The taming of oxygen: biocatalytic oxyfunctionalisations
The scope and limitations of oxygenases as catalysts for preparative organic synthesis is discussed.
Computational modelling of oxygenation processes in enzymes and biomimetic model complexes
With computational resources becoming more efficient and more powerful and at the same time cheaper, computational methods have become more and more popular for studies on biochemical and biomimetic systems.
Structural and redox requirements for the action of anti-diabetic vanadium compounds
The transformation of non-oxido VIV to oxido VIV species under physiological conditions is necessary for a vanadium compound to exhibit pharmacological anti-diabetic activity.
Ligand tuning of single-site manganese-based catalytic antioxidants with dual superoxide dismutase and catalase activity
A bio-inspired Mn(II) complex with a linear pentadentate ligand and an alternating NSNSN coordination displays excellent dual SOD/CAT-like antioxidant activity and good stability in aqueous environment.
Analysis of the residual alignment of a paramagnetic multiheme cytochrome by NMR
Agreement between the molecular alignment tensor and the combined effect of four hemes in a cytochrome, revealed by residual dipolar couplings.
Artificial heme-proteins: determination of axial ligand orientations through paramagnetic NMR shifts
An empirical equation, describing the relationship between paramagnetic shifts and axial ligand orientations has been applied to an artificial bis-histidine ferriheme-protein, in order to determine the geometry of the active site.
What does the Sr-substituted 2.1 Å resolution crystal structure of photosystem II reveal about the water oxidation mechanism?
The structure of the water oxidising complex in the Sr-substituted X-ray crystal structure of photosystem II and its differences relative to the Ca-containing system, have been rationalized by a density functional study.
New catalytic model systems of tyrosinase: fine tuning of the reactivity with pyrazole-based N-donor ligands
Two models of tyrosinase containing bidentate ligands with pyrazole moieties are synthesized and characterized with respect to their catalytic activity.
Spectroelectrochemistry of FeIII- and CoIII-mimochrome VI artificial enzymes immobilized on mesoporous ITO electrodes
UV-visible absorption spectroelectrochemistry elucidated the different redox behaviours of FeIII- and CoIII-mimochrome VI artificial enzymes, adsorbed on mesoporous conductive films of ITO.
Evidence that steric factors modulate reactivity of tautomeric iron–oxo species in stereospecific alkane C–H hydroxylation
The steric bulk of tetradentate ligands dictates the relative reactivity patterns of high valent iron oxido/hydroxido tautomers.
Stabilisation of μ-peroxido-bridged Fe(III) intermediates with non-symmetric bidentate N-donor ligands
Peroxide-bridged binuclear iron(III)-complexes based on bidentate ligands were identified as stable intermediates in the disproportionation of H2O2 by tris-homoleptic iron(II)-complexes.
Orbital contributions to CO oxidation in Mo–Cu carbon monoxide dehydrogenase
Orbital analysis provides new insight into the Mo/Cu CODH mechanism with a calculated reaction barrier in excellent agreement with experiment.
First- and second-sphere contributions to Fe(II) site activation by cosubstrate binding in non-heme Fe enzymes
Factors that lead to coordinative unsaturation in non-heme-Fe(II) enzymes include sterics, facial triad carboxylate H-bonding, and strong cosubstrate donor ligation.
H2O2 activation with biomimetic non-haem iron complexes and AcOH: connecting the g = 2.7 EPR signal with a visible chromophore
Mechanistic studies revealed a new S = 1/2 intermediate (λmax = 465 nm) in the reaction of electron-rich aminopyridine Fe(II) complexes with H2O2/HOAc.
Catalytic oxidation of alkanes by iron bispidine complexes and dioxygen: oxygen activation versus autoxidation
Organic substrates (specifically cis-1,2-dimethylcyclohexane, DMCH) are oxidized by O2 in the presence of iron(II)–bispidine complexes.
Hiking on the potential energy surface of a functional tyrosinase model – implications of singlet, broken-symmetry and triplet description
With regard to excitation by visible light, the low-lying triplet state appears to be an alternative for induction of biological hydroxylation activity.
Bromoperoxidase activity of amavadin dissected: a DFT investigation
Bromoperoxidase catalytic activity exerted by oxidated amavadin [V(HIDPA)2]− (HIDPA = 2,2′-(hydroxyimino) dipropionate) in mono- and bis-protonated forms has been investigated by DFT.
Probing kojic acid binding to tyrosinase enzyme: insights from a model complex and QM/MM calculations
We present a structural model of tyrosinase inhibited by kojic acid. The binding mode on the enzyme is refined by QM/MM calculations.
Shining light on integrity of a tetracobalt-polyoxometalate water oxidation catalyst by X-ray spectroscopy before and after catalysis
Survival test passed: the Co4-oxo core of a polyoxometalate facilitates water oxidation in aqueous solution and thus is of high interest in energy science. The molecule is indeed is a real catalyst surviving the reaction cycle without any detectable structural modification.
Access channel residues Ser315 and Asp137 in Mycobacterium tuberculosis catalase-peroxidase (KatG) control peroxidatic activation of the pro-drug isoniazid
Asp137 to Ser replacement in Mycobacterium tuberculosis KatG enlarges a substrate access channel greatly enhancing activation of the pro-drug isoniazid.
Mechanistic insight into halide oxidation by non-heme iron complexes. Haloperoxidase versus halogenase activity
This work presents the first detailed study on mechanistic aspects of halide oxidation by non-heme iron complexes.
Oxidation of water by a nonhaem diiron(IV) complex via proton-coupled electron transfer
A nonhaem (μ-oxo)diiron(IV) complex was found to oxidize water to a hydroxyl radical via PCET, instead of forming an O–O bond.
Catalytic and regiospecific extradiol cleavage of catechol by a biomimetic iron complex
Oxidative C–C bond cleavage of 3,5-di-tert-butylcatechol to 4,6-di-tert-butyl-2-pyrone takes place catalytically on biomimetic iron complexes of a urea-derived facial tridentate ligand.
Light driven water oxidation by a single site cobalt salophen catalyst
A cobalt(II) salophen complex enables water oxidation in photoactivated sacrificial cycles under visible light.
About this collection
This web theme, Guest Edited by Wesley R Browne (University of Groningen) and Ebbe Nordlander (Lund University), will showcase current achievements and future perspectives in this exciting field of research and is focused on highlighting the thriving field of bioinorganic and bioinspired oxidation chemistry. The collection is supported by the COST Action on Bioinorganic oxidation chemistry CM1003.