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Themed collection Bioinspired reactivity and coordination chemistry

24 items
Editorial

Bioinspired reactivity and coordination chemistry

Welcome to this issue of Dalton Transactions featuring the themed issue “Bioinspired reactivity and coordination chemistry”.

Graphical abstract: Bioinspired reactivity and coordination chemistry
Perspective

Small-molecule activation with iron porphyrins using electrons, photons and protons: some recent advances and future strategies

Substituted tetraphenyl Fe porphyrins are versatile molecular catalysts for the activation of small molecules (such as O2, H+ or CO2), which could lead to renewable energy storage, the direct production of fuels or new catalytic relevant processes.

Graphical abstract: Small-molecule activation with iron porphyrins using electrons, photons and protons: some recent advances and future strategies
From the themed collection: 2019 Frontier and Perspective articles
Perspective

Recent advances in bioinspired proton-coupled electron transfer

Fundamental aspects of PCET continue to attract attention. Understanding this reaction type is desirable for small-molecule activation and solar energy conversion.

Graphical abstract: Recent advances in bioinspired proton-coupled electron transfer
From the themed collection: 2019 Frontier and Perspective articles
Frontier

Coordination-induced structural changes of DNA-based optical and electrochemical sensors for metal ions detection

This article highlights the coordination-induced structural changes of DNA-based optical, electrochemical and optical–electrochemical-combined sensors for metal ions detection.

Graphical abstract: Coordination-induced structural changes of DNA-based optical and electrochemical sensors for metal ions detection
From the themed collection: 2019 Frontier and Perspective articles
Communication

Transfer of hydrosulfide from thiols to iron(II): a convenient synthetic route to nonheme diiron(II)–hydrosulfide complexes

The synthesis and reactivity of an unprecedented nonheme diiron(II)–hydrosulfide complex via Fe(II) mediated C–S bond cleavage of thiols.

Graphical abstract: Transfer of hydrosulfide from thiols to iron(ii): a convenient synthetic route to nonheme diiron(ii)–hydrosulfide complexes
Communication

Transformation of the hydride-containing dinitrosyl iron complex [(NO)2Fe(η2-BH4)] into [(NO)2Fe(η3-HCS2)]via reaction with CS2

Hydride-insertion reactivity of DNIC [(NO)2Fe(η2-BH4)] promotes the reductive transformation of CS2 into DNIC [(NO)2Fe(η3-HCS2)] featuring Fe 3dz2-to-HCS2 π* backbonding interaction.

Graphical abstract: Transformation of the hydride-containing dinitrosyl iron complex [(NO)2Fe(η2-BH4)]− into [(NO)2Fe(η3-HCS2)]−via reaction with CS2
Communication

Biophysical analysis of cancer stem cell-potent copper(II) coordination complexes

Copper(II) coordination complexes, 1 and 2, containing nonsteroidal anti-inflammatory drugs (NSAIDs) potently kill breast cancer stem cells (CSCs) and bulk breast cancer cells.

Graphical abstract: Biophysical analysis of cancer stem cell-potent copper(ii) coordination complexes
Paper

G-Quadruplex binding optimization by gold(III) insertion into the center of a porphyrin

Gold(III) porphyrins have a square planar geometry and an extra positive charge, compatible with stronger electrostatic and π-stacking interactions.

Graphical abstract: G-Quadruplex binding optimization by gold(iii) insertion into the center of a porphyrin
Open Access Paper

Restricted rotation of an Fe(CO)2(PL3)-subunit in [FeFe]-hydrogenase active site mimics by intramolecular ligation

Terminal ligand fixation by covalent linkage to the bridging bdt ligand hinders ligand rotations.

Graphical abstract: Restricted rotation of an Fe(CO)2(PL3)-subunit in [FeFe]-hydrogenase active site mimics by intramolecular ligation
Paper

Structure of sirohydrochlorin ferrochelatase SirB: the last of the structures of the class II chelatase family

The crystal structure of sirohydrochlorin ferrochelatase SirB was finally unveiled toward a consideration of the structural diversity of class II chelatases.

Graphical abstract: Structure of sirohydrochlorin ferrochelatase SirB: the last of the structures of the class II chelatase family
Paper

Biliverdin–copper complex at physiological pH

In physiological settings, biliverdin and Cu2+ build a paramagnetic complex with formal structure: radical cation/Cu1+ or radical anion/Cu3+.

Graphical abstract: Biliverdin–copper complex at physiological pH
Paper

In vitro cytotoxicity and in vivo zebrafish toxicity evaluation of Ru(II)/2-mercaptopyrimidine complexes

Ru(II)/2-mercaptopyrimidine complexes active against cancer cells did not present toxic effects during embryonic and larval development of zebrafish.

Graphical abstract: In vitro cytotoxicity and in vivo zebrafish toxicity evaluation of Ru(ii)/2-mercaptopyrimidine complexes
Paper

Hydrogenase biomimics containing redox-active ligands: Fe2(CO)4(μ-edt)(κ2-bpcd) with electron-acceptor 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) as a potential [Fe4–S4]H surrogate

The diiron centre and redox-active diphosphine are reduced in separate steps but there is little evidence of intramolecular electron transfer between the two.

Graphical abstract: Hydrogenase biomimics containing redox-active ligands: Fe2(CO)4(μ-edt)(κ2-bpcd) with electron-acceptor 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) as a potential [Fe4–S4]H surrogate
Paper

Molybdenum dinitrogen complex supported by a cyclohexane-based triphosphine ligand and dmpm

We report the first molybdenum dinitrogen complex supported by a cyclohexane-based triphosphine ligand.

Graphical abstract: Molybdenum dinitrogen complex supported by a cyclohexane-based triphosphine ligand and dmpm
Paper

Tuning a robust system: N,O zinc guanidine catalysts for the ROP of lactide

Four non-toxic, highly active and robust complexes have been used in the ring opening polymerisation of non-purifed lactide to substitute Sn(Oct)2.

Graphical abstract: Tuning a robust system: N,O zinc guanidine catalysts for the ROP of lactide
Paper

Insight into chalcogenolate-bound {Fe(NO)2}9 dinitrosyl iron complexes (DNICs): covalent character versus ionic character

The synthesis, characterization and transformation of the thermally unstable {Fe(NO)2}9 dinitrosyl iron complex (DNIC) [(OMe)2Fe(NO)2] (2) were investigated.

Graphical abstract: Insight into chalcogenolate-bound {Fe(NO)2}9 dinitrosyl iron complexes (DNICs): covalent character versus ionic character
Open Access Paper

The interaction of aluminum with catecholamine-based neurotransmitters: can the formation of these species be considered a potential risk factor for neurodegenerative diseases?

What are the molecular basis of the detrimental role of the aluminum ion within the catecholamine biosynthesis pathway?

Graphical abstract: The interaction of aluminum with catecholamine-based neurotransmitters: can the formation of these species be considered a potential risk factor for neurodegenerative diseases?
Paper

Physical properties, ligand substitution reactions, and biological activity of Co(III)-Schiff base complexes

A subset of fluorinated Co(III) Schiff base complexes was synthesized, and their structural, ligand exchange, and anticancer properties were investigated.

Graphical abstract: Physical properties, ligand substitution reactions, and biological activity of Co(iii)-Schiff base complexes
Open Access Paper

Dinuclear manganese(III) complexes with bioinspired coordination and variable linkers showing weak exchange effects: a synthetic, structural, spectroscopic and computation study

High-resolution HFEPR indicates weak exchange interactions between MnIII ions in agreement with DFT calculations.

Graphical abstract: Dinuclear manganese(iii) complexes with bioinspired coordination and variable linkers showing weak exchange effects: a synthetic, structural, spectroscopic and computation study
Open Access Paper

Monitoring H-cluster assembly using a semi-synthetic HydF protein

An artificial enzyme, incorporating an organometallic iron complex, is used to probe the activation mechanism of [FeFe] hydrogenase.

Graphical abstract: Monitoring H-cluster assembly using a semi-synthetic HydF protein
Paper

Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton reduction

N/S replacement in Ni-cyclam complexes highlights the importance of biologically relevant sulfur ligands in the CO2 and proton reduction.

Graphical abstract: Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton reduction
Paper

Role of 2nd sphere H-bonding residues in tuning the kinetics of CO2 reduction to CO by iron porphyrin complexes

A series of iron porphyrins that vary only in the distal H-bonding network exhibit turnover frequencies (TOFs) ranging from 1.0 s−1 to 103 s−1.

Graphical abstract: Role of 2nd sphere H-bonding residues in tuning the kinetics of CO2 reduction to CO by iron porphyrin complexes
Paper

Synthesis, structure, docking and cytotoxic studies of ferrocene–hormone conjugates for hormone-dependent breast cancer application

Ferrocene–estrogen conjugates can be recognized by ERα, suggesting that estrogens could serve as vectors to target specifically breast cancer cell lines.

Graphical abstract: Synthesis, structure, docking and cytotoxic studies of ferrocene–hormone conjugates for hormone-dependent breast cancer application
Paper

Mesoporous silica nanoparticles functionalised with a photoactive ruthenium(II) complex: exploring the formulation of a metal-based photodynamic therapy photosensitiser

A ruthenium(II) complex was loaded onto mesoporous silica nanoparticles and the phototherapeutic activity of the materials was tested in cancer cells.

Graphical abstract: Mesoporous silica nanoparticles functionalised with a photoactive ruthenium(ii) complex: exploring the formulation of a metal-based photodynamic therapy photosensitiser
24 items

About this collection

Coordination chemistry plays a fundamental role in many biological processes, from respiration and photosynthesis to protein folding. Biological systems exhibit formidable control over reactivity through the choice of metal, coordinating ligand set, and redox environment. The diversity offered by biological coordination chemistry has inspired inorganic chemists amongst others to design and develop a multitude of small molecule biomimetics for various applications, and study biological processes using inorganic tools. Guest edited by Kogularamanan Suntharalingam and Ulf-Peter Apfel, this themed issue seeks to highlight the area of bioinspired reactivity and coordination chemistry.

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