Changes in the near-edge X-ray absorption fine structure spectra of long-chain diacetylene derivatives through photopolymerization in Langmuir–Blodgett films

Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004     

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.     

Schottky metal library for ZNO-based UV photodiode fabricated by the combinatorial ion beam-assisted deposition

A binary alloy Schottky barrier diode on zinc oxide (ZnO) was developed using the combinatorial ion beam-assisted deposition system. The compositional fraction of the binary alloy was continuously varied using the composition-spread technique, to control the Schottky barrier height. After metal deposition, patterned Schottky diodes were fabricated on a ZnO single-crystal substrate. Pt-Ru alloy was selected from the work function viewpoint. Our experiments showed that the compositional fraction of the Schottky binary alloys changed continuously as designed and the Schottky barrier heights measured by current-voltage (I-V) measurements increased with increasing Pt content. Maximum barrier height difference for ZnO was 137 meV. Using ion beam deposition in parallel with the combinatorial system showed that the Schottky barrier heights for ZnO can be controlled by binary metal alloying.     

Peroxyoxalate chemiluminescence detection of condensates of malondialdehyde with thiobarbituric acids using a flow system.

The peroxyoxalate chemiluminescence(CL) detection method for the evaluation of the CL intensity of malondialdehyde(MDA) condensates with seven 2-thiobarbituric acid derivatives is described. The method consists of a flow injection technique together with a CL detection system using bis(2,4,6-trichlorophenyl) oxalate(TCPO) and hydrogen peroxide as chemiluminogenic reagents. Linear correlations between CL intensity and concentration are obtained for pmol levels of condensates. Among the condensates, 1,3-diethyl-2-thiobarbituric acid(DETBA)-MDA shows the largest CL intensity. High performance liquid chromatography (HPLC)/CL detection of DETBA-MDA and 1,3-diphenyl-2-thiobarbituric acid(DPTBA)-MDA using a mixture of TCPO and hydrogen peroxide in acetonitrile as a postcolumn reagent solution is also described. The detection limits for DETBA-MDA and DPTBA-MDA are 20 and 200 fmol, respectively, per 20 microL injection at a signal-to-noise ratio of 2. This HPLC/CL detection system was applied to the determination of MDA in rat brains by using DETBA as a fluorescent derivatizing reagent.     

Electrochiroptical systems based on biphenyl-2,2′-diyl-type dicationic dyes: strong chiroptical signals through the transmission of point chirality to axial chirality

Huge CD amplitude (A = +538) was attained by diastereomeric preference (50% de) for the title dication with two bis[4-(R)-sec-butoxyphenyl]methylium units in benzene at 23 °C. Intramolecular π-π stacking is the origin for effective transmission of point chirality to axial chirality to attain the chiroptical enhancement of 400-times. Thanks to the strong CD signaling, chiroptical changes upon electrolysis could be readily detected, thus realizing a new class of electrochiroptical response systems. Chiroptical properties could also be modified by solvent polarity.     

Copper(II)-catalyzed oxidation of d-alpha-tocopherol by oxygen in aqueous solution

alpha-Tocopherol (alpha-Toc) was solubilized in aqueous solutions using 13 solubilizing agents and the products of oxidation by oxygen in the presence and the absence of Cu(II) were analyzed by HPLC. In the presence of Cu(II), the oxidation was accelerated and 5-formyl-7,8-dimethyltocol and alpha-tocoquinone were the major oxidation products. Their yields greatly increased in the presence of Cu(II). The yields and the rates of formation of the products were dependent on the properties of solubilizing agents and other conditions as well as the presence of Cu(II) or other metal ions. It is suggested that slight changes in the structure of the solubilizing agents affect the course of the reaction.     

Sensitive determination of diazepam and N-desmethyldiazepam in human material using capillary gas chromatography-mass spectrometry

A reliable and sensitive capillary gas chromatographic-mass spectrometric method was developed for the detection and determination of diazepam and its major metabolite, N-desmethyldiazepam, in human material. Medazepam served as the internal standard. Quantitative determination was achieved using mass fragmentography with selected ions of m/z 256 for diazepam and m/z 242 for N-desmethyldiazepam and medazepam. The limit of detection was 1 ng/g and the recoveries were 98.54 +/- 3.95% for diazepam and 98.66 +/- 6.48% for N-desmethyldiazepam. The calibration graph was linear over the concentration range from 1.0 ng/g to 1.0 microgram/g for diazepam and N-desmethyldiazepam. Using this method, trace amounts of diazepam and N-desmethyldiazepam were detected in the tissues of an autopsied individual.     

The synthesis of isoquinoline alkaloid and its related compounds using alanine derivatives as chiral auxiliaries

Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline (16) in a highly enantioselective manner.