Synthesis,Characterization and Application of New Rhodium Complexes for Indirect Electrochemical Cofactor Regeneration

Electroenzymatic synthesis often suffers from electrochemical reaction steps which proceed slower than the coupled enzyme reaction. For indirect electrochemical cofactor regeneration, we here report two new mediators with superior properties compared to the established rhodium complex (2,2′‐bipyridyl)(pentamethylcyclopentadienyl)rhodium [Cp*Rh(2,2′‐bipyridine)]. After constructing a robotic system for fast and reliable cyclic voltammetry measurements, we screened twelve rhodium complexes with substituted 2,2′‐bipyridine ligands for their reduction potentials and catalytic activity towards the reduction of NADP. Promising complexes were investigated in more detail by cyclic voltammetry and under batch electrolysis conditions. The new complexes Cp*Rh(5,5′‐methyl‐2,2′‐bipyridine) and Cp*Rh(4,4′‐methoxy‐2,2′‐bipyridine) reduced NADP to NADPH three times faster than the established mediator, resulting in volumetric productivities of up to 136 mmol L⁻¹ d⁻¹ and turnover frequencies of up to 113 h⁻¹. This increased reaction rate of these new mediators makes indirect electrochemical approach significantly more competitive to other methods of cofactor regeneration. Abbreviations: ADH=alcohol dehydrogenase; Ag|AgCl=silver|silver chloride reference electrode; bpy=2,2′‐bipyridine; ci=current increase; Cp*=pentamethylcyclopentadienyl; CV=cyclic voltammetry; Ep=peak potential; equiv=equivalent; NADP/NADPH=nicotinamide adenine dinucleotide phosphate oxidised/reduced form.     

Two placebo-controlled crossover studies in healthy subjects to evaluate gastric acid neutralization by an alginate–antacid formulation (Gaviscon Double Action)

Objective: To investigate the intragastric acid neutralization activity of a combined alginate-antacid formulation.

Significance: Published studies have investigated the reflux-suppressing alginate component of Gaviscon Double Action (Gaviscon DA; RB, UK) but intragastric acid neutralization activity of the antacid component has not been evaluated in vivo.

Methods: Intragastric pH monitoring, using a custom-made 10-electrode catheter, was evaluated in a two-part exploratory study in healthy subjects; Part I (n?=?6) tested suitability of the catheter using antacid tablets (Rennie; Bayer, Germany); Part II (n?=?12) evaluated gastric acid neutralization activity of Gaviscon DA liquid (20?ml) versus placebo in fasted subjects using a randomized, open-label, crossover design. The primary endpoint was the percentage of time that intragastric pH ≥4 was measured during 30?min post-treatment. A confirmatory study of identical design was subsequently conducted (n?=?20).

Results: Monitoring pH using the multielectrode catheter was a viable approach, directly detecting changes in intragastric pH following a single dose of antacid tablets. In the exploratory study, the percentage of time that pH ≥4 during 30?minutes post-treatment was 46.8% with Gaviscon DA liquid versus 4.7% with placebo (p?=?0.0004). These findings were supported by the confirmatory study, where pH ≥4 was recorded 50.8% of the time with Gaviscon DA versus 3.5% with placebo (p?=?0.0051). In this study, Gaviscon DA was safe and well tolerated.

Conclusions: These studies demonstrate the effective acid neutralizing capacity of Gaviscon DA versus placebo in healthy, fasted subjects. This adds to the evidence base for the combination of alginates and antacids.     

Covid-19 pandemic and the unprecedented mobilisation of scholarly efforts prompted by a health crisis: Scientometric comparisons across SARS,MERS and 2019-nCoV literature

Scientometrics - During the current century, each major coronavirus outbreak has triggered a quick and immediate surge of academic publications on its respective topic. The spike in research...     

Grafting kinetics of poly(methyl methacrylate) on microparticulate silica

Grafting of poly(methyl methacrylate) (PMMA) on microparticulate silica was achieved by initiating the polymerization of MMA by 4,4′-azobis(4-cyanopentanoic acid) that was covalently bound to the silica surface. The initiator seems to be destabilized upon binding it to the silica surface. The kinetics of the graft polymerization are described and are largely affected by the Trommsdorff effect, which makes it possible to graft a high amount of PMMA on silica.     

Free and esterified cholesterol in developing feline white matter

The content of free and esterified cholesterol was examined in the cervical spinal cord lateral funiculus and in the corpus callosum of the cat during postnatal development. The concentration of free cholesterol increased with development from 8 to 56 μg/mg in the lateral funiculus and from 4 to 37 μg/mg in the corpus callosum. The total content per specimen increased 130 and 70 times, respectively. The major part of the postnatal increase in the free cholesterol occurred late postnatally. The concentration of esterified cholesterol decreased with development from 0.96 to 0.07% and from 9.50 to 0.30% of total sterol in the lateral funiculus and corpus callosum, respectively. In both regions, the total content per specimen increased with maturation. Throughout development, the content of cholesteryl ester was higher in the corpus callosum than in the lateral funiculus. A transient increase in esterified cholesterol concentration was seen during the first postnatal days in the lateral funiculus and 3 weeks postnatally in the corpus callosum. The results suggest that most of the postnatal increase of free cholesterol in the white matter is related to a continued growth of established myelin sheaths and not to de novo myelination. The transient increase in concentration of esterified cholesterol in the early postnatal lateral funiculus coincides in time with a spontaneous myelin sheath disintegration. This supports the view that the ester peak may be primarily related to myelin breakdown rather than to myelin production. The significance of the high ester concentration in the neonatal corpus callosum and the ester peak seen during initial myelination remains obscure and calls for further developmental morphological studies.     

Living in highly dynamic polluted river floodplains, do contaminants contribute to population and community effects?

The aim of this paper was to collect evidence for the effects of contaminants on biota in a highly dynamic river Rhine floodplain. To this purpose we reviewed the results of circa 10 studies performed in this floodplain. The floodplain was contaminated with elevated levels of cadmium, copper, PAHs, and PCBs and high levels of zinc which were at some sites above legislative values. The results showed that the present contaminants were accumulated by the floodplain inhabiting organisms, but meanwhile population and community effects were ambiguous. Only for the mayfly Ephoron virgo clear effects were detected at the level of the single floodplain. The absence of clear population and community effects is puzzling since at lower contaminant concentrations adverse effects were detected in other environments. Factors that may mask toxic effects include flooding and food quality and quantity. We conclude that given the site specific conditions, being an open, eutrophic system with a highly dynamic flooding pattern, assessment of the contribution of toxicants to observed population density or biomass and community composition requires 1] an increase in number of replicates; 2] a larger scale of investigation and 3] comparison to stable systems with comparable contamination levels.     

Higher Tool Productivity due to New Generation of PVD Coatings

PVD coating technology has seen many new developments in the past few years. HIPIMS⁺ is an example of these developments with excellent results on tool productivity and lifespan. The technology combines the advantages of arc evaporation with those of magnetron sputtering and results in a dense and defect‐free coating with tuneable residual stress. The coatings have been tested successfully by international tool manufacturers. Additional developments can be seen in DLC coatings and the hydrogen‐free variety ta‐C. These coatings are suitable for low temperature deposition and machining of special materials.     

Numerische Analyse geschweißter Verbindungen von Duplexstahl und Quarzglas

Numerical analysis of welded joints between duplex steel and quartz glass. Welded joints are a vital element in structural engineering. Originating from conventional carbon steel welding in construction, recent advancements in welding technology now allow the joint of modern high‐strength steel and glass materials. With today's methods, an analysis of the welded joints' structural behaviour can be conducted by experiment, as well as by numerical analysis. Particularly for the numeric analysis, capturing the non‐linear thermal and mechanical properties of the materials is important, in order to allow a realistic determination of temperature, microstructure and residual stresses for different types of joints. Simulations of multi‐layered weld joint on duplex steel show, that a targeted heat treatment during MAG‐welding by variation of the welding parameters achieves a beneficial ratio between ferrite and austenite which, for example, ensures a high resistance of the weld to corrosion. The material quartz glass can generally be welded as butt‐weld with a CO₂‐laser. The simulations of a welded joint of a plate and a pipe show, that an optimization of the welding technology of preheat laser beam and welding laser beam is necessary, in order to reduce the thermal impact during the welding process, as well as residual stress in the joint. At the Department of Steel Structures at the Bauhaus‐Universität Weimar, numerical simulations of welded joints between steel and glass materials are a current and topical research focus.