article and Find Full Text PDFEur J Inorg Chem
May 2024
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
Lytic polysaccharide monooxygenases (LPMOs) are Cu-dependent metalloenzymes that catalyze the hydroxylation of strong C-H bonds in polysaccharides using O or HO as oxidants (monooxygenase/peroxygenase). In the absence of C-H substrate, LPMOs reduce O to HO (oxidase) and HO to HO (peroxidase) using proton/electron donors. This rich oxidative reactivity is promoted by a mononuclear Cu center in which some of the amino acid residues surrounding the metal might can accept and donate protons and/or electrons during O and HO reduction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Sichuan University, School of Chemistry, 29 Wangjiang Road, 610064, Chengdu, CHINA.
Electrocatalytic transfer alkyne semi-hydrogenation with H2O as hydrogen source is industrially promising for selective electrosynthesis of high value-added alkenes while inhibiting byproduct alkanes. Although great achievements, their development has remarkably restricted by designing atomically sophisticated electrocatalysts. Here, we reported single-crystalline mesoporous copper nanoplates (meso-Cu PLs) as a robust yet highly efficient electrocatalyst for selective alkene electrosynthesis from transfer semi-hydrogenation reaction of alkyne in H2O.
View Article and Find Full Text PDFFood Chem
January 2025
Department of Chemistry, College of Science, University of Sulaimani, Qliasan St., 46002 Sulaymaniyah, Kurdistan region, Iraq. Electronic address:
Chemically-synthesized Nanozymes that are widely used as alternatives to enzymes face challenges such as high precursor costs, complex preparation processes, and limited catalytic efficiency. To overcome these drawbacks, we introduce naturally derived nanozymes, nanomineralzymes, as a promising alternative, offering benefits like affordability, cost-effectiveness, and scalability. Chalcopyrite (CP, CuFeS) was sourced from a mineral deposit, and CP nanoparticles were produced by milling.
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