Chemoenzymatic Hydrogen Production from Methanol through the Interplay of Metal Complexes and Biocatalysts

Microbial methylotrophic organisms can serve as great inspiration in the development of biomimetic strategies for the dehydrogenative conversion of C₁ molecules under ambient conditions. In this Concept article, a concise personal perspective on the recent advancements in the field of biomimetic catalytic models for methanol and formaldehyde conversion, in the presence and absence of enzymes and co-factors, towards the formation of hydrogen under ambient conditions is given. In particular, formaldehyde dehydrogenase mimics have been introduced in stand-alone C₁-interconversion networks. Recently, coupled systems with alcohol oxidase and dehydrogenase enzymes have been also developed for in situ formation and decomposition of formaldehyde and/or reduced/oxidized nicotinamide adenine dinucleotide (NADH/ NAD⁺). Although C₁ molecules are already used in many industries for hydrogen production, these conceptual bioinspired low-temperature energy conversion processes may lead one day to more efficient energy storage systems enabling renewable and sustainable hydrogen generation for hydrogen fuel cells under ambient conditions using C₁ molecules as fuels for mobile and miniaturized energy storage solutions in which harsh conditions like those in industrial plants are not applicable.     

Design of new organic superacids with fused and isolated pyrrole and cyclopentadiene rings and assessment of effect of –BX2 (X = H,F, Cl,CN) substituents on the acidity enhancement: A DFT analysis

New classes of organic Brønsted acids were designed with pyrrole and cyclopentadiene scaffolds, and their acidity was assessed theoretically by the B3LYP/6-311++G(d,p) method. The hydrogen atom of NH group in pyrrole was substituted by an –BX₂ (X = H, F, Cl, CN, CF₃). The boron atom stabilizes the conjugated bases by interaction with the center of negative charge after deprotonation. The acidity of the compounds was promoted by substitution of the hydrogen atoms of the rings with CN moiety as a strong electron withdrawing group. Also, after deprotonation, delocalization of the negative charge in both pyrrole and cyclopentadiene rings causes stability of the conjugated bases and consequently enhances the acidity. The charge delocalization in the neutral acids and their conjugated bases was compared using nucleus-independent chemical shift index. Enthalpies and Gibbs free energies of deprotonation in gas phase, ∆H_acid and ∆G_acid, were used as a measure of acidity. Both compounds with isolated and fused pyrrole and cyclopentadiene rings were investigated and it was found that the formers are more acidic. Using these strategies, several acids and superacids with wide range of acidity with ∆G_acid values of 244 to 328 kcal mol⁻¹ were obtained.     

Fast DNA and protein microarray tests for the diagnosis of hepatitis C virus infection on a single platform

Hepatitis C virus (HCV) is a major cause of chronic liver disease and liver cancer, and remains a large health care burden to the world. In this study we developed a DNA microarray test to detect HCV RNA and a protein microarray to detect human anti-HCV antibodies on a single platform. A main focus of this study was to evaluate possibilities to reduce the assay time, as a short time-to-result (TTR) is a prerequisite for a point-of-care test. Significantly reducing hybridisation and washing times did not impair the assay performance. This was confirmed first using artificial targets and subsequently using clinical samples from an HCV seroconversion panel derived from a HCV-infected patient. We were able to reduce the time required for the detection of human anti-HCV antibodies to only 14 min, achieving nanomolar sensitivity. The protein microarray exhibited an analytical sensitivity comparable to that of commercial systems. Similar results were obtained with the DNA microarray using a universal probe which covered all different HCV genotypes. It was possible to reduce the assay time after PCR from 150 min to 16 min without any loss of sensitivity. Taken together, these results constitute a significant step forward in the design of rapid, microarray-based diagnostics for human infectious disease, and show that the protein microarray is currently the most favourable candidate to fill this role.     

Efficiency enhancement of a two-beam free-electron laser using a nonlinearly tapered wiggler

A nonlinear and non-averaged model of a two-beam free-electron laser(FEL) wiggler that is tapered nonlinearly in the absence of slippage is presented.The two beams are assumed to have different energies,and the fundamental resonance of the higher energy beam is at the third harmonic of the lower energy beam.By using Maxwell’s equations and the full Lorentz force equation of motion for the electron beams,coupled differential equations are derived and solved numerically by the fourth-order Runge-Kutta method.The amplitude of the wiggler field is assumed to decrease nonlinearly when the saturation of the third harmonic occurs.By simulation,the optimum starting point of the tapering and the slopes for reducing the wiggler amplitude are found.This technique can be applied to substantially improve the efficiency of the two-beam FEL in the XUV and X-ray regions.The effect of tapering on the dynamical stability of the fast electron beam is also studied.     

Seymour's Second Neighborhood Conjecture for Tournaments Missing a Generalized Star

Seymour's Second Neighborhood Conjecture asserts that every digraph (without digons) has a vertex whose first out‐neighborhood is at most as large as its second out‐neighborhood. We prove its weighted version for tournaments missing a generalized star. As a consequence the weighted version holds for tournaments missing a sun, star, or a complete graph. © 2011 Wiley Periodicals, Inc. J Graph Theory 71:89–94, 2012     

Asymptotic symmetry of geometries with Schrödinger isometry

We show that the asymptotic symmetry algebra of geometries with Schrödinger isometry in any dimension is an infinite-dimensional algebra containing one copy of Virasoro algebra. It is compatible with the fact that the corresponding geometries are dual to non-relativistic CFTs whose symmetry algebra is the Schrödinger algebra which admits an extension to an infinite-dimensional symmetry algebra containing a Virasoro subalgebra.     

A mesoscopic model of the intermixing during nanoenergetic materials processing

A general mesoscopic model for the simulation of thin-film vapor deposition applied to energetic materials, specifically bimetallic multilayers, is presented. We describe the setup of this mesoscopic simulator developed in the frame of a multiscale study by implementing ab initio data into a set of differential equations. We present numerical results relative to the formation of barrier layers as a result of interdiffusion between successive bimetallic AlNi multilayers. The key role of the vacancies species created during deposition is highlighted.     

Efficiency enhancement of a two-beam free-electron laser using a nonlinearly tapered wiggler

A nonlinear and non-averaged model of a two-beam free-electron laser (FEL) wiggler that is tapered nonlinearly in the absence of slippage is presented. The two beams are assumed to have different energies, and the fundamental resonance of the higher energy beam is at the third harmonic of the lower energy beam. By using Maxwell's equations and the full Lorentz force equation of motion for the electron beams, coupled differential equations are derived and solved numerically by the fourth-order Runge-Kutta method. The amplitude of the wiggler field is assumed to decrease nonlinearly when the saturation of the third harmonic occurs. By simulation, the optimum starting point of the tapering and the slopes for reducing the wiggler amplitude are found. This technique can be applied to substantially improve the efficiency of the two-beam FEL in the XUV and X-ray regions. The effect of tapering on the dynamical stability of the fast electron beam is also studied.