Quantification of 5-fluoro-2'-deoxyuridine in plasma by gas chromatography and negative-ion chemical ionization mass spectrometry.

A sensitive and specific method using gas chromatography and negative-ion chemical ionization mass spectrometry is described for the determination of 5-fluoro-2'-deoxyuridine (FdUrd) in plasma. The method is based on the formation of the pentafluoropropionyl derivative of FdUrd and of its stable isotope as internal standard after sample clean-up by solid-phase extraction and purification by high-performance liquid chromatography. Quantification in plasma was possible down to 300 pg/ml. The method was applied to the analysis of plasma levels of FdUrd in mice and dogs.     

O2>-DEPENDENT and -INDEPENDENT PHOTOOXIDATION OF QUERCETIN IN THE PRESENCE and ABSENCE OF RIBOFLAVIN and EFFECTS OF ASCORBATE ON THE PHOTOOXIDATION

Abstract— The self-sensitized photooxidation of quercetin was not suppressed by superoxide dismutase (SOD), but suppressed by ascorbate. During the suppression of quercetin photooxidation, ascorbate was oxidized. These results suggest the reduction of oxidized quercetin to quercetin by ascorbate. Quercetin photooxidation in the presence of both riboflavin and EDTA was suppressed by SOD by about 90%. The result suggests the participation of O₂^- in the photooxidation of quercetin. The participation of O₂^- in the quercetin oxidation was confirmed by a xanthine-xanthine oxidase system. Based on these results the physiological and pharmacological functions of quercetin are discussed.     

Longitudinal flow characteristics of vertically falling liquid films without concurrent gas flow

Flow characteristics of liquid films vertically falling along the outer wall of a circular tube without concurrent gas flow are experimentally studied, and attention is given to the longitudinally developing liquid film flow in the flow direction. Flow measurements are carried out by the methods of needle contact and electric capacity, and the obtained data are statistically processed.There exists a definite difference in flow characteristics such as wave motion patterns, film thicknesses, critical Reynolds number, and so on, depending strongly on the longitudinal distance in the flow direction as well as the liquid film Reynolds number. Measured probability distributions of interfacial waves can be well expressed by the functions of probability distribution statistically well-known as normal, logarithmic normal and gamma distributions. In terms of these functions, interfacial wave patterns are definitely classified over the whole experimental flow regime. As a rule, interfacial wave motion proceeds vigorously with increases of the longitudinal distance and Reynolds number; however, there exists a flow condition that wave fluctuation never grows up but declines regardless of an increase of Reynolds number.     

Photopolymerization mechanisms of acrylates in poly(methyl methacrylate) films

Photoinitiation processes for photopolymer coating layers have been investigated with respect to quenching rates by a laser flash photolysis using a total reflection cell, as well as to the decomposition‐quantum yield of a sensitizer dye and a radical‐generating reagent by a gel permeative chromatographic analysis (GPC); the sensitizer dye,2‐[p‐(diethylamino)styryl]naphtho[1,2‐d]‐thiazole (DNT) and the radical‐generating reagent, 2,2′‐bis(2‐chlorophenyl)‐4,4′,5,5′‐tetraphenyl‐1,1′‐bi‐1H‐imidazole (BI). From experiments using flash photolysis, strong fluorescence was observed at excitation of 355 nm laser pulse, though no transient absorption was observed. The fluorescence was statically quenched by BI with a quenching distance, R = 11 Å. From the experiments using GPC, the high‐quantum yield of decomposition (Φ) was obtained as Φ (DNT) = 3 and Φ (BI) = 9 for DNT and BI in the presence of acrylate monomers, trimethyrolpropanetri‐acrylate (TMPTA), at 488 nm exposure of 3.36 mJ cm which was required to form a photo‐hardened image, however no decomposition of DNT and BI was detected in the absence of TMPTA. The results imply that the photoinitiator system undergoes efficient static‐dye sensitization and efficient polymerization of the acrylate monomers accompanied with the chain decomposition of DNT and BI. Copyright © 1999 John Wiley & Sons, Ltd.     

The stereochemical investigation of 3-Aryl-4-methyl-1,2,3-oxathiazolidine 2-oxides using NMR

The title compounds were prepared by the reaction of the corresponding N-2-hydroxyisopropylanilines with thionyl chloride in the presence of triethylamine, and their pmr and cmr spectra were examined. On the basis of the chemical shifts due to the γ- and δ-effects, the stereochemical structures are discussed.     

Effect of surface charge of magnetite nanoparticles on their internalization into breast cancer and umbilical vein endothelial cells

Internalization of magnetite nanoparticles with diameter of approximately 40 nm into normal and cancer cells was examined by microscopic observation and flow cytometry. Magnetite nanoparticles were synthesized by hydrolysis in an aqueous solution containing ferrous chloride with organic amines as a base. It was demonstrated that the difference in surface charge of magnetite nanoparticles brought about the difference in uptake efficiency. The nanoparticles with positive charge showed higher internalization into human breast cancer cells than the nanoparticles with negative charge, while the degree of internalization of the positively- and negatively-charged nanoparticles into human umbilical vein endothelial cells (HUVEC) was almost the same.     

The β relaxation behavior of bisphenol-type resins

The β relaxation of a phenoxy resin and a number of related uncured and cured bisphenol-type epoxide resins was studied using a torsion pendulum. Two molecular mechanisms are proposed to contribute to the β relaxation in the range from ?55 to ?80°C. One is the motion of the hydroxyether group and the other is related to motions of the crosslink itself. The β-relaxation peak temperature was found to increase with the concentration of hydroxyether groups in the matrix. Motion of the crosslinks in the matrix gives rise to a contribution to the β peak at ?80°C. In addition, motion of the diphenyl propane group is proposed to result in a relaxation process at ca. ?110°C.     

Distribution of the amplitude of the self-oscillation of the electrical potential difference observed in an organic phase of a water-oil-water liquid membrane system.

The electrical potential differences were measured at various points in an organic phase of a water-oil-water liquid membrane system in which self-oscillations of an electrical potential difference occurred across a three-phases-liquid membrane by using an H-shaped cell. The electrical potential difference oscillated in the direction through the two aqueous phases, but not in its vertical direction. The amplitude of the self-oscillation greatly changed around the place where the horizontal tube was connected to the vertical tube, which had no surfactant.     

Theoretical study of trans-metalation process in palladium-catalyzed borylation of iodobenzene with diboron

Trans-metalation process in the palladium-catalyzed borylation of iodobenzene with diboron was theoretically investigated with the DFT method. Palladium(II) hydroxo phenyl complex, Pd(OH)(Ph)(PH(3))(2), and the fluoro analogue easily undergo the trans-metalation with diboron, B(2)(eg)(2) (eg = -OCH(2)CH(2)O-), to afford Pd(Ph)(Beg)(PH(3))(HO-Beg) and Pd(Ph)(Beg)(PH(3))(F-Beg), respectively, where B(2)(eg)(2) is adopted as a model of bis(pinacolato)diboron used experimentally. The electron re-distribution in the trans-metalation clearly indicates that the B-B bond scission occurs in a heterolytic manner. In the chloro analogue, PdCl(Ph)(PH(3))(2), however, the trans-metalation occurs in a homolytic manner with much difficulty, which is consistent with the experimental result. The significant differences between the chloro complex and the other hydroxo and fluoro complexes are easily interpreted in terms that hydroxo and fluoro ligands can form strongly bonding interaction with B(2)(eg)(2) but the chloro ligand cannot.