Themed collection Spotlight Collection: Bioinorganic Chemistry

This review provides an overview of current knowledge and recent developments in the field of photolabile first-row transition metal–nitrosyl complexes, focusing on the structural and electronic properties, photoreactivity, photodissociation mechanisms, and therapeutic applications.

This review presents discrete metal complexes that catalyse or photocatalyse reactions within living cells or living organisms.

A mechanism involving O–O bond formation via radical coupling of two subunits is proposed for a dinuclear iron complex. The mechanism can proceed at low overpotentials and agrees with the experimental kinetics.

Engineered metalloproteins that mimic the active sites of natural copper metalloenzymes are used to systematically investigate the influence of aromatic residues within the secondary coordination sphere on reactivity.

A covalently linked Fe(III)porphyrin dimer-based paramagnetic sensory cavity is designed for an accurate detection and simultaneous identification of substrate binding inside or outside the paramagnetic cavity.

Supramolecular interaction of a Ru₁₅ oligomeric catalyst with polymeric carbon nitride forms CN_TM–Ru₁₅ hybrid system, achieving high photoelectrochemical water-splitting activity, enhanced stability, and >89% faradaic efficiency for O₂ at neutral pH.

The kinetics study herein experimentally demonstrates that an inner-sphere ET mechanism is involved in the conversion of triplet O₂ into a powerful oxidant by an RS–Fe complex. Hydrogen-bond donors are shown to destabilize the transition-state.

The present work outlines a general methodology for designing efficient catalytic machineries that can easily be tweaked to meet the demands of the target reactions.

Spectroscopy and kinetics are used to evaluate the role of the secondary coordination sphere in substrate/product binding as well as reactivity in the nitrification enzyme cytochrome P460.

Peak and half-peak potentials poorly approximate standard reduction potentials (E⁰), especially for compounds that dissociate upon reduction. We determine E⁰ of disulfides and show cysteine disulfide radical anion to be a powerful biological reductant.

Proton transfer in the membrane domain of complex I.

We illuminate that cytochrome c (Cyt c) directly interacts with amyloid-β (Aβ) and alters Aβ amyloidogenesis in a peroxide-dependent manner, which demonstrates its new role towards the amyloid pathology associated with Alzheimer's disease.

We repurposed the metal-binding site of a cupin superfamily protein into the 2-His-1-carboxylate facial triad, which is the common motifs in natural non-heme enzymes, to construct artificial metalloenzymes that can catalyze new-to-nature reactions.

A spectroscopic and computational study reveals that bulky electron-withdrawing imido substituents stabilize a rare S = 1 iron(IV)–bisimido complex with a pseudo doubly degenerate ground electronic structure, accounting for its facile HAT reactivity.

Binding of exogenous cyanide to the active site H-cluster in [FeFe] hydrogenase stabilizes new active-site states with an overoxidized diiron cofactor showing how σ-donor/π-acceptor interactions influence the electronic structure of metallocofactors.

Crystallographic, spectroscopic, and computational studies on diiron(II) hydride complexes reveal rapid hydride motions that cause major changes in the electronic structures of the iron sites.

An iridium(III) two-photon photosensitizer was demonstrated to effectively trigger melanoma cell death by a combination of ferroptosis and ICD, and also cause the systemic induction of an immune response.

A schematic reaction mechanism of C–C coupling reaction by engineered CYP450.

The synthesis of Mn^V and Cr^V nitride complexes of a pro-radical tetradentate bis-phenol bis-N-heterocyclic carbene ligand H₂L^C2O2 was investigated.

Herein, we have developed a hydrolytically stable biotinylated Pt(IV) complex conjugated with a histone deacetylase inhibitor (SAHA) as a multi-functional tumour targeted chemotherapeutic agent.

The dual-size-selective chelators py-macrodipa and py₂-macrodipa were investigated for their abilities to complex [¹¹¹In]In³⁺. These chelators form highly stable complexes of this diagnostic radiometal under mild radiolabeling conditions.

Frog M ferritins retain their cage assembly and encapsulated iron mineral in simulated gastric fluid. Fabrication with chitosan further enhanced the cage stability and iron retention capability of ferritins.

Methyl piperazine functionalized Pt(II) complexes with general formula L-PtCl were prepared, structurally characterized and studied for their in vitro mechanistic anticancer effect in pancreatic ductal adenocarcinoma cells.

Cyclometalated Ir(III) tetrazine complexes were developed to act as mitochondria-targeted photosensitizers for efficient two-photon photodynamic therapy.

Ru(II)–phosphine–mercapto complexes are cytotoxic against breast cancer cells.

Rare examples of trinuclear [Ni–N₂–M–N₂–Ni] core (M = Ca, Mg) with linear bridged dinitrogen ligands are reported in this work.

This study contrasts the Cu(II)/Ni(II)/Zn(II) complex stability of GroEL1 C-terminal domains: His-rich ABS (M. abscessus) and Glu/His-rich XEN (M. xenopi). ABS forms more stable complexes, favoring histidine over glutamic acid for metal ion binding.

Eu(III) and Tb(III) complexes with specific fluorescence-enhanced detection performance for Pb²⁺ ions. The Eu(III) complex exhibits the lowest detection limit for Pb²⁺ ions among the systems described.

Diverse [FeFe]-H₂ase mimics are available by cross-metathesis of [FeFe]-H₂ase mimics bearing a double bond in the ADT-bridge nitrogen moiety and vinylmetallocenes, vinyl half-sandwich, or octahedral Ir-complexes.

A monofunctional Pt(II) complex PtL induces DNA single-strand breaks in triple negative breast cancer and triggers lysosome-dependent cell death by modulating lysosomal function.

Don't waste good iron for nails (or good men for soldiers) but save it for treating cancer! The lipophilic Fe(III) chelator chlorquinaldol has the remarkable ability to transport iron across the cell membrane afford potent broad-spectrum in vitro anticancer activity against a panel of cancer cell lines.

The wtCC peptide exhibits a high metal binding ability. The catalytic activity of the nickel(II) complex is similar to that of the nickel complex of the native NiSOD fragment.

The anticancer antimetabolite, 5-fluorouracil (5-FU) is caged within a lipophilic Ru(II)-diphosphine (dppe) core in [Ru^II(dppe)₂(5-FU)]PF₆ (Ru-DPPE-5FU), and its therapeutic potential towards LN229 glioblastoma cells was evaluated.

Application of ferrocenium-containing sumanene buckybowl derivatives as innovative, effective, and selective anticancer agents is described.