On-line liquid chromatography and circular dichroism detection of stereo-isomers of alpha-tocopherol derivatives generated by an electrochemical reaction

The electrochemical oxidation of (+/-)-alpha-tocopherol on a porous graphite electrode was performed in the presence of methanol, and successive separation and detection of the products were performed by an on-line liquid chromatography/mass spectrometry system. Three products were identified, one of which was determined to be alpha-tocopheryl quinone, because its m/z was 469 [M+Na](+). The other two products showed identical mass and UV spectra, and were suspected to be diastereomers of 9-methoxy-alpha-tocopheron, because their molecular weights were m/z 483 [M+Na](+), and also because it is known that the chemical oxidation of alpha-tocopherol by benzoyl peroxide or N-bromosuccinimide in the presence of methanol should provide 9-methoxy-alpha-tocopheron. To confirm that these two compounds were diastereomers, a circular dichroism detector was used. The signs of both peaks detected by the circular dichroism detector at 230 nm were opposite. In addition to observations of identical mass and ultraviolet spectra, these results indicated that the two products were diastereomers of 9-methoxy-alpha-tocopheron, whose stereochemistry is different at the newly generated chiral center of the 9-position. The on-line use of a circular dichroism detector with an electrochemical cell/liquid chromatography system may expand the utility of the system to study the metabolism of a chiral drug.     

Synthesis of n-alkyl-n-(1-hydroxyperoxyalkyl)nitrosamines by oxygenation of lithiated dialkylnitrosamines

N-Alkyl-N(1-hydroperoxyalkyl)nitrosamines were synthesized from N,N-dialkylnitrosamines by lithiation with lithium diisopropylamide, followed by oxygenation with oxygen in good yields.     

Polymerisation von Methylmethacrylat mit dem Benzoin-Pyridin-CCl4-Systemen. Substituenten- und L?sungsmittel-Effekte

Ohne Zusammenfassung     

SVL fluorescence and duschinskii effect in the S1 state of pyridine

SVL fluorescence spectra from principal bands in the S₁ state of pyridine h₅ and -d₅ were measured. A large displacement of the normal coordinate origin of v_6a and the Duschinskii rotation of v_10a and v_16a were established.     

Correction method for X-ray fluorescent determination of chromium in high-alloy steels and nickel-base alloys

Summary A new interelement correction method has been developed for the X-ray fluorescent determination of chromium in high-alloy steels and nickel-base alloys. The calibration equation which was derived from the JIS (Japanese Industrial Standards) model is applicable over wide ranges of compositions by preparation of only Fe-Cr binary standards.The new approach gave better accuracy than that based on Rasberry-Heinrich correction model. The accuracies (_d) were 0.08% for high-alloy steels and 0.14% for nickel-base alloys.

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Korrekturmethode für die röntgenfluorescenzspektrometrische Bestimmung von Chrom in hochlegierten Stählen und Nickellegierungen

Zusammenfassung Die Eich-Gleichung für das neue Korrekturverfahren wurde vom JIS-Modell (Japanese Industrial Standards) abgeleitet und ist über einen weiten Bereich von Zusammensetzungen durch Herstellung von lediglich binären Fe-Cr-Standards einsetzbar. Das beschriebene Verfahren bietet eine bessere Genauigkeit als die Methode nach dem Korrekturmodell von Rasberry-Heinrich. Sie betrug 0,08% für hochlegierte Stähle und 0,14% für Nickellegierungen.

     

Lattice vibrational spectra of vitreous silica densified by pressure

The results of the measurement of Raman scattering spectra and infra-red absorption spectra of densified vitreous silica are reported. Raman active-low frequency vibrations are largely changed by compression.     

Characterization of a laser-plasma extreme-ultraviolet source using a rotating cryogenic Xe target

A laser-plasma source for extreme-ultraviolet (EUV) light that uses a rotating cryogenic solid-state Xe target has been characterized. We focused on parameters at the wavelength of 13.5 nm with 2% bandwidth required for an EUV lithography source and investigated improvements of the conversion efficiency (CE). With the drum rotating, there was an increase in CE and less fast ions compared with the case for the drum at rest. It is considered that the Xe gas on the target surface can produce optimal-scale plasma, and satellite emission lines in Xe plasma effectively increase the EUV intensity, and the ion number is decreased by the gas curtain effect. The dependence of CE on the laser wavelength, laser energy and intensity also studied. As a result, the maximum CE was 0.9% at 13.5 nm with 2% bandwidth under the optimal condition. By continuous irradiation of a Nd:YAG slab laser at a repetition rate of 320 Hz and an average power of 110 W, the target continuously generated EUV light with an average power of 1 W at 13.5 nm with 2% bandwidth. The achieved performances provide valuable information for the design of a future EUV lithography source.     

Design and synthesis of 5'-deoxy-5'-phenyladenophostin A, a highly potent IP3 receptor ligand

[structure: see text] 5'-Deoxy-5'-phenyladenophostin A (5), designed as a useful IP(3) receptor ligand based on the previous structure-activity relationship studies, was successfully synthesized via two key stereoselective glycosidation steps. This compound proved to be a highly potent IP(3) receptor agonist.     

Clathrate-hydrate film growth along water/hydrate-former phase boundaries—numerical heat-transfer study

This paper describes two analytic models for the heat-transfer-controlled lateral growth of a clathrate-hydrate film along a planar interface between liquid water and an immiscible hydrate-forming fluid (or guest fluid), such as methane or carbon dioxide. The two models are different from each other only regarding the assumption of the film-front geometry. Either model assumes the film to be uniform and constant in thickness, ignoring possible changes in the thickness on a time scale relevant to its lateral growth. Another fundamental assumption employed in the model is that the film's hydrate-forming front is maintained at the hydrate/guest/water three-phase equilibrium temperature, thereby forming a two-dimensional temperature distribution in the surrounding three-phase space. Based on these assumptions, the transient, two-dimensional conductive heat transfer from the film front into the three phases is formulated and numerically solved to give the instantaneous rate of lateral film growth (i.e., the linear speed of the film-front) along the water/guest-fluid interface, while the film thickness is arbitrarily assumed as a fitting parameter. By comparing the predicted rates of film growth with the corresponding experimental data obtained with methane or carbon dioxide as the guest fluid, we estimated the film thickness to be about 10–20 μm for the methane hydrate at a pressure of 9.06 MPa and about 0.5 μm for the carbon-dioxide hydrate at a pressure of 5 MPa.