A5048633322- Metal-Catalyzed Oxygenation Mechanisms
- Synthesis and Catalytic Reactions
- Enzyme-mediated dye degradation
- Electrochemical Analysis and Applications
- Catalytic C–H Functionalization Methods
- Pharmacogenetics and Drug Metabolism
- Photochemistry and Electron Transfer Studies
- Electrocatalysts for Energy Conversion
- X-ray Diffraction in Crystallography
- Cancer Treatment and Pharmacology
- Catalytic Processes in Materials Science
- Metal complexes synthesis and properties
- Metalloenzymes and iron-sulfur proteins
- Chemical Reactions and Isotopes
- Crystallization and Solubility Studies
- Cyclopropane Reaction Mechanisms
- Advanced oxidation water treatment
- Advanced Nanomaterials in Catalysis
Xiamen University
2021-2024
Henan Normal University
2018
ConspectusThis Account describes the manner whereby nature controls Fenton-type reaction of O–O homolysis hydrogen peroxide and harnesses it to carry out various useful oxidative transformations in metalloenzymes. H2O2 acts as cosubstrate for heme-dependent peroxidases, P450BM3, P450SPα, P450BSβ, P450 decarboxylase OleT, well nonheme enzymes HppE copper-dependent lytic polysaccharide monooxygenases (LPMOs). Whereas heme peroxidases use Poulos-Kraut heterolytic mechanism activation, some...
Paclitaxel is a famous chemotherapeutic agent, but its microbial production poses long-standing challenge due to poor product selectivity. Taxadiene-5α-hydroxylase (CYP725A4) plays crucial role in the biosynthesis of paclitaxel, catalyzing oxidation taxadiene and iso-taxadiene. This process yields several products, including byproducts 5(12)-oxa-3(11)-cyclotaxane (OCT) 5(11)-oxa-3(11)-cyclotaxane (iso-OCT), as well target compound taxadien-5α-ol (T5OH). Despite extensive studies, molecular...
Exploring the catalytic promiscuity of enzymes is a longstanding challenge and current topic interest. Our group previously modified cytochrome P450BM3 monooxygenase to perform peroxygenase activity with assistance from rationally designed dual-functional small molecule (DFSM). However, DFSM-facilitated P450-H2O2 system showed limited peroxidase activity. On basis mechanistic analysis possible competitive oxidation pathways, present work applies protein engineering strategy mutating...
It is a great challenge to optionally access diverse hydroxylation products from given substrate bearing multiple reaction sites of sp3 and sp2 C-H bonds. Herein, we report the highly selective divergent alkylbenzenes by an engineered P450 peroxygenase driven dual-functional small molecule (DFSM). Using combinations various P450BM3 variants with DFSMs enabled more than half all possible hydroxylated each excellent regioselectivity (up >99 %), enantioselectivity % ee), high total turnover...
pH buffer plays versatile roles in both biology and chemistry. In this study, we unravel the critical role of accelerating degradation lignin substrate peroxidase (LiP) using QM/MM MD simulations nonadiabatic electron transfer (ET) proton-coupled (PCET) theories. As a key enzyme involved degradation, LiP accomplishes oxidation via two consecutive ET reactions subsequent C–C cleavage cation radical. The first one involves from Trp171 to active species Compound I, while second Differing common...
Abstract A new approach to generate 2,4,6‐trisubstituted pyridines was successfully developed based on the cyclization of α,β‐unsaturated oximes catalyzed by copper(I). The method takes advantage inherent properties pyridines. In this transformation, play dual roles in formation nucleophilic copper(II) enamide and as acceptor Michael addition.
Cluster-continuum model calculations were conducted to decipher the mechanism of water oxidation catalyzed by a mononuclear copper complex. Among various O-O bond formation mechanisms investigated in this study, most favorable pathway involved nucleophilic attack OH- onto .+ L-CuII -OH- intermediate. During such process, initial binding proximity would result spontaneous , leading OH⋅ radical and CuII species. The further coupling between was associated with barrier 14.8 kcal mol-1 H2 O2...
Abstract It is a great challenge to optionally access diverse hydroxylation products from given substrate bearing multiple reaction sites of sp 3 and 2 C−H bonds. Herein, we report the highly selective divergent alkylbenzenes by an engineered P450 peroxygenase driven dual‐functional small molecule (DFSM). Using combinations various P450BM3 variants with DFSMs enabled more than half all possible hydroxylated each excellent regioselectivity (up >99 %), enantioselectivity % ee ), high total...
The Cover Feature shows the mononuclear copper complex-catalyzed water oxidation proceeds via an H2O2 intermediate, which is further oxidized to O2. This process analogous reverse of O2 activation and reduction occurring in natural copper-dependent monooxygenase. present finding could have far-reaching implications on reactivity catalysis active site both synthetic biological systems. More information can be found Research Article by P. Wu et al.
pH plays versatile roles in both biology and chemistry. For instance, can regulate the long-range electron transfer (ET) many proteins. However, mechanistic basis of pH-dependent ET processes remain unclear. In this study, we unravel critical role accelerating lignin peroxidase (LiP) using QM/MM MD simulations nonadiabatic PCET theories. As a key enzyme involved degradation, LiP accomplishes one-electron oxidation via two consecutive reactions: first one involves from Trp171 to active...