Metal-Catalyzed Oxygenation Mechanisms

The endogenous metabolite hypochlorite activates indoleamine 2,3-dioxygenase-1 for catalysis: Functional and mechanistic implications

This paper identifies sodium hypochlorite as an endogenous activator of IDO1, revealing a hypohalous acid-dependent catalytic mechanism for L-Trp oxidation.

Self-S-sulfonation in a bacterial persulfide dioxygenase mediates thiol persulfide detoxification

This paper identifies a self-S-sulfonation mechanism in bacterial persulfide dioxygenase CstB that converts thiol persulfides to thiosulfate without sulfite release.

Influence of Primary Coordination Sphere on Anion Rebound Selectivity in Nonheme Fe Enzyme-Catalyzed C(sp3)-H Functionalization: A Comparative Experimental and Computational Study of EgtB and ACCO

This paper compares experimental and computational studies of EgtB and ACCO to understand how their coordination sphere affects anion rebound selectivity in nonheme Fe enzyme-catalyzed C(sp3)-H functionalization.

Non-Canonical Cytochrome P450 Enzymes in Nature

The paper identifies and characterizes non-canonical CYPs lacking the conserved cysteine ligand, revealing new ligands like serine and selenocysteine in microbial genomes.

Highly Stable Mn(V)-Nitrido and Nitrogen-Atom Transfer Reactivity within a De Novo Protein

This paper designs a de novo protein to stabilize a Mn(V)-nitrido complex and demonstrates its use in enantioselective aziridination with high turnover and enantiomeric ratio.

Low-barrier hydrogen-bond powers long-range radical transfer in the metal-free ribonucleotide reductase

This study identifies a low-barrier hydrogen bond as the key to long-range radical transfer in metal-free ribonucleotide reductase.

The Mycobacterium smegmatis bd-II terminal oxidase employs a 1 carboxylate shift mechanism

This study characterizes the Mycobacterium smegmatis bd-II terminal oxidase using biochemical and structural methods, revealing a 1 carboxylate shift mechanism for oxygen reduction.

Quantitative mapping of methionine sensitivity to oxidation in the copper-bound PcuC chaperone

The paper quantifies methionine oxidation sensitivity in apo- and Cu-bound PcuC using a methionine-specific probe, showing increased oxidation of coordinating methionines upon Cu binding.

Redox robustness drives LPMO evolution

This study investigates how evolutionary pressures shaped LPMO enzymes to enhance redox robustness through copper re-oxidation and radical scavenging mechanisms.

CURE-ating the substrate scope and functional residues of nonheme iron(II) α-ketoglutarate dependent hydroxylase BesE

This study investigates the substrate specificity and functional residues of the nonheme iron(II) α-ketoglutarate-dependent hydroxylase BesE using chemical synthesis and enzymology.

A New Interpretation for Oxygen Atom-Transfer Reactions for the Berg-Holm Oxo-Molybdenum Enzyme Model: Evidence for a Highly Active Oxygen Atom Transfer Acceptor

The paper reinterprets kinetic data for oxygen atom-transfer reactions in a molybdenum enzyme model, showing a highly reactive monoxomolybdenum(IV) complex with a much higher oxygen transfer rate.

Dynamic metal coordination controls chemoselectivity in radical halogenases

This study shows that dynamic metal coordination and a minimal hydrogen-bond network control chemoselectivity in radical halogenases.

High-Resolution X-ray Structure of Gln143Asn Manganese Superoxide Dismutase Captures Multiple Hydrogen Peroxide Binding Sites

The paper presents a high-resolution X-ray structure of a Gln143Asn MnSOD variant, revealing multiple H2O2 binding sites beyond the canonical LIG and PEO positions.

Role of glutamate 292 and lysine 331 in catalysis for the flavoenzyme (S)-6-hydroxynicotine oxidase from Shinella sp. HZN7

This study identifies Glu292 and Lys331 as critical residues in NctB's catalytic mechanism, showing that Glu292 optimizes Lys331's role in dioxygen activation despite lacking the conserved lysine found in other FAO enzymes.

Human mitochondrial ferritin exhibits highly unusual iron-O2 chemistry distinct from that of cytosolic ferritins

The paper shows mitochondrial ferritin uses a unique iron-O2 chemistry mechanism involving a conserved Tyr residue and mixed-valent ferroxidase centre, differing from cytosolic ferritin.

Unexpected Activities of CYP152 Peroxygenases towards Non-carboxylic Substrates Reveal Novel Substrate Recognition Mechanism and Catalytic Versatility

This study reveals that CYP152 peroxygenases can degrade aromatic pollutants without a carboxyl group, showing new substrate recognition and catalytic mechanisms.

The role of Tyr34 in proton-coupled electron transfer of human manganese superoxide dismutase

This study investigates the role of Tyr34 in MnSOD catalysis using neutron diffraction, X-ray spectroscopy, and quantum chemistry calculations, revealing its impact on proton-coupled electron transfer.

Unravelling an Efficient O2/Reductant-Dependent Catalytic Route in Heme Peroxygenases for Sustainable Applications

This paper identifies an O2/reductant-dependent catalytic pathway in heme peroxygenases that avoids H2O2-induced inactivation, enabling efficient and sustainable chemical transformations.

Sequential oxidation of L-lysine by a non-heme iron hydroxylase

The paper demonstrates sequential oxidation of L-lysine by a non-heme iron hydroxylase and computationally analyzes structural elements that enable this reactivity.

Double crossed? Structural and computational studies of an unusual crosslinked heme in Methylococcus capsulatus cytochrome P460

This study identifies a double crosslink between lysine and heme in Methylococcus capsulatus cytochrome P460 using structural biology and QM/MM simulations.

2.6-A resolution cryo-EM structure of a class Ia ribonucleotide reductase trapped with mechanism-based inhibitor N3CDP

This paper presents a 2.6-A resolution cryo-EM structure of E. coli class Ia RNR trapped with inhibitor N3CDP, revealing details of radical transfer and PCET mechanism.