Direct Observation of the Electroadsorptive Effect on Ultrathin Films for Microsensor and Catalytic‐Surface Control

Microchemical sensors and catalytic reactors make use of gases during adsorption in specific ways on selected materials. Fine‐tuning is normally achieved by morphological control and material doping. The latter relates surface properties to the electronic structure of the bulk, and this suggests the possibility of electronic control. Although unusual for catalytic surfaces, such phenomena are sometimes reported for microsensors, but with little understanding of the underlying mechanisms. Herein, direct observation of the electroadsorptive effect by a combination of X‐ray photoelectron spectroscopy and conductivity analysis on nanometre‐thick semiconductor films on buried control electrodes is reported. For the SnO₂/NO₂ model system, NO₃ surface species, which normally decay at the latest within minutes, can be kept stable for 1.5 h with a high coverage of 15 % under appropriate electric fields. This includes uncharged states, too, and implies that nanoelectronic structures provide control over the predominant adsorbate conformation on exterior surfaces and thus opens the field for chemically reactive interfaces with in situ tunability.     

Further results on integral generalized inverses of integral matrices

This paper further investigates integral generalized inverses of integral matrices.     

Decreased crystallinlty of hydrocellulose I during alkali-catalyzed depolymerization

When cotton hydrocellulose I is extracted with refluxing aqueous 0.6 M sodium hydrogen carbonate, alkali-catalyzed depolymerization occurs, causing a 40% loss of weight. An overall decrease in x-ray diffractive crystal-Unity of the residue has been previously reported. However, since degradation is presumed to occur preferentially in a less-ordered or “amorphous” domain of the polymer, an increase in crystallinity would have been expected. We have now shown that a diminished crystallinity index is exhibited by replicate samples, but does not occur during refluxing in the absence of alkali. Furthermore, it is not an artifact caused by drying conditions or by environmental or instrumental instability during measuring. The anomalous change in crystallinity may be accounted for by an increase in the ratio of surface area to volume of crystallites during degradation. A higher ratio would necessarily produce a decrease in crystallinity through an enhanced contribution from the disordered surface component to the scattering. Experimental evidence for this hypothesis is provided by the decrease now found in the effective lateral crystallite dimension perpendicular to the 002 plane.     

Pyrrolizidine-Derived Alkaloids: Highly Toxic Components in the Seeds of Crotalaria cleomifolia Used in Popular Beverages in Madagascar

Seeds of Crotalaria cleomifolia (Fabaceae) are consumed in Madagascar in preparation of popular beverages. The investigation of extracts from the seeds of this species revealed the presence of high amounts of alkaloids from which two pyrrolizidine-derived alkaloids were isolated. One of them was fully characterized by spectroscopic and spectrometric methods, which was found to be usaramine. Owing to the high toxicity of these alkaloids, issuing a strong warning among populations consuming the seeds of Crotalaria cleomifolia must be considered.     

Three-dimensional effects on regular reflection in steady supersonic flows

The reflection of shock waves between two symmetrical wedges is investigated for the case of three-dimensional flows. Oblique shadowgraphs at various optical angles of yaw and pitch were used to examine the nature of fully three-dimensional flows, with wedge aspect ratios as low as 0.25 being considered. These images were used to construct surface models of the overall flow field for various reflection patterns and aspect ratios, which provides a visual indication of the flow field shape. For a Mach number of 3.1, and suitable wedge angles, the flow field with regular reflection on the tunnel centreline and Mach reflection further out is examined. The point of transition from regular reflection to the peripheral Mach surfaces is identified for various wedge angles and aspect ratios. It is shown that the transition points move outwards from the central plane as the aspect ratio decreases. This shows that three-dimensional flows favor regular reflection, because of the increasing curvature of the incident shock as the wedge becomes narrower, causing a decrease in the local angle of incidence. The height of the Mach stem is shown to be highly dependent on the geometry of the test wedge models. The Mach stem height decreases with aspect ratio due to the three-dimensional relieving effect, where the increase in lateral flow relieves the pressure over the surfaces of the wedges. Experimental evidence of the existence of the strong oblique shock solution in steady flows is presented.Received: 7 July 2003, Revised: 20 October 2003, Accepted: 6 November 2003, Published online: 10 February 2004PACS: 47.40.Nm Correspondence to: B.W. Skews     

Fast‐scanning high‐flux microprobe for biological X‐ray fluorescence microscopy and microXAS

There is a growing interest in the biomedical community in obtaining information concerning the distribution and local chemical environment of metals in tissues and cells. Recently, biological X‐ray fluorescence microscopy (XFM) has emerged as the tool of choice to address these questions. A fast‐scanning high‐flux X‐ray microprobe, built around a recently commissioned pair of 200 mm‐long Rh‐coated silicon Kirkpatrick–Baez mirrors, has been constructed at BioCAT beamline 18ID at the Advanced Photon Source. The new optical system delivers a flux of 1.3 × 10¹² photons s^?1 into a minimum focal spot size of ～3–5 µm FWHM. A set of Si drift detectors and bent Laue crystal analyzers may be used in combination with standard ionization chambers for X‐ray fluorescence measurements. BioCAT's scanning software allows fast continuous scans to be performed while acquiring and storing full multichannel analyzer spectra per pixel on‐the‐fly with minimal overhead time (<20 ms per pixel). Together, the high‐flux X‐ray microbeam and the rapid‐scanning capabilities of the BioCAT beamline allow the collection of XFM and micro X‐ray absorption spectroscopy (microXAS) measurements from as many as 48 tissue sections per day. This paper reports the commissioning results of the new instrument with representative XFM and microXAS results from tissue samples.     

Periodic pulses of calcium ions in a chemical system

By coupling the bromate-sulfite-ferrocyanide oscillating chemical reaction with the complexation of calcium ion by EDTA, we construct a system that generates periodic pulses of free Ca(2+) with an amplitude of 2 orders of magnitude and a period of ca. 20 min. These pulses may be observed either with a calcium ion-selective electrode or with Arsenazo(III) as an indicator. We describe the systematic design procedure and the properties of this first abiotic calcium-based chemical oscillator.     

Development of a novel high-throughput assay for the investigation of GlyT-1b neurotransmitter transporter function

The glycine transporter (GlyT-1b) is a Na(+)/Cl(-)-dependent electrogenic transporter which mediates the rapid re-uptake of glycine from the synaptic cleft. Based on its tissue distribution, GlyT-1 has been suggested to co-localise with the NMDA receptor where it may modulate the concentration of glycine at its co-agonist binding site. This data has led to GlyT-1 inhibitors being proposed as targets for disorders such as schizophrenia and cognitive dysfunction. Radiolabelled uptake assays (e.g. [(3)H]glycine) have been traditionally used in compound screening to identify glycine transporter inhibitors. While such an assay format is useful for testing limited numbers of compounds, the identification of novel glycine uptake inhibitors requires a functional assay compatible with high-throughput screening (HTS) of large compound libraries. Here, the authors present the development of a novel homogenous cell-based assay using the FLIPR membrane potential blue dye (Molecular Devices) and FLEXstation. Pharmacological data for the GlyT-1 inhibitors Org 24598 and ALX 5407 obtained using this novel electrogenic assay correlated well with the conventional [(3)H]-glycine uptake assay format. Furthermore, the assay has been successfully miniaturised using FLIPR(3) and therefore has the potential to be used for high-throughput screening.     

Vibration of an elastic tensegrity structure

The dynamic behavior of a simple elastic tensegrity structure is examined, in order to validate observations that the natural damping of the elastic elements in such a structure is poorly mobilized, due to the natural flexibility of the equilibrium position of the structure. It is confirmed, analytically and numerically, that the energy decay of such a system is slower than that of a linearly-damped system.     

The preparation and properties of neutral diamide ionophores for group IIa metal cations

The preparation of a series of neutral ligands featuring ether and N-methyl-N-carbethoxypentylamide groups is described. These ligands as well as related ones bearing other diamide groups are shown to selectively chelate Group IIA cations by picrate extraction from water to methylene chloride. The changes in UV absorption of aromatic rings and amide groups in the ligands upon titration with metal salts in methanol allow the estimation of the stoichiometry of complexation and the ordering of cation binding. The observed selectivity sequences of cation extraction and binding are briefly discussed. Preliminary proton and ¹³C NMR studies on the effect of addition of Group IIA cation salts to several of the ligands in methanol suggest that most of the complexation occurs at the central ether and amide groups. ¹³C NMR T₁ changes by the Inversion Recovery Fourier Transform method are in agreement with the cation-induced shift data.