Sensitivity study of the contact situation between the brake pad and the disc

The contact situation between the brake pad and the disc during the braking process is of particular importance concerning the squeal behavior of brake systems. After the braking process, the surface topography of brake pads can be measured using a confocal microscope. An algorithm to calculate the contact between two surfaces has been developed at the Institute of Dynamics and Vibrations. The algorithm calculates the deflection of asperities under a normal load regarding an elastic material behavior. A normal load is applied to a measured surface topography of the brake pad; the counter body (brake disc) is represented by a flat surface. The potential contact area, the locally distributed forces, deflections and normal stiffness of the pad are computed. Since there is an uncertainty in the relative position between the pad and the disc and hence the real contact situation during the braking process is not known, different contact situations must be considered during the simulations. Concerning various tilt angles of the pad that can arise during the vibrations of the brake system, a sensitivity study has been carried out. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Trans‐A2B‐corroles Bearing a Coumarin Moiety ‐ From Synthesis to Photophysics

Four dyads comprised of corrole and coumarin units have been synthesised. Three coumarincarboxaldehydes were synthesized and transformed into the corresponding trans‐A₂B‐corroles by reaction with 5‐(pentafluorophenyl)dipyrromethane. It has been proven that this type of direct condensation can lead to the corresponding corroles in moderate yields. The reaction of hydroxybenzaldehydes with vinylphosphonium salts has been identified as the most general method for the preparation of formyl‐coumarins with various patterns of substituents. The dyad consisting of ketobiscoumarin and corrole was synthesized by Sonogashira coupling. Spectroscopic and photophysical investigations revealed that there is an efficient energy transfer from the coumarin moiety to corrole in all four dyads. Energy transfer can be clearly ascribed to a dipole–dipole mechanism (Förster) for all dyads that contain luminescent coumarins and to an electron exchange mechanism (Dexter) for the dyad with the non‐luminescent one. In the case of the dyad that bears coumarin with a hydroxy group at position 5, an electron‐transfer was detected from corrole to coumarin. The latter process is possible because of the suitably low reduction potential of coumarins of this type.     

A simple and effective synthesis of activated vinylphosphonates from 3-methoxy-2-diethoxyphosphorylacrylate

A facile, efficient and general one-step procedure for the synthesis of 3-substituted 2-diethoxyphosphorylacrylates from 3-methoxy-2-diethoxyphosphorylacrylate 1b and nitrogen, carbon and phosphorus nucleophiles is presented. Reaction of 1b with 3,5-dimethoxyphenol in the presence of trifluoromethanesulfonic acid yields 3-diethoxyphosphoryl-5,7-dimethoxychromen-2-one.     

Effect of thermal treatment on potato starch evidenced by EPR,XRD and molecular weight distribution

Effect of heating of the potato starch on damages of its structure was investigated by quantitative electron paramagnetic resonance (EPR) spectroscopy, X‐ray diffraction and determination of the molecular weight distribution. The measurements were performed in the temperature range commonly used for starch modifications optimizing properties important for industrial applications. Upon thermal treatment, because of breaking of the polymer chains, diminishing of the average molecular weights occurred, which significantly influences generation of radicals, evidenced by EPR. For the relatively mild conditions, with heating parameters not exceeding temperature 230 °C and time of heating equal to 30 min a moderate changes of both the number of thermally generated radicals and the mean molecular weight of the starch were observed. After more drastic thermal treatment (e.g. 2 h at 230 °C), a rapid increase in the radical amount occurred, which was accompanied by significant reduction of the starch molecular size and crystallinity. Experimentally established threshold values of heating parameters should not be exceeded in order to avoid excessive damages of the starch structure accompanied by the formation of the redundant amount of radicals. This requirement is important for industrial applications, because significant destruction of the starch matrix might annihilate the positive influence of the previously performed intentional starch modification. Copyright © 2015 John Wiley & Sons, Ltd.     

Thermodynamic dissociation constants of silychristin, silybin, silydianin and mycophenolate by the regression analysis of spectrophotometric data

Mixed dissociation constants of four drug acids, i.e. silychristin, silybinin, silydianin and mycophenolate at various ionic strengths I of range 0.01 and 0.30 and at temperatures of 25 and 37 °C were determined using the SQUAD(84) regression analysis program applied to pH-spectrophotometric titration data. The proposed strategy of an efficient experimentation in a protonation constants determination, followed by a computational strategy for the chemical model with a protonation constants determination, is presented on the protonation equilibria of silychristin. The thermodynamic dissociation constant pK_a^T was estimated by non-linear regression of {pK_a, I} data at 25 and 37 °C: for silychristin pK_a,1^T=6.52(16) and 6.62(1), pK_a,2^T=7.22(13) and 7.41(5), pK_a,3^T=8.96(9) and 8.94(9), pK_a,4^T=10.17(7) and 10.03(8), pK_a,5^T=11.89(4) and 11.63(7); for silybin pK_a,1^T=7.00(4) and 6.86(5), pK_a,2^T=8.77(11) and 8.77(3), pK_a,3^T=9.57(8) and 9.62(1), pK_a,4^T=11.66(3) and 11.38(1); for silydianin pK_a,1^T=6.64(7) and 7.10(6), pK_a,2^T=7.78(5) and 8.93(1), pK_a,3^T=9.66(9) and 10.06(11), pK_a,4^T=10.71(7) and 10.77(7), pK_a,5^T=12.26(5) and 12.14(5); for mycophenolate pK_a^T=8.32(1) and 8.14(1). Goodness-of-fit tests for various regression diagnostics enabled the reliability of parameter estimates to be found.     

Size exclusion chromatography for analyses of fibroin in silk: optimization of sampling and separation conditions

A direct goal of this paper was to improve the methods of sample preparation and separation for analyses of fibroin polypeptide with the use of size exclusion chromatography (SEC). The motivation for the study arises from our interest in natural polymers included in historic textile and paper artifacts, and is a logical response to the urgent need for developing rationale-based methods for materials conservation. The first step is to develop a reliable analytical tool which would give insight into fibroin structure and its changes caused by both natural and artificial ageing. To investigate the influence of preparation conditions, two sets of artificially aged samples were prepared (with and without NaCl in sample solution) and measured by the means of SEC with multi angle laser light scattering detector. It was shown that dialysis of fibroin dissolved in LiBr solution allows removal of the salt which destroys stacks chromatographic columns and prevents reproducible analyses. Salt rich (NaCl) water solutions of fibroin improved the quality of chromatograms.     

Real‐space analysis of radiation‐induced specific changes with independent component analysis

A method of analysis is presented that allows for the separation of specific radiation‐induced changes into distinct components in real space. The method relies on independent component analysis (ICA) and can be effectively applied to electron density maps and other types of maps, provided that they can be represented as sets of numbers on a grid. Here, for glucose isomerase crystals, ICA was used in a proof‐of‐concept analysis to separate temperature‐dependent and temperature‐independent components of specific radiation‐induced changes for data sets acquired from multiple crystals across multiple temperatures. ICA identified two components, with the temperature‐independent component being responsible for the majority of specific radiation‐induced changes at temperatures below 130 K. The patterns of specific temperature‐independent radiation‐induced changes suggest a contribution from the tunnelling of electron holes as a possible explanation. In the second case, where a group of 22 data sets was collected on a single thaumatin crystal, ICA was used in another type of analysis to separate specific radiation‐induced effects happening on different exposure‐level scales. Here, ICA identified two components of specific radiation‐induced changes that likely result from radiation‐induced chemical reactions progressing with different rates at different locations in the structure. In addition, ICA unexpectedly identified the radiation‐damage state corresponding to reduced disulfide bridges rather than the zero‐dose extrapolated state as the highest contrast structure. The application of ICA to the analysis of specific radiation‐induced changes in real space and the data pre‐processing for ICA that relies on singular value decomposition, which was used previously in data space to validate a two‐component physical model of X‐ray radiation‐induced changes, are discussed in detail. This work lays a foundation for a better understanding of protein‐specific radiation chemistries and provides a framework for analysing effects of specific radiation damage in crystallographic and cryo‐EM experiments.     

Nanostructuring carbon supports for optimal electrode performance in biofuel cells and hybrid fuel cells

The efficiencies of dioxygen reduction on common carbonaceous materials were compared using voltammetry and fuel cell measurements. Carbon paper (CP), carbon fibre (CF) or carbon cloth (CC) conducting supports were covered under water pump pressure with multiwalled carbon nanotubes (MWCNTs) to increase the working surface of the electrode, improve connectivity with enzyme molecules and provide direct electron transfer. Laccase was the biocathode catalyst catalyzing 4-electron reduction of oxygen to water on the nanostructured electrode. CP carbon paper was selected as the favourable electrode substrate, since it provided best durability holding firmly the carbon nanotubes together with the enzyme at the electrode surface. Zinc disc or fructose dehydrogenase was used as anode in the hybrid fuel cell and biofuel cell, respectively. The characteristics under externally applied resistances and potential-time dependencies under flowing solution conditions were evaluated. The hybrid fuel cell based on Zn anode and CP supported laccase cathode gave the best results in terms of power and open circuit potential (OCP). The full biofuel cell based on laccase and fructose dehydrogenase shows lower OCP but the power–time dependencies were similar to those of the hybrid biofuel cell. The nanostructured surfaces show good supercapacitor properties due to the presence of carbon nanotubes at the electrode surface. The fuel cells undergo self-charging/discharging and, therefore, can be conveniently employed in pulsed-work regime to power external devices.