Zur Mahlerschen Vermutung im Komplexen

Ohne ZusammenfassungVorgetragen am 20. 10. 1959 auf der Tagung der DMV in Münster.     

Size-selected synthesis of PtRu nano-catalysts: reaction and size control mechanism

A rapid synthesis method for the preparation of PtRu colloids and their subsequent deposition on high surface area carbons is presented. The reaction mechanism is shown to involve the oxidation of the solvent, ethylene glycol, to mainly glycolic acid or, depending on the pH, its anion, glycolate, while the Pt(+IV) and Ru(+III) precursor salts are reduced. Glycolate acts as a stabilizer for the PtRu colloids and the glycolate concentration, and hence the size of the resulting noble metal colloids is controlled via the pH of the synthesis solution. Carbon-supported PtRu catalysts of controlled size can be prepared within the range of 0.7-4 nm. Slow scan X-ray diffraction and high-resolution transmission electron microscopy show the PtRu catalysts to be crystalline. The Ru is partly dissolved in the face-centered cubic Pt lattice, but the catalysts also consist of a separate, hexagonal Ru phase. The PtRu catalysts appear to be of the same composition independent of the catalyst size in the range of 1.2-4 nm. Particular PtRu catalysts prepared in this work display enhanced activities for the CH(3)OH electro-oxidation reaction when compared to two commercial catalysts.     

Detached eddy simulation of cyclic large scale fluctuations in a simplified engine setup

Computational Fluid Dynamics using RANS-based modelling approaches have become an important tool in the internal combustion engine development and optimization process. However, these models cannot resolve cycle to cycle variations, which are an important aspect in the design of new combustion systems. In this study the feasibility of using a Detached Eddy Simulation (DES) SST model, which is a hybrid RANS/LES model, to predict cycle to cycle variations is investigated. In the near wall region or in regions where the grid resolution is not sufficiently fine to resolve smaller structures, the two-equation RANS SST model is used. In the other regions with higher grid resolution an LES model is applied. The case considered is a geometrically simplified engine, for which detailed experimental data for the ensemble averaged and single cycle velocity field are available from Boreé et al. [Boreé, J., Maurel, S., Bazile, R., 2002. Disruption of a compressed vortex, Physics of Fluids 14 (7), 2543–2556]. The fluid flow shows a strong tumbling motion, which is a major characteristic for modern turbo-charged, direct-injection gasoline engines. The general flow structure is analyzed first and the extent of the LES region and the amount of resolved fluctuations are discussed. Multiple consecutive cycles are computed and turbulent statistics of DES SST, URANS and the measured velocity field are compared for different piston positions. Cycle to cycle variations of the velocity field are analyzed for both computation and experiment with a special emphasis on the useability of the DES SST model to predict cyclic variations.     

Effects of nitren extraction on a dissolving pulp and influence on cellulose dissolution in NaOH–water

A commercial dissolving pulp was treated with aqueous solutions containing 3, 5 and 7 % of an organometalic complex (nitren) with the aim to selectively extract xylan and study its impact on the conventional physical–chemical properties of the pulp. The influence of these treatments on the pulp dissolution in a moderate solvent (8 % NaOH aqueous solution) was assessed by measuring the dissolution yields and the dissolution mechanisms. The results of this study show that nitren treatment has the effect of removing a large part of the xylan present in a dissolving pulp. It is also removing mannans and most important, it is influencing cellulose in two ways, (1) extracting it with more intensity when the nitren concentration increases, and (2) decreasing its mean molecular mass, also more evident with nitren concentration increase. The nitren extractions are favourable for the dissolution in cold NaOH–water, being more effective with higher concentrations. This chemical modification of the fiber surface leads to the disassembly of the primary wall. This allows an easier access of the NaOH reagent to regions not accessible on the initial fibres, which with the decrease of the cellulose molecular weight allows an easier dissolution and gives different dissolution mechanisms.     

Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations

The redox activity of cysteine sulfur allows numerous post‐translational protein modifications involved in the oxidative regulation of metabolism, in metal binding, and in signal transduction. A combined approach based on infrared multiple photon dissociation spectroscopy at the Centre Laser Infrarouge d'Orsay (CLIO) free electron laser facility, calculations of IR frequencies, and finite temperature ab initio molecular dynamics simulations has been employed to characterize the gas‐phase structures of deprotonated cysteine sulfenic, sulfinic, and sulfonic acids, [cysSO_x]^? (x=1, 2, 3, representing the number of S‐bound oxygen atoms), which are key intermediates in the redox‐switching chemistry of proteins. The ions show different structural motifs owing to preferential binding of the proton to either the carboxylate or sulfur‐containing group. Due to the decreasing basicity of the sulfenic, sulfinic, and sulfonic terminals, the proton bound to SO^? in [cysSO]^? migrates to the carboxylate in [cysSO₃]^?, whereas it turns out to be shared in [cysSO₂]^?. Evidence is gathered that a mixture of close‐lying low‐energy conformers is sampled for each cysteine oxo form in a Paul ion trap at room temperature.     

Single Particle Extinction and Scattering allows novel optical characterization of aerosols

We apply to aerosols the optical method of Single Particle Extinction and Scattering recently proposed for characterizing liquid suspensions and specifically adapted to the aim. It provides simultaneous measurements of the real and imaginary parts of the field scattered in the forward direction by single airborne particles passing through a tightly focused laser beam. The intensity of transmitted light is collected in the forward direction, thus realizing a self-reference interferometric scheme relying on the fundamentals of the optical theorem. A high frequency (20 MS/s), extended dynamics (12 bits) sampling is performed by a cheap segmented photodiode, and a specific pulse shape analysis is exploited to validate the signals against a precise mathematical model. We show that accessing two independent physical quantities allows to exploit physical models to recover the aerosol size distribution from the measurement of the refractive index, either real or even complex. Laboratory measurements have been performed with polydisperse aerosols made of water droplets and NaCl in the submicron range, and the system has been accurately characterized. Examples of measurements of graphite nanoparticles and Pyrethrum smoke are shown. Limitations are discussed.