Detecting unalloyed tin in LiSn2(PO4)3-based anodes with Mössbauer spectroscopy

The first discharge of the Li⁺ ion anode material LiSn₂(PO₄)₃ was investigated with Mössbauer spectroscopy and electrochemical techniques. Mössbauer spectroscopy provided insight into the structure of the tin atoms of the fully discharged anode materials. Spectra consist of overlapping peaks, which are assigned to noncrystalline β-Sn and Li–Sn alloy domains. An analysis of the relative intensities of the Mössbauer spectra shows the relative abundance of β-Sn increases at the expense of the Li–Sn alloy as the discharge rate increases. Cell polarization occurs at higher discharge rates, leading to inefficient electrode utilization and poor cycling performance. Sluggish Li⁺ ion diffusion through the amorphous Li₃PO₄ network that is formed early in the discharge process might be responsible for the poor electrochemical performance and the accumulation of unalloyed tin.     

Optimization of the CHARMM additive force field for DNA: Improved treatment of the BI/BII conformational equilibrium

The B-form of DNA can populate two different backbone conformations: BI and BII, defined by the difference between the torsion angles ε and ζ (BI = ε-ζ < 0 and BII = ε-ζ > 0). BI is the most populated state, but the population of the BII state, which is sequence dependent, is significant and accumulating evidence shows that BII affects the overall structure of DNA, and thus influences protein-DNA recognition. This work presents a reparametrization of the CHARMM27 additive nucleic acid force field to increase the sampling of the BII form in MD simulations of DNA. In addition, minor modifications of sugar puckering were introduced to facilitate sampling of the A form of DNA under the appropriate environmental conditions. Parameter optimization was guided by quantum mechanical data on model compounds, followed by calculations on several DNA duplexes in the condensed phase. The selected optimized parameters were then validated against a number of DNA duplexes, with the most extensive tests performed on the EcoRI dodecamer, including comparative calculations using the Amber Parm99bsc0 force field. The new CHARMM model better reproduces experimentally observed sampling of the BII conformation, including sampling as a function of sequence. In addition, the model reproduces the A form of the 1ZF1 duplex in 75 % ethanol, and yields a stable Z-DNA conformation of duplex (GTACGTAC) in its crystal environment. The resulting model, in combination with a recent reoptimization of the CHARMM27 force field for RNA, will be referred to as CHARMM36.     

On the analyses of fluorescence depolarisation data in the presence of electronic energy migration. Part I: Theory and general description

A new and general procedure is described for a detailed analysis of time-resolved fluorescence depolarisation data in the presence of electronic energy migration. An isotropic ensemble of bifluorophoric molecules (D(1)-R-D(2)) has been studied to demonstrate its utility. Intramolecular donor-donor energy migration occurs between the two donor groups (D), which are covalently connected to a rigid linker group (R). These groups undergo restricted reorientational motions with respect to the R group. The analysis of depolarisation data basically involves the search for best-fit parameters which describe the local reorientational motions, the intermolecular D(1)-D(2) distance, as well as the mutual orientations of the donors. For this, the analysis is partly performed on the Fourier domain and the best-fit parameters are determined by using an approach based on a Genetic Algorithm. The energy migration process has been described by using Monte Carlo simulations and an extended F?rster theory (EFT). It is found that the EFT provides the least time-consuming computational method. Since one-photon and two-photon excited fluorescence experiments can be applied for energy migration studies, a general and unified theoretical formulation is given.     

Electronic Structure of an [FeFe] Hydrogenase Model Complex in Solution Revealed by X-ray Absorption Spectroscopy Using Narrow-Band Emission Detection

High-resolution X-ray absorption spectroscopy with narrow-band X-ray emission detection, supported by density functional theory calculations (XAES-DFT), was used to study a model complex, ([Fe(2)(μ-adt)(CO)(4)(PMe(3))(2)] (1, adt = S-CH(2)-(NCH(2)Ph)-CH(2)-S), of the [FeFe] hydrogenase active site. For 1 in powder material (1(powder)), in MeCN solution (1'), and in its three protonated states (1H, 1Hy, 1HHy; H denotes protonation at the adt-N and Hy protonation of the Fe-Fe bond to form a bridging metal hydride), relations between the molecular structures and the electronic configurations were determined. EXAFS analysis and DFT geometry optimization suggested prevailing rotational isomers in MeCN, which were similar to the crystal structure or exhibited rotation of the (CO) ligands at Fe1 (1(CO), 1Hy(CO)) and in addition of the phenyl ring (1H(CO,Ph), 1HHy(CO,Ph)), leading to an elongated solvent-exposed Fe-Fe bond. Isomer formation, adt-N protonation, and hydride binding caused spectral changes of core-to-valence (pre-edge of the Fe K-shell absorption) and of valence-to-core (K?(2,5) emission) electronic transitions, and of Kα RIXS data, which were quantitatively reproduced by DFT. The study reveals (1) the composition of molecular orbitals, for example, with dominant Fe-d character, showing variations in symmetry and apparent oxidation state at the two Fe ions and a drop in MO energies by ～1 eV upon each protonation step, (2) the HOMO-LUMO energy gaps, of ～2.3 eV for 1(powder) and ～2.0 eV for 1', and (3) the splitting between iron d(z(2)) and d(x(2)-y(2)) levels of ～0.5 eV for the nonhydride and ～0.9 eV for the hydride states. Good correlations of reduction potentials to LUMO energies and oxidation potentials to HOMO energies were obtained. Two routes of facilitated bridging hydride binding thereby are suggested, involving ligand rotation at Fe1 for 1Hy(CO) or adt-N protonation for 1HHy(CO,Ph). XAES-DFT thus enables verification of the effects of ligand substitutions in solution for guided improvement of [FeFe] catalysts.     

A practical electromediated ipso-hydroxylation of aryl and alkyl boronic acids under an air atmosphere

An efficient electromediated aerobic ipso-hydroxylation reaction of aryl and alkyl boronic acids has been developed. Furthermore, mechanistic insight into the role of superoxide anions in this reaction has also been provided based on electrochemical studies and experimental results.     

Sparsity of the average curvature information matrix

We present a theorem regarding the average curvature properties of partially separable functions which need not be differentiable or continuous. This has implications for derivative-free optimization methods which make use of average curvature information to select the set of search directions. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic Ellipsometry Characterisation and Estimation of the Hamaker Constant of Cellulose

Calculations of Hamaker constants using Lifshitz theory require the availability of accurate dielectric data, especially in the visible-ultraviolet region. We present spectroscopic ellipsometry data on well-defined cellulose films of a limited thickness range (100–140 layers) deposited on an oxidised and hydrophobised silicon substrate. The spectral data, representing measurements from a perpendicular orientation to the fibre deposition direction, was used for estimates of the necessary spectral parameters, i.e. the oscillator strengths and characteristic frequencies in the UV-range. Our calculations show that cellulose has a relatively low Hamaker constant in air (58 zJ) and water (8.0 zJ). The implications for the surface energy estimates of cellulose and colloidal interactions between cellulose and various types of fillers and coating colours are indicated.