Temperature stabilized optical waveguide modulator

A low drive-voltage optical modulator using a Ti-diffused UNbO₃ optical waveguide has been fabricated. Stabilization against ambient temperature change was realized by using a miniature halfwave plate. The halfwave voltage, 3 dB bandwidth, optical insertion loss and extinction ratio were 3·8 V (at 1·06m wavelength), 850 MHz, 10 dB and 13 dB, respectively. A reduction scheme for the optical absorption caused by metallic electrodes, and an analysis of the modulator high frequency response are also reported.     

Synthesis and nanostructure of strong polyelectrolyte brushes in amphiphilic diblock copolymer monolayers on a water surface

We synthesized an ionic amphiphilic diblock copolymer, poly(hydrogenated isoprene)-b-poly(styrenesulfonic acid) (PIp-h2-b-PSS), by living anionic polymerization, and the nanostructure of its monolayer spread on a water surface was directly investigated by the in situ X-ray reflectivity technique. The monolayer of the diblock copolymer on a water surface had a smooth hydrophobic PIp-h2 layer on water and a "carpet"/polymer brush double layer in a hydrophilic sodium polystyrene sulfonate (PSSNa) layer under the water. The surface pressure dependence and PSSNa chain length dependence of the PIp-h2 layer thickness and the brush nanostructure were quantitatively studied. The effect of salt concentration in the subphase was also investigated in aqueous solutions containing 0-2 M NaCl. The salt effect on monolayer structure occurred at around 0.2 M. The thickness of the PSS brush layer decreased at salt concentrations above 0.2 M, while no structural change was observed below 0.2 M. This critical salt concentration is thought to be related to the balance of ionic concentrations inside the brush and in bulk solution.     

Synthesis of bis(alk-3-en-1-ynyl)benzene with either E- or Z-configuration via a one-pot three-component coupling reaction and its optical properties

A convenient, efficient and stereoselective synthesis of a range of bis(alk-3-en-1-ynyl)benzenes with E- and Z-configuration is described. The protocol involves Cu-mediated cross-coupling reaction of (E)- and (Z)-alk-1-enyldisiamylboranes with (trimethylsilyl)ethynyl bromide and Pd/Cu-catalyzed cross-coupling reaction with diiodobenzene. The sequential cross-coupling reaction proceeds readily under extremely mild conditions in a one-pot manner to afford bis(alk-3-en-1-ynyl)benzenes in good to excellent yields. The optical properties of the products are also described.     

Deoxyfluorination of alcohols using N,N-diethyl-α,α-difluoro-(m-methylbenzyl)amine

Deoxyfluorination of alcohols was carried out using N,N-diethyl-α,α-difluoro-(m-methylbenzyl)amine (DFMBA). Primary alcohols were effectively converted to fluorides under microwave irradiation or conventional heating. Deoxyfluorination of an anomeric hydroxy group in sugars by DFMBA proceeded at below room temperature and glycosyl fluorides could be obtained in good yields. The deoxyfluorination reaction chemoselectively proceeded and various protecting groups on the sugar can survive under the reaction conditions.     

The first example of regiospecific magnesium carbenoid 1,3-CH insertion: its mechanism and stereochemistry

Addition reaction of two geometrical isomers of 1-chlorovinyl p-tolyl sulfoxides, derived from unsymmetrical ketones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl acetate gave single isomers of the adduct, respectively. Treatment of each diastereomer with i-PrMgCl resulted in the formation of magnesium carbenoids. Highly regiospecific 1,3-CH insertion reaction was found to take place from the magnesium carbenoids to afford cyclopropanes in high yields. Stereochemistry of the adducts, reaction mechanism, and origin of the regiospecificity are discussed.     

Evaluation of postoperative hepatobiliary function by deconvolution analysis of hepatobiliary image data by 99mTc-N-pyridoxyl-5-methyltryptophan

Dynamic hepatobiliary image data were analyzed by the mathematical deconvolution to derive the transfer function (TF) which represents the impulse response function of the liver following direct bolus injection of a tracer into the liver. Biliary flow was evaluated by TF in patients with previous hepatobiliary surgery to detect abnormal flow causing problems such as cholangitis. Serial image data were collected for 60 min after intravenous injection of 37-75 MBq (1-2 mCi) of 99mTc-N-pyridoxyl-5-methyltryptophan (99mTc-PMT). TF was obtained by the matrix algorithm, using regional hepatogram as output and time-activity curve over the heart as input function. Minimum, mean and maximum transit time (Max. TT) were determined from TF. The functional image for each of the transit times was constructed by displaying the distribution of the values for matrix elements with a color scale. In this study, a critical Max. TT of 60 min was used to detect abnormal biliary flow. Of 30 cases, 9 positive cases were discriminated from 21 negative cases on the basis of the finding of presence or absence of areas with Max. TT of more than 60 min anywhere in the liver. Bowel activity overlapping the liver was excluded in the judgment. The validity of this method was evaluated in comparison with the clinical courses after surgery with (8 cases) or without (22 cases) problems. The results were sensitivity of 88%, specificity of 91%, accuracy of 90% and positive predictive value of 78%.(ABSTRACT TRUNCATED AT 250 WORDS)     

Study on Segmental Motion and Ion Binding in Polyelectrolyte Solutions by Ultrasonic Spectroscopy

The ultrasonic absorption spectra of aqueous solutions of polyacrylate (PA), polyphosphate (PP), and polystyrenesulfonate (PSS), neutralized by tetramethylammonium hydroxide (TMAOH), were measured. The effects of addition of tetramethylammonium chloride (TMACl) and sodium chloride (NaCl) to the polyelectrolyte solutions were investigated in the frequency range from 500 kHz to 100 MHz. Two ultrasonic relaxation processes due to the local segmental motions were observed. The relaxation frequency for TMAPP solution decreased as the ionic strength was increased by the addition of TMACl. For the other two polymer solutions, the ionic strength did not affect the relaxation spectra. The addition of NaCl led to an increase of the ultrasonic absorption, which was ascribed to ion binding. The ultrasonic absorption due to the ion binding was estimated by subtracting the contribution of the segmental motion from the measuring ultrasonic spectra. The volume changes accompanying the ion binding for polyacrylate and polyphosphate salts were estimated to be 5 and 8 cm³-mol^?1, respectively.     

Photocrosslinking of poly(2,3-epithiopropyl methacrylate) by the oxidation of pendant episulfide groups

In the photocrosslinking of poly(2,3-epithiopropyl methacrylate) (PETMA) films the effect of the pendant episulfide group's oxidation on the crosslinking of PETMA was investigated. Thermal crosslinking of PETMA is promoted by peroxides such as benzoyl peroxide and hydrogen peroxide. IR spectrum of the crosslinked PETMA showed that the reaction proceeded through the oxidation of episulfide groups by the peroxides. The anthracene (An) sensitized photocrosslinking of PETMA films also proceeded via the oxidation of episulfide groups by singlet oxygen. It was found that residual tetrahydrofuran (THF) in the films remarkably increased the rate of the photocrosslinking and/or reduced the induction period. From the further investigation concerning casting solvents it was found that residual CS₂, CCl₄, and CHCl₃ in films increased the rate of the photocrosslinking and/or reduced the induction period of the photocrosslinking. The disappearance rate of An in the films was also increased by the presence of residual CS₂, CCl₄, and CHCl₃, differring from the result of THF. These results were explained by a difference in lifetime of singlet oxygen in the films. From the results were explained by a difference in lifetime of singlet oxygen in the films. From the results concerning the effects of hydroperoxides such as THF hydroperoxide and t-butyl hydroperoxide on the photocrosslinking of PETMA films the acceleration effect of the residual THF was deduced to be due to the promotion of singlet oxygen-oxidation of sulfide groups by protic compounds such as THF hydroperoxide and H₂O in the THF.     

Perfluoro-1,3,5-tris(p-oligophenyl)benzenes: Amorphous Electron-Transport Materials with High-Glass-Transition Temperature and High Electron Mobility

Perfluoro-1,3,5-tris(p-quaterphenyl)benzene (PF-13Y) and perfluoro-1,3,5-tris(p-quinquephenyl)benzene (PF-16Y) have been synthesized and characterized. They showed higher glass transition temperatures compared with perfluoro-1,3,5-tris(p-terphenyl)benzene (PF-10Y). Organic light-emitting diodes were fabricated using these materials as the electron-transport layers. PF-13Y and -16Y are better electron transporters than PF-10Y. The electron mobilities of PF-10Y and Alq₃ were measured by the time-of-flight technique. PF-10Y showed higher electron mobilities (10⁻⁴ cm²/V s) and weaker electric field dependence compared with Alq₃.     

High-pressure synthesis of cyclic phenylacetylene oligomer

New conjugated oligomers were prepared by reacting phenylacetylene under high pressure of 0.11 to 0.92 GPa at 100–200°C for 0–5 h. The number-average molecular weight M?_n, the weight-average molecular weight M?_w, and the oligomer yield increased with pressure, tem-perature, and time. The average molecular weight of the oligomer showed the maximum value (M?_n: 830, M?_w: 2400) under 0.92 GPa, the maximum pressure, where phenylacetylene was oligomerized at a constant temperature. The structure of the oligomer was investigated from ESR, infrared, UV–VIS, field desorption mass (FDMS) spectra, and ¹³C NMR spec-trum. Analysis of the FDMS spectrum revealed that the molecular weight of the oligomer was multiple of the monomer. ¹³C NMR spectrum of the oligomer showed the absence of sp-carbon (? C?). We found that the oligomer had a cyclic structure. The cyclic oligomers of pentamer or more were new compounds. © 1995 John Wiley & Sons, Inc.