Über die Einwirkung von Bleitetraacetat auf Phenole, 11. Mitt.: Darstellung neuer o- und p-Benzochinolacetate und o-Chinonondiacetate

Zusammenfassung Es wird die Oxydation von Phenolen untersucht, die neben anderen Substituenten in einer o-Stellung Isopropyl-,sec.-Butylodertert.-Butylreste tragen². Die erhaltenen o-Chinolacetate sind von Interesse, weil nach erfolgtem Umsatz aus den erhaltenen verschiedenen Reaktionsprodukten die genannten Reste entfernt werden können³.Auch aus Phenolen, die in bestimmten Stellen eine Nitrooder Phthaliminogruppe enthielten, wurden o-Chinolacetate hergestellt.Zur Trennung der bei der Oxydation erhaltenen Chinolacetate wurde die Dünnschichtchromatographie eingesetzt.Mit 1 AbbildungAuszug aus der DissertationF. Takacs, Univ. Wien, 1964.10. Mitt.:F. Wessely, J. Swoboda undV. Guth Mh. Chem.95, 649 (1964).     

Activated water desorption from poly(methylvinylidene cyanide)

We have investigated water desorption from the polymer poly(methylvinylidene cyanide). The angle resolved thermal desorption spectra show large deviations from the cosn theta distribution for water desorption from poly(methylvinylidene cyanide) indicative of an activated desorption process. The Arrhenius plots obtained from Polanyi-Wigner analysis of the thermal desorption data suggest that a two-state model of desorption applies, while theory suggests that lattice strain in the polymer plays a key role in the thermal desorption of water.     

Monoclonal antibody proteomics: discovery and prevalidation of chronic obstructive pulmonary disease biomarkers in a single step

We define mAb proteomics as the global generation of disease specific antibodies that permit mass screening of biomarkers. An integrated, high-throughput, disease-specific mAb-based biomarker discovery platform has been developed. The approach readily provided new biomarker leads with the focus on large-scale discovery and production of mAb-based, disease-specific clinical assay candidates. The outcome of the biomarker discovery process was a highly specific and sensitive assay, applicable for testing of clinical validation paradigms, like response to treatment or correlation with other clinical parameters. In contrast to MS-based or systems biology-based strategies, our process produced prevalidated clinical assays as the outcome of the discovery process. By re-engineering the biomarker discovery paradigm, the encouraging results presented in this paper clearly demonstrate the efficiency of the mAb proteomics approach, and set the grounds for the next steps of studies, namely, the hunt for candidate biomarkers that respond to drug treatment.     

Gradient-driven fluctuations in microgravity

Equilibrium fluctuations of thermodynamic variables, such as density or concentration, are known to be small and typically occur at a molecular length scale. In contrast, theory predicts that non-equilibrium fluctuations grow very large both in amplitude and spatial size. On earth, the presence of gravity and buoyancy forces severely limits the development of the fluctuations. We will present the results of a 14-year long international collaboration on an experiment on non-equilibrium fluctuations in a single liquid and in a polymer solution under microgravity conditions. Non-equilibrium conditions are generated by applying a temperature gradient across millimetre-size liquid slabs. Phase modulations introduced by fluctuations are measured using a quantitative shadowgraph method, with the optical axis parallel to the temperature gradient. Thousands of images are analysed and their two-dimensional power spectra yield the fluctuation structure function S(q), once data are reduced accounting for the instrumental transfer function T(q). The mean-squared amplitude of the fluctuations exhibits an impressive power-law dependence at larger q and a crossover at low q showing that the fluctuation size is limited by the sample thickness. The shape of the structure function, its increase due to removing gravity, and its dependence on applied gradient are in reasonable agreement with available theoretical predictions.     

Interfacial Speciation Determines Interfacial Chemistry: X-ray-Induced Lithium Fluoride Formation from Water-in-salt Electrolytes on Solid Surfaces

Super-concentrated “water-in-salt” electrolytes recently spurred resurgent interest for high energy density aqueous lithium-ion batteries. Thermodynamic stabilization at high concentrations and kinetic barriers towards interfacial water electrolysis significantly expand the electrochemical stability window, facilitating high voltage aqueous cells. Herein we investigated LiTFSI/H₂O electrolyte interfacial decomposition pathways in the “water-in-salt” and “salt-in-water” regimes using synchrotron X-rays, which produce electrons at the solid/electrolyte interface to mimic reductive environments, and simultaneously probe the structure of surface films using X-ray diffraction. We observed the surface-reduction of TFSI⁻ at super-concentration, leading to lithium fluoride interphase formation, while precipitation of the lithium hydroxide was not observed. The mechanism behind this photoelectron-induced reduction was revealed to be concentration-dependent interfacial chemistry that only occurs among closely contact ion-pairs, which constitutes the rationale behind the “water-in-salt” concept.     

用塞曼双频激光器作光源的一种新颖长扫描表面的仪器设计

本文报道一套光学结构用于同步辐射反射镜表面轮廓高精度大面积的测量。采用了光学外差测量与接收技术,以伺服聚焦双折射透镜组分离“o”光与“e”光的聚焦区域,并再共轴组合比较其相位差,从而获得表面起伏的误差值。线性运动的测量工作台使镜面可测量范围从数微米到一米,而最小起伏量及曲率可达很高的测量精度。     

Über die katalytische Hydrierung von o-Chinondiacetaten

Zusammenfassung Durch Hydrierung von methylsubstituierten o-Chinondiacetaten gelingt es, reine Brenzcatechinmonoacetate zu erhalten. In mehreren Fällen tritt im Laufe der Hydrierung Umesterung ein; d. h. es liegt der ursprüngliche Oxosauerstoff in Form einer Acetatgruppierung vor. Es wird aber auch ein Fall beschrieben, bei dem diese Umesterung nicht eintritt.Herrn Prof. Dr. tech.A. Brukl zum 70. Geburtstag gewidmet (F. W.).     

Nested neutron microfocusing optics on SNAP

The high source intensity of the Spallation Neutron Source (SNS), together with efficient detectors and large detector solid angles, now makes possible neutron experiments with much smaller sample volumes than previously were practical. Nested Kirkpatrick–Baez supermirror optics provide a promising and efficient way to further decrease the useable neutron sample size by focusing polychromatic neutrons into microbeams. Because the optics are nondispersive, they are ideal for spallation sources and for polychromatic and wide bandpass experiments on reactor sources. Theoretical calculations indicate that nested mirrors can preserve source brilliance at the sample for small beams and for modest divergences that are appropriate for diffraction experiments. Although the flux intercepted by a sample can be similar with standard beam-guided approaches, the signal-to-background is much improved with small beams on small samples. Here we describe the design, calibration and performance of a nested neutron mirror pair for the Spallation Neutrons At Pressure (SNAP) beamline at the SNS. High-pressure neutron diffraction is but one example of a large class of neutron experiments that will benefit from spatially-resolved microdiffraction.