Intramolecular Friedel-Crafts type reaction of vinyloxiranes linked to an ester group

The 7-endo Friedel-Crafts cyclization of arylpropyl vinyloxiranes was found to proceed regio- and stereoselectively to afford polyfunctional seven-membered carbocycles in excellent yields.     

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.

---

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

     

ULTRA-LOW-LIGHT LEVEL CAMERA FOR PHOTON COUNTING IMAGING

Abstract— A new ultra-low-light level camera svstem has been developed to detect a single photon. Operation principles and some characteristics are presented.     

PVTx relationships and solid-liquid equilibria for the m-xylene-p-xylene system under high pressures

PVTx relationships of the m-xylene-p-xylene system have been measured with a glass piezometer at 283.15 and 298.15 K and pressures up to 200 MPa, or up to the point of solidification of m-xylene where this occurred at a lower pressure. Freezing pressures of m-xylene were observed as a discontinuity in the volume at increasing pressure. Approximate solid-liquid equilibria under high pressures were obtained from the freezing pressure measurement. The Carnahan-Starling-van der Waals (CS-vdW) equation of state was used to correlate the PVTx data. The solid-liquid equilibria under high pressures were calculated with the CS-vdW equation of state for the liquid phase and a simple equation of state for the solid phase. In order to test the validity of the calculation method, the solid-liquid equilibrium relationships of the benzene-cyclohexane system were also calculated. It was found that the solid molar volume should be treated as a function of temperature and/or pressure to fit the experimental data.     

Fundamental imaging properties of transillumination laser computed tomography based on coherent detection imaging method.

The coherent detection imaging (CDI) method uses the optical heterodyne detection technique. CW and single frequency lasers having long coherence lengths are used to exploit the maximum advantages of heterodyne detection, such as high directionality, selectivity and sensitivity. The CDI method based on optical heterodyne detection enables selective filtering of the directional coherence-retaining emergent photons, which leads to image reconstruction from projections, similar to X-ray computed tomography (CT). So far we have demonstrated the advantages and capabilities of the measurement technique for transillumination optical computed tomography in biomedicine. Here, we investigate the fundamental imaging properties of CDI method, such as its high directionality and quantitativeness, with preliminary physical phantom experiments. The results show that the CDI method satisfies the requirements for CT reconstruction under the first order approximation, and enables quantitative measurements in the sense that the relationship between estimated and actual concentration retains a satisfactory linearity.     

Sensitive determination of tyrosine metabolites, p-hydroxyphenylacetic acid, 4-hydroxy-3-methoxyphenyl-acetic acid and 4-hydroxy-3-methoxymandelic acid, by gas chromatography-negative-ion chemical-ionization mass spectrometry. Application to a stable isotope-labelled tracer experiment to investigate their metabolism in man

A method has been established for studying the dynamic metabolism of tyrosine to its metabolites in humans using a deuterium-labelled amino acid. Phenylalanine-d5 was administered orally to human subjects (5 mg/kg) and the levels of p-hydroxyphenylacetic acid-d4, 4-hydroxy-3-methoxyphenylacetic acid-d3, and 4-hydroxy-3-methoxymandelic acid-d3 excreted into urine every hour were determined by gas chromatography-negative-ion chemical-ionization mass spectrometry. This method was also applied to some patients with depression and it was possible to detect a slight alteration in the excretion of some compounds compared with the control.     

An application of fragment interaction analysis based on local MP2

We have developed a method named ‘fragment interaction analysis based on local MP2’ (abbreviated as FILM). This method enables us to decompose the interaction energy associated with dispersion interactions into contributions of localized occupied orbitals. In this study, the basis set dependence of the results derived from FILM was examined. The results suggested that the individual ratio of pair correlation energies of selected orbital pairs to the total dispersion interaction was almost independent of the basis set size. As an illustrative example, detailed analysis was performed on the human immunodeficiency virus type 1 protease complexed with lopinavir molecule.     

Dedekind symbols with plus reciprocity laws

Dedekind symbols are generalizations of the classical Dedekind sums (symbols), and the symbols are determined uniquely by their reciprocity laws, up to an additive constant. For Dedekind symbols D and F, we can consider two kinds of reciprocity laws: D(p,q)−D(q,−p)=R(p,q) and F(p,q)+F(q,−p)=T(p,q). The first type, which we call minus reciprocity laws, have been studied extensively. On the contrary, the second type, which we call plus reciprocity laws, have not yet been investigated. In this note we study fundamental properties of Dedekind symbols with plus reciprocity law F(p,q)+F(q,−p)=T(p,q). We will see that there is a fundamental difference between Dedekind symbols with minus and plus reciprocity laws.     

Enhancement of the Lewis acidity by substitution of sulfur-containing hetero aromatics in triarylboranes

Triarylboranes bearing two thiophene, dimethylthiophene, or benzothiophene units were synthesized. X-ray crystallographic analysis revealed the planar structure around the boron atom and non-bonding S-S interaction of the thiophene. They exhibited several intense absorption bands in the UV region. They were stable in the air for months and showed extremely strong Lewis acidities.