Application of microdialysis for study of caffeine distribution into brain and cerebrospinal fluid in rats.

The usefulness of microdialysis was examined for the chronological determination of caffeine concentration in the brain and cerebrospinal fluids (CSF) following intravenous administration of caffeine in rats. The recovery percent of caffeine by microdialysis, the concentration ratio of caffeine in the dialysate against that in the brain tissue or CSF was determined. The recovery percent was proved to be constant at 5 different steady-state plasma concentrations of caffeine (0.1-280 nmol/ml) and in different collecting periods of dialysate ranging from 30 s to 10 min. The mean recovery percent in the brain and CSF were 10.9 and 13.1%, respectively. Thus, microdialysis was proved useful for determination of drug concentration in the tissue and biological fluids with time resolution of more than 30 s. The microdialysis method was then applied for the chronological determination of caffeine concentration in the brain and CSF following intravenous bolus administration. The estimated caffeine concentration in the brain and CSF was the same as those obtained by direct determination in isolated brain and CSF, respectively. Transfer of caffeine from plasma to brain and CSF were further pharmacokinetically analyzed using a modified 2-compartment model. In this kinetic model, the transfer of caffeine between the CSF and brain was neglected, since the mutual transfer of caffeine was not detected in in vivo experiments. Calculated curves were well fitted on observed caffeine concentrations in the plasma, brain and CSF.     

Sensitive H(2) detection by use of thermal-lens Raman spectroscopy without a tunable laser

A new nonlinear Raman spectroscopy technique for trace-gas detection was proposed and demonstrated. The technique involved the use of a thermal-lens detection scheme to monitor thermal emission from the stimulated Raman process. We termed this technique thermal-lens Raman spectroscopy, and it was combined with a novel scheme involving a nonlinear Raman spectroscopy without a tunable laser. This technique was applied to detecting trace hydrogen molecules in the atmosphere by use of a pulsed Nd:YAG laser and a continuous-wave He-Ne probe laser. A detection limit of 9 parts in 10(6) was attained.     

Molecular structure of 1,1-difluoroethylene as determined by gas phase electron diffraction and microwave data

The structure of 1,1-difluoroethylene was determined, from gas phase electron diffraction data obtained independently in Leiden and Tokyo and the rotational constants of F₂CCH₂, F₂CCHD and F₂CCD₂ derived from the microwave study by Chauffoureaux. The two electron diffraction data agreed without significant discrepancy. From a joint least squares analysis of the diffraction and microwave data, the following r_g bond distances and r_z bond angles were derived: CC = 1.340 ± 0.006 Å, C-F = 1.315 ± 0.003 Å, C-H = 1.091 ± 0.010 Å, ∠C-C-F = 124.7 ± 0.3°, ∠C-C-H = 119.0 ± 0.4°, where the uncertainties represent estimated limits of error.     

Selective and Efficient Iodination of the p-Positions of Calix[4]arene Derivatives

Selective and very convenient methods of iodination of calix[4]arenes using ICl or NIS have been demonstrated, preparing mono(p-iodo) and 1,3-di(p-iodo) derivatives of calix[4]arenecrown-4 and -5, as well as mono(p-iodo) derivative of tris(O-propyl)calix[4]arene in good yields.     

H2 generation during dry grinding of kaolinite

H2 generation during mechanochemical treatment of kaolinite by dry grinding was examined by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and BET surface area measurement. The H2 concentration in the mill pot, measured by gas chromatography, increased with grinding time up to a maximum concentration of 156 ppm (0.35 micromol) after 600 min. This H2 generation is considered to occur as a result of three processes: (1) structural destruction characterized by the delamination and loss of hydroxyl groups as a result of dry grinding, (2) transformation of liberated hydroxyls into water molecules by mechanochemical effects such as prototropy, and (3) H2 generation through reaction between surface water molecules and mechanoradicals created by the rupture of Si-O or Al-O-Si bonds. Although the surface area plateaued after 240 min grinding, the H2 concentration continued to increase, indicating that surface mechanoradicals are created during this later grinding stage. Thus, H2 generation can be used as an indicator of mechanoradical formation during mechanochemical treatment.     

Hair analysis of nicotine and cotinine for evaluating tobacco smoke exposure by liquid chromatography-mass spectrometry

A simple liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for the determination of nicotine and cotinine in human hair was established. In the procedure, a hair sample (10 mg) was washed with dichloromethane and digested in 2.5 M sodium hydroxide. The digest was extracted with dichloromethane and then 25 mM hydrochloric acid in methanol was added to the extract, to prevent loss of analytes. The solution was evaporated and redissolved in the mobile phase, methanol/10 mM ammonium acetate (30/70, v/v). A 20 microL aliquot of redissolved solution was subjected to analysis. Nicotine and cotinine in human hair were quantified by using deuterated analytes as internal standards. The quantification limits were 8 microg/L for nicotine and 0.9 microg/L for cotinine. The proposed method was applied to measure the concentrations of nicotine and cotinine in hair of smokers and non-smokers to evaluate their self-reported smoking and exposure to environmental tobacco smoke. In both cases, the method provided good selectivity, accuracy and precision.     

Involvement of human small fragment nuclease in the resistance of human cells to UV-C-induced cell death

Human small fragment nuclease (Sfn) is one of the cellular proteins that were reported to degrade small, single-stranded DNA and RNA. However, the biological role of Sfn in cellular response to various stressors such as UV-C (mainly 254 nm wavelength ultraviolet ray) remains unclear. We have examined whether modulation of human SFN gene expression affects cell survival capacity against UV-C-induced cell death, analyzing colony survival ability in UV-C-sensitive human RSa cells treated with short double-stranded RNA (siRNA) specific for SFN messenger RNA (mRNA). The expression levels of SFN mRNA in the siRNA-treated RSa cells decreased to about 15% compared with those in the control siRNA-treated cells. The siRNA-treated RSa cells showed lower colony survival and higher activity of caspase-3 after UV-C irradiation than the control siRNA-treated RSa cells. Furthermore, the removal capacity of cyclobutane pyrimidine dimers (CPD) in the siRNA-treated RSa cells decreased compared with the control siRNA-treated RSa cells. There was no difference in the colony survival and CPD removal capacity after UV-C irradiation between the control siRNA-treated RSa cells and mock-treated RSa cells. These results suggest that SFN expression is involved in resistance of RSa cells to UV-C-induced cell death through the roles it plays in the DNA repair process.     

Thermoresponsive shuttling of rotaxane containing trichloroacetate ion

A thermoresponsive rotaxane shuttling system was developed with a trichloroacetate counteranion of an ammonium/crown ether-type rotaxane. Chemoselective thermal decomposition of the ammonium trichloroacetate moiety on the rotaxane yielded the corresponding nonionic rotaxane accompanied by a positional change of the crown ether on the axle. The rotaxane skeleton facilitated effective dissociation of the acid, markedly lowering the thermal decomposition temperature.