Themed collection Editor's Choice – Serena DeBeer
Energy storage: pseudocapacitance in prospect
This question and its implications are discussed in detail.
Mechanisms of catalytic reduction of CO2 with heme and nonheme metal complexes
This critical review discusses the thermal and photocatalytic mechanisms of one-, two-, four-, six- and eight-electron reduction of CO2 with metal complex catalysts.
Electrochemical imaging of cells and tissues
This minireview summarizes the recent achievements of electrochemical imaging platforms to map cellular functions in biological specimens using electrochemical scanning nano/micro-probe microscopy and 2D chips containing microelectrode arrays.
Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy
Combined X-ray free-electron laser techniques pinpoints loci of intersections between potential energy surfaces of a photo-excited 3d transition-metal centered molecule.
Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
Pendent borane Lewis acids provide an avenue for changing a ligand's field strength through acid/base interactions; this strategy was highlighted within a series of biologically-relevant high spin iron hydrides.
Metal vs. ligand protonation and the alleged proton-shuttling role of the azadithiolate ligand in catalytic H2 formation with FeFe hydrogenase model complexes
Real-time spectroscopic observation of electron transfer-induced protonation reactivity elucidates the role of the second sphere basic site in a H2 evolution catalyst.
Origin of the overall water splitting activity of Ta3N5 revealed by ultrafast transient absorption spectroscopy
A detailed transient absorption spectroscopy study efficiently correlates charge carrier dynamics with the overall water splitting efficiency in Ta3N5 photocatalyst.
NosL is a dedicated copper chaperone for assembly of the CuZ center of nitrous oxide reductase
The Cu(I)-binding protein NosL functions specifically as an assembly factor for the unique CuZ centre of nitrous oxide reductase (N2OR).
Scrutinizing metal–ligand covalency and redox non-innocence via nitrogen K-edge X-ray absorption spectroscopy
A series of nitrogen K-edge XAS data obtained for coordination complexes of diverse transition metals is used to calibrate computational pre-edge peak energies and to afford estimates of metal–ligand covalencies. The approach is extended to probe an inner-sphere aminyl radical ligand.
One metal is enough: a nickel complex reduces nitrate anions to nitrogen gas
A nickel complex was found to be capable of stepwise reducing nitrate to dinitrogen gas using carbon monoxide as the reaction partner.
Heterodinuclear zinc and magnesium catalysts for epoxide/CO2 ring opening copolymerizations
Eight heterodinuclear catalysts comprising Zn(II) and Mg(II) metal centres show high activity and selectivity for CO2/epoxide ring-opening copolymerization. Detailed kinetic analyses are reported and a chain-shuttling mechanistic hypothesis proposed.
Controlling a burn: outer-sphere gating of hydroxylamine oxidation by a distal base in cytochrome P460
One amino acid makes the difference between a metalloenzyme and a metalloprotein in two otherwise effectively identical cytochrome P460s.
Studying the phosphoryl transfer mechanism of the E. coli phosphofructokinase-2: from X-ray structure to quantum mechanics/molecular mechanics simulations
Phosphofructokinases catalyze the ATP-dependent phosphorylation of fructose-6-phosphate and they are highly regulated.
Influence of intramolecular secondary sphere hydrogen-bonding interactions on cytochrome c oxidase inspired low-spin heme–peroxo–copper complexes
Structural/electronic influence of metalloenzyme-inspired synthetic heme–peroxo–copper models containing intramolecular hydrogen bonding interactions.
Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization
We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy2(bpm)(fod)6] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2-bipyrimidine).
X-ray Raman optical activity of chiral molecules
Resonant and off-resonant Raman Optical Activity signals in the X-ray regime (XROA) are predicted.
Direct observation of the intermediate in an ultrafast isomerization
Using a combination of two-dimensional infrared (2D IR) and variable temperature Fourier transform infrared (FTIR) spectroscopies the rapid structural isomerization of a five-coordinate ruthenium complex is investigated.
Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies
A combined experimental and theoretical approach reveals correlations of metal L-edge X-ray absorption energies to local charge and spin densities.
Engineering a bifunctional copper site in the cupredoxin fold by loop-directed mutagenesis
Loop directed mutagenesis leads to a cupredoxin withthe strongest copper–thiolate bond known to date, high reduction potential and imidazole binding properties.
Energetic insights into two electron transfer pathways in light-driven energy-converting enzymes
We report Em values of (bacterio-)chlorophylls for one-electron reduction in both electron-transfer branches of PbRC, PSI, and PSII.
C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex
The (photo) chemical oxidation of a (TAML)FeIII complex using outer-sphere oxidants results in valence tautomerisation and C–H activation governed by exogenous anions.
Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy
Complementary ultrafast techniques provide clear observation of charge hopping between metals in dinuclear complexes.