Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.     

Composition spread metal thin film fabrication technique based on ion beam sputter deposition

A composition spread metal thin film fabrication technique based on ion beam sputter deposition method was developed. The technique enables us to fabricate any desired part or a complete binary/ternary composition spread metal thin films onto a single substrate by sequentially sputtering different target materials. Composition spread metal thin films can be deposited directly on a dielectric film in patterned electrode shape for C-V and I-V measurements. The system could be especially useful in the search for new multi-component metal gate materials.     

Self-assembly patterning of colloidal crystals constructed from opal structure or NaCl structure

We developed a novel self-assembly process to fabricate an orderly array of particle wires constructed from a close-packed colloidal crystal without preparation of patterned templates. A substrate was immersed vertically into a SiO2 colloidal solution, and the liquid surface moved downward upon evaporation of solution. Particles formed a mono-/multiparticle layer, which was cut by the periodic drop-off of solution. The orderly array of particle wires was successfully fabricated, showing the suitability of the self-assembly process for the fabrication of nano-/microstructures constructed from nano-/microparticles or blocks. The mechanism of the assembly process and control of thickness, width, and interval of particle wires were further discussed. Moreover, an array of particle wires constructed not from close-packed face-centered cubic (or hexagonal close packed) structure but from two kinds of particles was realized to fabricate an array of particle wires with NaCl structure by this self-assembly process.     

Determination of 21-hydroxycorticosteroids in human urine by high-performance liquid chromatography with fluorescence detection

A simple and sensitive high-performance liquid chromatographic method with fluorescence detection for the determination of nineteen 21-hydroxycorticosteroids is described. The corticosteroids are oxidized by cupric acetate to form the corresponding glyoxal derivatives. The derivatives are converted into fluorescent quinoxalines by reaction with 1,2-diamino-4,5-methylenedioxybenzene, a fluorogenic reagent for alpha-dicarbonyl compounds. The quinoxalines are separated within 70 min on a reversed-phase column (TSK gel ODS-120T) by stepwise elution with mixtures of methanol, acetonitrile, and 1.0 M ammonium acetate. The detection limits are 0.14-29.4 pmol at a signal-to-noise ratio of 3 in a 50-microliter injection volume. This sensitivity permits precise determination of hydrocortisone, cortisone, corticosterone, and their tetrahydro derivatives in 500 microliters of normal human urine.     

Instantons and representations of an associative algebra

We give the correspondence between instantons onS ⁴ and some representations of an associative algebra. For the given structure group, we get simultaneous imbeddings to (the inductive limit) of the moduli spaces for instantons onS ⁴ of all instanton numbers.     

Application of gas chromatograph-mass spectrometer-computer system to evaluation of 14C-labelled compounds

Usefulness of gas chromatograph-mass spectrometer-computer system (GC-MS-CPU) not only for measurement of specific activities of 14C-labelled compounds in a mixture but also for evaluation of 14C-labelled compounds in terms of examining their purities and elucidating chemical structures of the impurities was proved. A sample of methyl 2-(p-chlorophenyl-14Cn)-3-methylbutylate (III) synthesized from p-chlorophenyl-14Cn-acetonitrile (VI) was analyzed by GC-MS-CPU, and it was found that the labelled compound was contaminated with a small amount of the corresponding m-isomer (IV) having a very high specific activity. Further examination suggested that the contaminating m-isomer (IV) originated from m-chlorophenyl-14Cn-acetonitrile (IX) which had already contaminated in the starting material (VI), and also that cyanomethylation of p-dichlorobenzene-14Cn (VIII) by benzene-type reaction resulted in producing a mixture of p- and m-chlorophenyl-14Cn-acetonitriles (VI, IX).     

Dynamics and thermodynamics of dimerization of parallel G-quadruplexed DNA formed from d(TTAGn) (n=3-5)

Parallel G-quadruplexes formed from oligonucleotide sequences, d(TTAGn), where n = 3-5, have been shown to form a dimer through end-to-end stacking of 3'-terminal G-tetrads. The monomers and dimers of the G-quadruplexes are in dynamic equilibrium with an exchange rate of approximately 1 s-1. A thermodynamic study demonstrated that the dimerization of the G-quadruplexes is largely enthalpic in origin.     

Development of a chemical vapor sensor using piezoelectric quartz crystals with coated unusual lipids

Piezoelectric quartz crystal sensors were developed using lipids with various properties for highly sensitive detection of chemical vapors. Lipids with varying lengths of alkyl chains were coated onto 10 MHz AT-cut quartz crystal resonators and the response of these modified crystals to chemical vapors were measured. It was shown that hydrophilic compounds, such as ethanol and methanol, could be recognized efficiently by lipids having shorter alkyl chains, whereas lipids with longer alkyl chains showed affinity to more hydrophobic vapors, such as toluene, hexane and cyclohexane. Frequency changes caused by adsorption of alcohols could be enhanced when cholesterol was co-immobilized in the lipid layer. To confirm the assumption that the sensor-response might be affected by the properties of lipids derived from acyl chains, we have examined the effects of two types of newly synthesized unusual lipids on sensor response. When lipids having one triple bond each at different positions on their alkyl chains were coated onto quartz crystals separately, lower responses were observed compared to responses obtained for a sensor with immobilized, saturated phosphatidylcholine. Lipids containing -branched acyl chains, however, showed good affinity for organic vapors, and sensor responses improved 4–5-fold. Moreover, these sensors were shown to have sensitivity of the same order as the humans' sense of smell (10⁻⁵–10⁻⁶ w/w in liquid paraffin) when measured using standard odorants (isovaleric acid, skatole, etc.) for an olfactometry established in Japan.     

The effect of the counteranion on the formation of mesoporous materials under the acidic synthesis process

The presence of various counteranions at the interfacial region of the silicate-surfactant mesophase introduces opportunities for manipulation of the phase structure. Well-ordered 3D-hexagonal P63/mmc, cubic Pmn, 2D-hexagonal p6mm, and cubic Iad mesoporous materials have been synthesized with the same surfactant, cetyltriethylammonium bromide, in the presence of various acids. The counteranions of acidic media have resulted in increasing the surfactant packing parameter g in the order SO42- < Cl- < Br- < NO3-, which leads to the different time course of formation of mesostructures. The effect of counteranions on the formation of mesostructures is explained in terms of not only the adsorption strength on the headgroups of the surfactant micelle but also the rate of silica condensation affecting the charge density matching between the surfactant and silica. It has been found that the mesophase is always transformed from the larger g parameter into the smaller one. The distinct morphologies of the 3D-hexagonal P63/mmc mesophases have been rationally explained by supposing this particular mesostructure. The cubic Iad phase has been first synthesized under acidic conditions.