Controllable Synthesis of Few‐Layer Bismuth Subcarbonate by Electrochemical Exfoliation for Enhanced CO2 Reduction Performance

Two‐dimensional (2D) engineering of materials has been recently explored to enhance the performance of electrocatalysts by reducing their dimensionality and introducing more catalytically active ones. In this work, controllable synthesis of few‐layer bismuth subcarbonate nanosheets has been achieved via an electrochemical exfoliation method. These nanosheets catalyse CO₂ reduction to formate with high faradaic efficiency and high current density at a low overpotential owing to the 2D structure and co‐existence of bismuth subcarbonate and bismuth metal under catalytic turnover conditions. Two underlying fast electron transfer processes revealed by Fourier‐transformed alternating current voltammetry (FTacV) are attributed to CO₂ reduction at bismuth subcarbonate and bismuth metal. FTacV results also suggest that protonation of CO₂^.? is the rate determining step for bismuth catalysed CO₂ reduction.     

Diverged Plant Terpene Synthases Reroute the Carbocation Cyclization Path towards the Formation of Unprecedented 6/11/5 and 6/6/7/5 Sesterterpene Scaffolds

Sesterterpenoids are a relatively rare class of plant terpenes. Sesterterpene synthase (STS)‐mediated cyclization of the linear C₂₅ isoprenoid precursor geranylfarnesyl diphosphate (GFPP) defines sesterterpene scaffolds. So far only a very limited number of STSs have been characterized. The discovery of three new plant STSs is reported that produce a suite of sesterterpenes with unprecedented 6/11/5 and 6/6/7/5 fused ring systems when transiently co‐expressed with a GFPP synthase in Nicotiana benthamiana. Structural elucidation, feeding experiments, and quantum chemical calculations suggest that these STSs catalyze an unusual cyclization path involving reprotonation, intramolecular 1,6 proton transfer, and concerted but asynchronous bicyclization events. The cyclization is diverted from those catalyzed by the characterized plant STSs by forming unified 15/5 bicyclic sesterterpene intermediates. Mutagenesis further revealed a conserved amino acid residue implicated in reprotonation.     

Crystal structure of Pt(S2COEt)2

The crystals of Pt(S₂COEt)₂ are orthorhombic, Pbca, with (at 20°C)a=7.799(3),b=7.368(6),c=20.588(7) Å.D _cale=2.46g cm^–3 forZ=4. The platinum atom resides on a crystallographic center of inversion and is bound to the four sulfur atoms of the xanthato ligand in a square planar geometry. The Pt–S distances are 2.313(6) and 2.320(7)Å with an intraligand S–Pt–S angle of 75.1(2)°.     

Azetidine,pyrrolidine and hexamethyleneimine at 170 K

The crystal structures of the cyclic amines azetidine (C₃H₇N), pyrrolidine (C₄H₉N) and hexamethyleneimine (homopiperidine, C₆H₁₃N), of the series (CH₂)_nNH, with n = 3, 4 and 6, respectively, have been determined at 170 K, following in situ crystallization from the melt. These structures provide crystallographic data to complete the homologous series of cyclic amines (CH₂)_nNH, for n = 2–6. Azetidine and pyrrolidine contain chains propagating along 2₁ screw axes, in which the molecules are linked by co-operative N—H...N hydrogen bonds. Azetidine has two molecules in its asymmetric unit, while pyrrolidine has only one. Hexamethyleneimine contains tetrameric hydrogen-bonded rings formed about crystallographic inversion centres, with two molecules in its asymmetric unit. The observation of crystallographically distinct molecules in the hydrogen-bonded chains of azetidine and cyclic hydrogen-bonded motifs in hexamethyleneimine is consistent with expectations derived from comparison with monoalcohols forming chains or rings by co-operative O—H...O hydrogen bonds. The next member of the cyclic amine series, heptamethyleneimine, forms a cubic plastic phase on cooling from the melt.     

Electrochemical quartz crystal microbalance study of azurin adsorption onto an alkanethiol self-assembled monolayer on gold

A quartz crystal microbalance coupled with electrochemistry was used to examine the adsorption of azurin on a gold electrode modified with a self-assembled monolayer of octanethiol. Azurin adsorbed irreversibly to form a densely packed monolayer. The rate of azurin adsorption was related to the bulk concentration of azurin in solution within the concentration range studied. At a high azurin concentration (2.75 muM), adsorption was rapid with a stable adsorption maximum attained in 2-3 min. At a lower azurin solution concentration (0.35 muM), the time to reach a stable adsorption maximum was approximately 30 min. Interestingly, the maximum surface concentration attained for all solution concentrations studied by the QCM method was 25 +/- 1 pmol cm-2, close to that predicted for monolayer coverage. The dissipation was monitored during adsorption, and only small changes were detected, implying a rigid adsorption model, as needed when using the Sauerbrey equation. Cyclic voltammetric data were consistent with a one-electron, surface-confined CuII/CuI azurin process with fast electron-transfer kinetics. The electroactive surface concentration calculated using voltammetry was 7 +/- 1 pmol cm-2. The differences between the QCM and voltammetrically determined surface coverage values reflect, predominantly, the different measurement methods but imply that all surface-confined azurin is not electrochemically active on the time scale of cyclic voltammetry.     

Dicobalt II-II, II-III, and III-III complexes as spectroscopic models for dicobalt enzyme active sites

A matched set of dinuclear cobalt complexes with II-II, II-III, and III-III oxidation states have been prepared and structurally characterized. In [(bpbp)Co2(O2P(OPh)2)2]n+ ( n = 1, 2, or 3; bpbp(-) = 2,6-bis(( N,N'-bis-(2-picolyl)amino)-methyl)-4-tertbutylphenolato), the nonbonded Co...Co separations are within the range 3.5906(17) to 3.7081(11) angstroms, and the metal ions are triply bridged by the phenolate oxygen atom of the heptadentate dinucleating ligand and by two diphenylphosphate groups. The overall structures and geometries of the complexes are very similar, with minor variations in metal-ligand bond distances consistent with oxidation state assignments. The CoIICoIII compound is a valence-trapped Robin-Day class II complex. Solid state 31P NMR spectra of the diamagnetic CoIIICoIII (3) and paramagnetic CoIICoIII (2) and CoIICoII (1) complexes show that 31P isotropic shifts broaden and move downfield by about 3000 ppm for each increment in oxidation state. Cyclic voltammetry corroborates the existence of the CoIICoII, CoIICoIII, and CoIIICoIII species in solution. The redox changes are not reversible in the applied scanning timescales, indicating that chemical changes are associated with oxidation and reduction of the cobalt centers. An investigation of the spectroscopic properties of this series has been carried out for its potential usefulness in analyses of the related spectroscopic properties of the dicobalt metallohydrolases. Principally, magnetic circular dichroism (MCD) has been used to determine the strength of the magnetic exchange coupling in the CoIICoII complex by analysis of the variable-temperature variable-field (VTVH) intensity behavior of the MCD signal. The series is ideal for the spectroscopic determination of magnetic coupling since it can occur only in the CoIICoII complex. The CoIICoIII complex contains a nearly isostructural CoII ion, but since CoIII is diamagnetic, the magnetic coupling is switched off, while the spectral features of the CoII ion remain. Analysis of the MCD data from the CoIICoIII complex has been undertaken in the theoretical context of a 4T1g ground-state of the CoII ion, initially in an octahedral ligand field that is split by both geometric distortion and zero-field splitting to form an isolated doublet ground state. The MCD data for the CoIICoII pair in the [(bpbp)Co2(O2P(OPh)2)2]+ complex were fitted to a model based on weak antiferromagnetic coupling with J = -1.6 cm (-1). The interpretation is confirmed by solid state magnetic susceptibility measurements.     

Hydrodynamic Rocking Disc Electrode Study of the TEMPO‐mediated Catalytic Oxidation of Primary Alcohols

The hydrodynamically thinned diffusion layer at a sinusoidally rocking disc is approximately uniform and can be expressed in terms of a diffusion layer thickness with D, the diffusion coefficient of the redox active species, v, the kinematic viscosity, Θ, the total rocking angle (here 90 degrees), and f, the rocking frequency (ranging here from 0.83 to 25 Hz). For the one‐electron oxidation of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) in aqueous carbonate buffer pH 9.5, it is shown that there is quantitative agreement between the expression for the diffusion layer thickness and experimental data. Next, for seven primary alcohols, the catalytic TEMPO‐mediated oxidation mechanism is investigated under rocking disc conditions. Chemical rate constants are evaluated (by varying the diffusion layer thickness) employing the DigiElch4.F simulation package. Trends in the chemical rate constants (compared with DFT calculations) suggest enhanced reactivity for methanol versus higher primary alcohols and for aromatic versus non‐aromatic primary alcohols. Rocking disc voltammetry allows quantitative mechanistic analysis in the laminar flow regime.     

Structures and solution dynamics of pseudorotaxanes mediated by alkali-metal cations

Kinetic stability studies of a series of pseudorotaxanes formed from electron-rich crown ethers (hosts and ) and naphthalene diimide (guest ) in the presence of alkali salt templates MX (where M(+) = Li(+) and Na(+), and X(-) = Cl(-), Br(-), I(-), NO(3)(-) and CF(3)SO(3)(-)) were performed by (1)H NMR. The switching between the (bound) host and its linkage isomer host (free) was monitored in solution in the presence and absence of alkali salts, to establish the relative thermodynamic stabilities in the series. We also report here six new crystal structures, for pseudorotaxanes of type: [.], [M(2)..](2+) and [M(2)..](2+). Their solution-phase structures are in good agreement with the solid-state structures determined by X-ray crystallography.     

Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization

A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ(-) monoanion. In the presence of M(x+)(MeCN), reaction with TCNQ(-)(MeCN) leads to deposition of M(x+)[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 mum in length and with diameters of less than 180 nm, and Co[TCNQ](2)(H(2)O)(2) as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal-TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.