Themed collection Editor's Choice – Serena DeBeer
Energy storage: pseudocapacitance in prospect
This question and its implications are discussed in detail.
Chem. Sci., 2019,10, 5656-5666
https://doi.org/10.1039/C9SC01662G
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.
Chem. Sci., 2018,9, 6017-6034
https://doi.org/10.1039/C8SC02220H
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.
Chem. Sci., 2018,9, 4546-4554
https://doi.org/10.1039/C8SC01035H
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.
Chem. Sci., 2019,10, 5749-5760
https://doi.org/10.1039/C8SC04023K
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.
Chem. Sci., 2019,10, 5539-5545
https://doi.org/10.1039/C9SC00561G
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.
Chem. Sci., 2019,10, 5582-5588
https://doi.org/10.1039/C9SC00876D
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.
Chem. Sci., 2019,10, 5353-5362
https://doi.org/10.1039/C9SC00217K
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).
Chem. Sci., 2019,10, 4985-4993
https://doi.org/10.1039/C9SC01053J
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.
Chem. Sci., 2019,10, 5044-5055
https://doi.org/10.1039/C8SC03350A
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.
Chem. Sci., 2019,10, 4767-4774
https://doi.org/10.1039/C9SC00717B
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.
Chem. Sci., 2019,10, 4618-4627
https://doi.org/10.1039/C9SC00385A
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.
Chem. Sci., 2019,10, 3756-3764
https://doi.org/10.1039/C9SC00195F
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.
Chem. Sci., 2019,10, 2882-2892
https://doi.org/10.1039/C9SC00094A
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.
Chem. Sci., 2019,10, 2893-2905
https://doi.org/10.1039/C8SC05165H
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).
Chem. Sci., 2019,10, 2101-2110
https://doi.org/10.1039/C8SC03170C
X-ray Raman optical activity of chiral molecules
Resonant and off-resonant Raman Optical Activity signals in the X-ray regime (XROA) are predicted.
Chem. Sci., 2019,10, 898-908
https://doi.org/10.1039/C8SC04120B
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.
Chem. Sci., 2019,10, 113-117
https://doi.org/10.1039/C8SC03258K
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.
Chem. Sci., 2018,9, 6813-6829
https://doi.org/10.1039/C8SC00550H
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.
Chem. Sci., 2018,9, 6692-6702
https://doi.org/10.1039/C8SC01444B
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.
Chem. Sci., 2018,9, 4083-4092
https://doi.org/10.1039/C8SC00424B
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.
Chem. Sci., 2018,9, 3992-4002
https://doi.org/10.1039/C7SC05378A
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.
Chem. Sci., 2018,9, 860-875
https://doi.org/10.1039/C7SC04055E