Repetitive spectral subtraction method for the spectrophotometric determination of rare earth elements

Summary A new multiwavelength data-analysis method for the determination of multicomponent mixtures, the repetitive spectral subtraction method (RSSM), is proposed. In RSSM, spectral data are obtained at evenly spaced wavelengths in the range of interest, and the analysis of the spectrum is performed as repetitive determination-subtraction cycle. In the determination step, the series of data in the narrow wavelength range is used, which is specified as to include the most characteristic or the largest peak for each component. Assuming a linear background, the target component, which can be a small group of components, is simultaneously determined together with co-existing components. In the next subtraction step, the calculated contribution of the component is subtracted from the spectral data in the whole measured wavelength range, and the component is assigned as determined and is excluded from the following analysis. This determination-subtraction cycle is repeated until all the components are determined.With RSSM, a mixture of many components can be precisely determined by the use of most information contained in the spectrum. The accuracy of determination can be improved by automatic estimation of the background and the gradual decrease of interferences. In order to demonstrate the usefulness of RSSM, the 8 rare earth elements (Pr, Nd, Sm, Eu, Dy, Ho, Er, Tm) in the model mixtures were determined by spectrophotometry, and the results were compared with those of the usual correction factor method and the derivative method. Furthermore, the 8 rare earth elements were determined in ores, monazite and xenotime.

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Spektralphotometrische Bestimmung von Seltenen Erden mit Hilfe eines Verfahrens der wiederholten Subtraktion

     

A microsensor for adenosine-5′-triphosphate pH-sensitive field effect transistors

The sensor for adenosine-5′-triphosphate (ATP) is based on H⁺-ATPase immobilized via a polyvinylbutyral resin on a pH-sensitive field effect transistor. A linear relationship was obtained between the initial rate of change of the differential gate output voltage and the logarithm of the ATP concentration over the range 0.2–1.0 mM ATP. The optimum pH was 9.0 at 40°C but pH 7.0 was preferred for routine measurements. Only slight responses were obtained for 1 mM glucose, creatinine or urea. The ATP-sensing system exhibited a response to 1 mM ATP for at least 18 days.     

Discussion of substantially identical gel points among multiallyl monomers based on characterization of resultant network polymer precursors consisting of oligomeric primary polymer chains

No difference in the actual gel points was substantially observed among three isomeric diallyl phthalates such as diallyl phthalate (DAP), diallyl isophthalate, and diallyl terephthalate (DAT); this interesting gelation behavior was discussed further in terms of the correlation between gelation and the difference in cyclization modes, and also, the difference in reactivity between the uncyclized and cyclized radicals for cross‐linking. In the present work, we tried to extend the preceding discussion to the polymerization of triallyl trimellitate (TAT) because the molecular structure of TAT is presumed to essentially involve the characteristics of three isomeric diallyl phthalates and, therefore, the enhanced gelation was expected in TAT polymerization. However, no enhancement of gelation was observed. For a full understanding of the gelation in multiallyl cross‐linking polymerization, we explored further the polymerizations of DAP, DAT, and TAT, especially focusing on the characterization of resultant network polymer precursors (NPPs) using SEC‐MALLS‐viscometry providing the correlation of [η] versus M_w of fractionated samples. Notably, the structure of NPP consisting of oligomeric primary polymer chains generated from specific allyl polymerization would become core‐shell type dendritic with the progress of polymerization. The correlation between delayed gelation and decreased reactivity of dendritic NPP for intermolecular cross‐linking is discussed. Conclusively, the reactivity for intermolecular cross‐linking between NPPs decreased with the progress of polymerization leading to a delayed gelation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2871–2881, 2009     

Permeability control in electro‐sensitive microcapsules with immobilized ferroelectric liquid crystalline segments

Nylon‐polystyrene microcapsules with immobilized ferroelectric liquid crystalline segments were prepared, and permeability control of an encapsulated core material was investigated under an external electric field. A ferroelectric liquid crystal monomer possessing both mesogenicity and chirality responded effectively to the external electrical field. Permeation of the material (oxprenolol) contained in the inner aqueous core of the microcapsules was enhanced under a weak electric field (2 V). Furthermore, the permeability of oxprenolol did not depend on the external electric field in the absence of the ferroelectric liquid crystal segments. To clarify the controlled‐release mechanism of the core material, the light transmittance of the polymer membranes was quantitatively evaluated under an external electric field using a handmade polarized light transmittance apparatus. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1749–1757, 2008     

A generating function for sums of multiple zeta values and its applications

A generating function for specified sums of multiple zeta values is defined and a differential equation that characterizes this function is given. As applications, some relations for multiple zeta values over the field of rational numbers are discussed.

     

Computation of transition to turbulence in the compression stage of a reciprocating engine

The transition to turbulent flow in the compression stage of a reciprocating engine is studied by obtaining the finite-difference numerical solutions to the governing Navier-Stokes equations without using explicit turbulence models. A computational method is developed under the assumption that the flow is in a low-subsonic regime with strong compression. The numerical method is a simple extension of the well known MAC method. Computations were performed for three different chamber geometries at the engine speed of 1400 rpm. The results of the computations clearly demonstrate the transient process in which large tumbling vortices break down into smaller ones near the end of the compression process. The transition process is also caught experimentally by using Mach-Zehnder interferometry.     

Influence of the solvent on nature of gate effect in molecularly imprinted membrane

The solute diffusive permeability in a thin layer of a molecularly imprinted polymer (MIP) is affected by specific binding of the MIP with a template. This phenomenon, termed the "gate effect," would be widely applicable for the development of novel biomimetic sensors. However, the mechanism underlying the gate effect is not totally understood. We present here investigation of the role of specific adsorption of a template and solution content in MIPs on the gate effect. A molecularly imprinted self-supporting membrane was formed by copolymerization of methacrylic acid, 2-vinylpyridine, and triethyleneglycol dimethacrylate in the presence of L- (or D-) phenylalanine as a template. The template adsorbed by membrane with degree of enantio-selectivity in a mixed solvent of methanol and water. The amount of adsorption and binding selectivity showed little sensitivity to the solvent composition. The solution content in the membrane increased with increasing the methanol concentration of the solvent following a sigmoid curve with an inflection point at methanol concentration of 20 wt.%. The content increased in the presence of the template at methanol concentrations higher than the inflection point, and decreased at lower methanol concentrations. The creatinine permeability across the membrane estimated by batchwise dialysis increased in the presence of the template at 50 wt.% methanol in the solvent, and did not change at 20 wt.%. There was no permeability for creatinine in the pure water solvent. Both the solution content and the permeability were not affected by the presence of the enantiomer of the template. The results show that the choice of solvent controls more strongly the nature of the gate effect than the specific binding of the template.     

H Nmr Spectra of Oligosaccharide Substituted Cyclodextrins

ABSTRACT

¹H NMR spectra of some oligosaccharide substituted cyclodextrins composed of only α-D-glucose units are analysed. Chemical shifts of protons of each glucosyl group of the chain were determined by experiments with the HOHAHA pulse technique. In spite of the similar kinds of protons, dispersion of chemical shifts is observed. The most dispersed proton is the anomeric proton, and the largest change in the chemical shifts is 0.5 ppm.