H+H2 thermal reaction: a convergence of theory and experiment

New experimental and theoretical rate constants for two isotopologs of the simplest chemical reaction, H+H2-->H2+H, are presented. The theoretical results are obtained using accurate quantum dynamics with a converged Born-Oppenheimer potential energy surface and include non-Born-Oppenheimer corrections. The new experiments are carried out using a shock tube and complement earlier investigations over a very large T range, 167 to 2112 K. Experiment and theory now agree perfectly, within experimental error, bringing this 75-year-old scientific problem to completion.     

Storage management strategies in large-scale quantum dynamics calculations

We discuss the computational strategies related to memory and disk storage and to data movement between memory and disk in large-scale quantum dynamics calculations. The discussion includes practical implementations of various strategies for handling large data sets on various supercomputer architectures.This paper was presented at the International Conference on The Impact of Supercomputers on Chemistry, held at the University of London, London, UK, 13–16 April 1987     

Determination of calcium, iron and magnesium in rabbit arteries by inductively coupled plasma atomic emission spectrometry

Regional variations in arterial concentrations of Ca, Mg and Fe may influence susceptibility to atherosclerosis. However, investigation of such hypotheses requires the availability of a sensitive, reliable method for the determination of elements in small arterial samples. These biologically important elements are determined in rabbit arteries by inductively coupled plasma atomic emission spectrometry (ICP-AES). Arterial samples (aorta and iliac arteries) are collected from 4- and 6- to 7-month-old rabbits fed rabbit chow. Closed-vessel microwave acid digestion is used to prepare the samples. The accuracy of the method is tested with a NIST bovine liver (1577b) standard reference material, and the amount of each metal found is within the reported uncertainty in the certified concentration. Also, the recovery from artery samples spiked with 0.5 μg of each metal is nearly 100% (96-105% Ca, 93-105% Fe, and 92-104% Mg). The simultaneous multielement detection of Ca, Fe and Mg at levels more than 1000-fold higher than the detection limit, in arterial samples weighing as little as 5 mg, suggests that this method may be applicable to very small clinical samples or arterial samples from very small animals.     

The extrapolation of one-electron basis sets in electronic structure calculations: how it should work and how it can be made to work

We consider the extrapolation of the one-electron basis to the basis set limit in the context of coupled cluster calculations. We produce extrapolation coefficients that produce much more accurate results than previous extrapolation forms. These are determined by fitting to accurate benchmark results. For coupled cluster singles doubles energies, we take our benchmark results from the work of Klopper that explicitly includes the interelectronic distance. For the perturbative triples energies, our benchmark results are obtained from large even-tempered basis set calculations.     

Potential of Total Reflection and Grazing Incidence XRF for Contamination and Process Control in Semiconductor Fabrication

 The actual detection limits of total reflection X-ray fluorescence (TXRF) are determined and compared to those of destructive physical analytical methods like secondary ion mass spectrometry (SIMS) and chemical methods like vapour phase decomposition in combination with inductively coupled plasma-mass spectrometry (VPD-ICP-MS). The elements Ca, Ti, Cr, Fe, Cu were analyzed on a Si wafer with 10 nm thermal oxide using TXRF and VPD-ICP-MS. The deviation of the TXRF and the VPD-ICP-MS results is less than 30%. The thickness, composition and density of a Co/Ti two-layer stack were determined using angle dependent total reflection and grazing incidence X-ray fluorescence (A-TXRF). The obtained data were compared with X-ray reflectometry (XRR) and energy filtered transmission electron microscopy (EFTEM). The agreement between TEM and A-TXRF is excellent for the determination of the thickness of the metal layers. From these results we conclude, that A-TXRF permits the accurate determination of composition, thickness and density of thin metallic layers. The results are discussed regarding detection efficiency, acquisition time, accuracy and reproducibility.     

Trace detection of tetrahydrocannabinol (THC) with a SERS-based capillary platform prepared by the in situ microwave synthesis of AgNPs

In the present study, an ultra-sensitive and highly reproducible novel SERS-based capillary platform was developed and utilized for the trace detection of tetrahydrocannabinol (THC). The approach combines the advantages of microwave-assisted nanoparticle synthesis, plasmonics and capillary forces. By employing a microwave-assisted preparation method, glass capillaries were reproducibly coated with silver nanoparticles in a batch fabrication process that required a processing time of 3 min without needing to use any pre-surface modifications or add surfactants. The coated capillaries exhibited an excellent SERS activity with a high reproducibility and enabled the detection of low concentrations of target molecules. At the same time, only a small amount of analyte and a short and simple incubation process was required. The developed platform was applied to the spectroscopic characterization of tetrahydrocannabinol (THC) and its identification at concentration levels down to 1 nM. Thus, a highly efficient detection system for practical applications, e.g., in drug monitoring/detection, is introduced, which can be fabricated at low cost by using microwave-assisted batch synthesis techniques.     

Radioaktivität in Peremesin

Peremesin und andere cerhaltige Substanzen enthalten oft Radionuklide der Thoriumzerfallsreihe. Es wird die radiochemische Abtrennung der Radiumisotope MsTh₁ und ThX durch Mitfälung beschrieben, die die qualitative und näherungsweise auch die quantitative Bestimmung der Muttersubstanz ²³²Th ermöglicht. Das untersuchte Peremesin enthielt etwa 4,2 mg Th/g Peremesin.     

A new totally reflecting X-ray fluorescence spectrometer with detection limits below 10?11 g

Summary A new type of energy dispersive X-ray-fluorescence spectrometer with totally reflecting sample support is presented. At this instrument the incident beam is reflected twice before it is directed towards the sample support. The detection limits in diluted solutions are below 0.1 ppb for about 20 metals. The influence of the matrix is discussed.

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Ein neuartiges totalreflektierendes Röntgenfluorescenz-Spektrometer mit Nachweisgrenzen unter 10^–11 g

Zusammenfassung Ein neuer Typ eines energiedispersiven Röntgenfluorescenzspektrometers mit totalreflektierendem Probenträger wird vorgestellt. Bei diesem Gerät wird der einfallende Strahl zweimal an Quarzspiegeln reflektiert, bevor er auf den Probenträger gelenkt wird. Die Nachweisgrenzen liegen bei günstiger Matrix für 20 Metalle unter 0,1 ppb. Der Einfluß der Matrix wird diskutiert.

     

Properties of interfacial films formed by succinylated legumin from faba beans (Vicia faba L.)

The influence of succinylation on the interfacial behaviour and emulsifying properties of the main storage protein (legumin) from faba beans was studied. Results of surface tension measurements and surface shear rheometry and properties of n-decane-water emulsions indicate an increased interfacial activity by succinylation whereby the 65% succinylated legumin was the most active derivative.

The equilibrium surface pressure Π_e increased from 16.6 to 20.21 mN m⁻¹ and the critical association concentration, i.e. the subphase concentration at which the plateau of Π_e was reached, strongly decreased with succinylation from 76.6 × 10⁻⁶ to 0.84 × 10⁻⁶ g ml⁻¹. Spread and adsorbed films of legumin exhibited purely viscous behaviour under shear stress whereby the viscosity strongly increased with succinylation (from 7.93 to 93.36 μN s m⁻¹). The droplet size of legumin-stabilized emulsions decreased and the coalescence stability increased with succinylation. The comparison with acetylated legumin supports the view that the dissociated but rather globular subunit is the most interfacially active component of acylated legumin.