Experimental and computational investigation of Au25 clusters and CO2: a unique interaction and enhanced electrocatalytic activity

Atomically precise, inherently charged Au(25) clusters are an exciting prospect for promoting catalytically challenging reactions, and we have studied the interaction between CO(2) and Au(25). Experimental results indicate a reversible Au(25)-CO(2) interaction that produced spectroscopic and electrochemical changes similar to those seen with cluster oxidation. Density functional theory (DFT) modeling indicates these changes stem from a CO(2)-induced redistribution of charge within the cluster. Identification of this spontaneous coupling led to the application of Au(25) as a catalyst for the electrochemical reduction of CO(2) in aqueous media. Au(25) promoted the CO(2) → CO reaction within 90 mV of the formal potential (thermodynamic limit), representing an approximate 200-300 mV improvement over larger Au nanoparticles and bulk Au. Peak CO(2) conversion occurred at -1 V (vs RHE) with approximately 100% efficiency and a rate 7-700 times higher than that for larger Au catalysts and 10-100 times higher than those for current state-of-the-art processes.     

Quantification strategies for elemental imaging of biological samples using laser ablation-inductively coupled plasma-mass spectrometry

This review provides analysts with critical insights of current approaches for quantification by laser ablation-inductively coupled plasma-mass spectrometry in the field of elemental imaging. This encompasses both calibration strategies that have been used with success in imaging biological samples, as well as those with potential to improve analytical accuracy and precision if applied to imaging. Methods reviewed include the use of CRMs, laboratory prepared matrix matched standards, internal standardisation, online standard addition and a variety of novel approaches that makes elemental imaging accessible to a wider base of analysts. The importance of quantification and factors affecting its use in imaging will also be considered.     

Assignment of Relative Configuration of Desoxypropionates by 1H NMR Spectroscopy: Method Development,Proof of Principle by Asymmetric Total Synthesis of Xylarinic Acid A and Applications

The determination of the relative configuration of 1,3‐dimethyl‐substituted alkyl chains is possible by interpretation of ¹H NMR shift differences. Additionally, assignments are feasible in a variety of deuterated solvents, because the corresponding shift differences are not significantly influenced by the solvent. The trends for Δδ values depending on functional groups adjacent to the stereogenic centers are shown. Based on a thorough comparison with literature data, the relative configuration of natural products can be predicted. For this purpose, we derived an empirical rule for the ranges in which Δδ values usually occur. Furthermore, we were able to proof the validity of our method by the successful prediction of the relative configuration for the polyketide natural product xylarinic acid A, which was confirmed by the asymmetric total synthesis of its enantiomer. Based on the proposed simple analysis of published ¹H NMR data and the determination of the relevant chemical‐shift differences, we predicted the relative configurations of several previously unassigned natural products.     

Improvement of the mechanical and barrier properties of methylcellulose-based films by treatment with HEMA and silane monomers under gamma radiation

Methylcellulose (MC)-based films were prepared by casting from its 1% aqueous solution containing 0.5% vegetable oil, 0.25% glycerol and 0.025% Tween^®-80. Puncture strength (PS), puncture deformation (PD) and water vapor permeability (WVP) of the films were found to be 147 N/mm, 3.46 mm, and 6.34 g mm/m² day kPa, respectively. The monomer, 2-hydroxyethyl methacrylate (HEMA) (0.1–1%, w/w) was incorporated into the MC-based solution and films were prepared by casting. Films were then exposed to gamma radiation (5–25 kGy) and it revealed that 1% HEMA containing films showed the highest PS values (282 N/mm at 10 kGy). Silane monomer (3-aminopropyl tri-ethoxy silane) (0.1–1%, w/w) was also added into the MC-based films and were found to improve the strength of the films significantly. In comparison between HEMA and silane treatment onto MC-based films, it was observed that silane performed better strength and barrier properties. Surface morphology of the monomer treated films was examined by scanning electron microscopy and suggested better appearance than MC-based film.     

Infinite Dimensional Bicomplex Spectral Decomposition Theorem

This paper presents a bicomplex version of the Spectral Decomposition Theorem on infinite dimensional bicomplex Hilbert spaces. In the process, the ideas of bounded linear operators, orthogonal complements and compact operators on bicomplex Hilbert spaces are introduced and treated in relation with the classical Hilbert space M′ imbedded in any bicomplex Hilbert space M.     

Analysis of and numerical schemes for a mouse population model in Hantavirus epidemics

This paper considers a non-linear system of ordinary differential equations, which arises in the study of hantavirus epidemics. The system has the property that the total population obeys the logistic equation. For this system, we use linearization and the dynamical properties of the logistic equation to analyze the dynamics of the subpopulation system. In view of the usual numerical instabilities associated with standard finite difference methods used for simulating such systems, we construct non-standard finite difference (NSFD) schemes, which preserve the dynamic properties of the system, and may therefore be used for its simulation.     

Stability properties of a nonstandard finite difference scheme for a hantavirus epidemic model

This paper studies the stability properties of a nonstandard finite difference (NSFD) scheme used to simulate the dynamics of a mouse population model in hantavirus epidemics. It is shown that this difference scheme and the underlying system of differential equations have the same dynamics. The proof uses the fact that the total population obeys the logistic equation, as well as techniques from calculus, graphical analysis, and dynamical systems.