Crystal Structure and Spectroscopic Investigations of POF3

Phosphoryl fluoride was characterized by Raman spectroscopy and X‐ray diffraction analysis. The X‐ray structure was obtained by in‐situ crystallization. Phosphoryl fluoride crystallizes in the trigonal space group P$\bar{3}$ m1 with two formula units in the unit cell. In the crystal structure zigzag chains are observed which are formed by intermolecular P–O contacts. The Raman spectra of neat and matrix isolated POF₃ display an extra line, which indicates intermolecular interaction in the solid state. Therefore quantum chemically calculation of a POF₃ oligomer was performed. The theoretical calculation indicates that the extra Raman line is caused by side splitting of the P–O valence vibration.     

The numerical integration of relative equilibrium solutions. The nonlinear Schrodinger equation

We analyse different error propagation mechanisms for conservativeand nonconservative time-integrators of nonlinear Schrödingerequations. We use a geometric approach based on interpretingwaves as relative equilibria.     

Necessary and sufficient conditions of harmonicity of functions of infinitely many variables (Jacobian case)

A criterion of harmonicity of functions in a Hilbert space is given in the case of weakened mutual dependence of the second derivatives. Ukrainian Scientific and Industrial Wood Working Concern, Kiev. Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 46, No. 6 pp. 785–788, June, 1994     

Interfacial biocatalysis on charged and immobilized substrates: the roles of enzyme and substrate surface charge

An enzyme charge ladder was used to examine the role of electrostatic interactions involved in biocatalysis at the solid-liquid interface. The reactive substrate consisted of an immobilized bovine serum albumin (BSA) multilayer prepared using a layer-by-layer technique. The zeta potential of the BSA substrate and each enzyme variant was measured to determine the absolute charge in solution. Enzyme adsorption and the rate of substrate surface hydrolysis were monitored for the enzyme charge ladder series to provide information regarding the strength of the enzyme-substrate interaction and the rate of interfacial biocatalysis. First, each variant of the charge ladder was examined at pH 8 for various solution ionic strengths. We found that for positively charged variants the adsorption increased with the magnitude of the charge until the surface became saturated. For higher ionic strength solutions, a greater positive enzyme charge was required to induce adsorption. Interestingly, the maximum catalytic rate was not achieved at enzyme saturation but at an invariable intermediate level of adsorption for each ionic strength value. Furthermore, the maximum achievable reaction rate for the charge ladder was larger for higher ionic strength values. We propose that diffusion plays an important role in interfacial biocatalysis, and for strong enzyme-substrate interaction, the rate of diffusion is reduced, leading to a decrease in the overall reaction rate. We investigated the effect of substrate charge by varying the solution pH from 6.1 to 8.7 and by examining multiple ionic strength values for each pH. The same intermediate level of adsorption was found to maximize the overall reaction rate. However, the ionic strength response of the maximum achievable rate was clearly dependent on the pH of the experiment. We propose that this observation is not a direct effect of pH but is caused by the change in substrate surface charge induced by changing the pH. To prove this hypothesis, BSA substrates were chemically modified to reduce the magnitude of the negative charge at pH 8. Chemical modification was accomplished by the amidation of aspartic and glutamic acids to asparagine and glutamine. The ionic strength response of the chemically modified substrate was considerably different than that for the native BSA substrate at an identical pH, consistent with the trend based on substrate surface charge. Consequently, for substrates with a low net surface charge, the maximum achievable catalytic rate of the charge ladder was relatively independent of the solution ionic strength over the range examined; however, at high net substrate surface charge, the maximum rate showed a considerable ionic strength dependence.     

The International System of Units��a case for reconsideration

The International System of Units (SI) follows a concept that goes back to Maxwell. At that time, a logic sound foundation of mathematics was not yet available. This has lead to concepts and terms that are contradictory and in conflict with today??s standard mathematical concepts. The inconsistencies that have evolved in metrology due to the lack of appropriate notions are pointed out. This is most important, as the metrology is a field that is internationally well organized under the umbrella of the Meter Convention, an international treaty for acting on all matters relating to units of measurement. Committees and working groups under the Meter Convention have a leading role in the elaboration of important metrological guides, among others the International Vocabulary of Metrology. Therefore, it is highly desirable that their publications use well-founded concepts and terminology. It is consensus that it is desirable to find a system of units on invariant properties of nature and not on human artifacts, e.g., the prototype of the kilogram. However, the current proposals to improve that are in conflict with standard scientific concepts. It is shown in the paper how these inconsistencies can be avoided. The argumentation is based on the interpretation of numbers developed by mathematicians like Cantor, Dedekind, Peano, and others that have led the logic foundation of mathematics with set and number theory. This foundation excludes dogmas that have been forwarded in the last century under the umbrella of the Meter Convention.     

Iodide determination with chalcogenide glass electrodes

Journal of Solid State Electrochemistry - The fabrication and characterisation of potentiometric chalcogenide glass electrodes with selectivity for iodide in aqueous media are reported. While such...     

The role of electrostatic interactions in protease surface diffusion and the consequence for interfacial biocatalysis

This study examines the influence of electrostatic interactions on enzyme surface diffusion and the contribution of diffusion to interfacial biocatalysis. Surface diffusion, adsorption, and reaction were investigated on an immobilized bovine serum albumin (BSA) multilayer substrate over a range of solution ionic strength values. Interfacial charge of the enzyme and substrate surface was maintained by performing the measurements at a fixed pH; therefore, electrostatic interactions were manipulated by changing the ionic strength. The interfacial processes were investigated using a combination of techniques: fluorescence recovery after photobleaching, surface plasmon resonance, and surface plasmon fluorescence spectroscopy. We used an enzyme charge ladder with a net charge ranging from -2 to +4 with respect to the parent to systematically probe the contribution of electrostatics in interfacial enzyme biocatalysis on a charged substrate. The correlation between reaction rate and adsorption was determined for each charge variant within the ladder, each of which displayed a maximum rate at an intermediate surface concentration. Both the maximum reaction rate and adsorption value at which this maximum rate occurs increased in magnitude for the more positive variants. In addition, the specific enzyme activity increased as the level of adsorption decreased, and for the lowest adsorption values, the specific enzyme activity was enhanced compared to the trend at higher surface concentrations. At a fixed level of adsorption, the specific enzyme activity increased with positive enzyme charge; however, this effect offers diminishing returns as the enzyme becomes more highly charged. We examined the effect of electrostatic interactions on surface diffusion. As the binding affinity was reduced by increasing the solution ionic strength, thus weakening electrostatic interaction, the rate of surface diffusion increased considerably. The enhancement in specific activity achieved at the lowest adsorption values is explained by the substantial rise in surface diffusion at high ionic strength due to decreased interactions with the surface. Overall, knowledge of the electrostatic interactions can be used to control surface parameters such as surface concentration and surface diffusion, which intimately correlate with surface biocatalysis. We propose that the maximum reaction rate results from a balance between adsorption and surface diffusion. The above finding suggests enzyme engineering and process design strategies for improving interfacial biocatalysis in industrial, pharmaceutical, and food applications.     

Fluorescence Studies of Host–Guest Interaction of a Dansyl Amide Labelled Calix[6]arene

The fluorescence behavior of a calix[6]arene with a dansyl group as fluorescence marker (C6-DA) was investigated with respect to the inclusion properties of alkaloids as atropine and cocaine. A strong hypsochromic shift of the fluorescence band and a strong increase in fluorescence intensity is connected with the interaction of atropine to the lower rim of the C6-DA. The fluorescence increase is saturated at an atropine concentration above the 1:1 complex formation. Addition of cocaine to the complexed atropine-C6-DA leads to a decrease of the fluorescence intensity which could be explained by an exchange mechanism of the complexed molecules. The complexation of the atropine (the “belladonna effect”) is interpreted by electrostatic interaction (proton transfer from the carboxylic group to the nitrogen) with important contribution from hydrogen bonding by the guest OH-group.     

The Cauchy problem for the wave equation with Lévy Laplacian

We present the solution of the Cauchy problem (the initial-value problem in the whole space) for the wave equation with infinite-dimensional Lévy Laplacian Δ _L , $$ \frac{{\partial ^2 U(t,x)}} {{\partial t^2 }} = \Delta _L U(t,x) $$ in two function classes, the Shilov class and the Gâteaux class.