Synthesis of (±)-dimethyl curvularin based on the palladium-catalyzed carbonylation of 3,5-dimethoxybenzyl chloride using a butadiene telomer as a building block

Palladium-catalyzed carbonylation of 3,5-dimethoxybenzyl chloride (13) with benzyl 7-hydroxyoctanoate (12) afforded benzyl 7-(3,5-dimethoxyphenylacetoxy)octanoate (6) in 70% yield, which is the precursor of Curvularin (4). The ester (12) was easily prepared from the butadiene telomer obtained by the palladium-catalyzed reaction of butadiene with acetic acid.     

Studies on vocal fold injection and changes in pitch associated with alcohol intake

The current study was carried out with particular emphasis on the association between phonetic function tests and alterations in the appearance of the hypopharyngeal and laryngeal mucosa, such as capillary dilatation, edema, and vocal fold injection after alcohol intake. The results demonstrated the occurrence of previously unrecognized pathophysiological changes associated with synchronous phonetic functions in the vocal pathway after alcohol intake. Serum ethanol and aldehyde concentration levels were evaluated hourly for 2.5 h after ingestion of alcohol. When an electronystagmogram showed the typical pattern of alcohol intake, the study was initiated. Occasionally, rhinography was performed on subjects complaining of a stuffy nose after alcohol intake.     

Mössbauer spectroscopic study of frozen solutions of57Co using a specially designed cryostat for time differential coincidence emission Mössbauer spectroscopy of237Np

Experiments on the⁵⁷Fe Mössbauer effect in frozen solutions were carried out in order to demonstrate the capabilities of a cryostat which was developed for the emission Mössbauer spectroscopy of²³⁷Np. We confirmed the existence of an aliovalent state of⁵⁷Fe in the temperature range from 5.5 to 35 K. However, the relative amounts of Fe(II) and Fe(III) in the frozen matrix were almost constant for the temperature range from 5.5 to 150 K. The design, operation and capabilities of the cryostat are also described.     

Self‐polyaddition of triethylsilyl perfluoroisopropenyl ether

The results on radical self‐polyaddition reactivity of two trialkylsilyl perfluoroisopropenyl ethers, triethysilyl perfluoroisopropenyl ether [CF₂?C(CF₃)OSi(C₂H₅)₃] (FTEE) and dimethylphenylsilyl perfluoroisopropenyl ether [CF₂?C(CF₃)OSi(CH₃)₂C₆H₅] (DMPE), and two perfluoroisopropenyl carboxylates, 2‐butyroxypentafluoropropene [CF₂?C(CF₃)OCOC₃H₇] (BuFPP) and 2‐(methoxyacetoxy)pentafluoropropene [CF₂?C(CF₃)OCOCH₂OCH₃] (MFPP), are described. Radical self‐polyaddition of FTEE afforded a polymer as high as 1.87 × 10⁴ in molecular weight in the presence of radical generators such as benzoyl peroxide and di‐tert‐butyl peroxide. DMPE gave only addition products with initiating radicals. BuFPP and MFPP scarcely yielded even addition products with radical. The mechanism that the self‐polyaddition of FTEE was initiated by the addition of radical onto the perfluoroisopropenyl group followed by a 1,5‐shift to afford a methyl radical that attacked the perfluoroisopropenyl group of another FTEE molecule is proposed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2743–2754, 2003     

Analytical model of longitudinal tire traction in snow

An analytical model to estimate longitudinal traction of a tire in snow was developed and verified to have good predictability in comparison with measurements. Snow traction of a tire is composed of four kinds of forces in this model: braking force attributable to snow compression, shear force of snow in void (space between tread blocks), frictional force, and digging force (edge effect generated by sipes and blocks). The mechanical characteristics of snow were considered in the prediction of braking force and shear force, but were not considered in the prediction of other forces. The contribution of shear force of snow in void and the frictional force was large in static traction (traction just before a tire slips). On the other hand, the contributions of digging force and frictional force were large in situations involving high slip ratios.     

Extension of derivations in the algebra of compact operators

Let C(H) denote the C¹-algebra of all compact linear operators on a complex Hilbert space H. If δ is a closable ¹-derivation in C(H) which anti-commutes with an involutive ¹-antiautomorphism α and has finite spatial deficiency-indices, then there exists an infinitesimal generator δ₀ of a continuous action of R on C(H) which extends δ and anti-commutes with α. This is an analogue of the von Neumann's theorem which states that a symmetric operator commuting with a conjugation J has a self-adjoint extension which also commutes with J.     

Selectivity enhancement for trans-2-(2,3-anthracenedicarboximido)-cyclohexane-derived diastereomers in HPLC by using an ordered organic stationary phase.

2-(2,3-anthracenedicarboximido)cyclohexane derivatives (AC) have been known as the evolutionary diastereomerizing reagents for enantiomer discrimination in HPLC with ODS. However, a substantial separation of diastereomers can be observed only at lower temperatures, such as -40 degrees C. Therefore, in this work, poly(octadecyl acrylate)-grafted silica, ODAn was applied as an alternative stationary phase to ODS for the separation of AC-derived diastereomers. As a result, complete separation was achieved even under the conventional condition: for example, methanol as the mobile phase and 0 degrees C as the column temperature. An investigation on the temperature dependency of the selectivity demonstrated that ODAn shows a remarkable increase in selectivity at temperatures below 30 degrees C, which almost agreed with the peak-top temperature of the endothermic peak in a DSC thermogram for ODA35 immersed in a mobile phase. The better separation would be derived from a highly ordered structure of ODAn and a carbonyl-pi interaction with AC-derived diastereomers.     

Regio-controlled hydrogen-deuterium exchange of biologically important indoles under uv irradiation

Photochemical hydrogen-deuterium exchange reaction of biologically important indoles is reported. The regioselectivity of the photodeuteration was found to be controlled by the ammonium group of the side chain.