Synthesis of (Z)-1-bromo-1-alkenes and terminal alkynes from anti-2,3-dibromoalkanoic acids by microwave-induced reaction

(Z)-1-Bromo-1-alkenes were stereoselectively prepared in high yields in a short reaction time by microwave irradiation of the corresponding anti-2,3-dibromoalkanoic acids in a Et₃N/DMF system. A one-pot synthesis of terminal alkynes and enynes from 2,3-dibromoalkanoic acids were also developed by microwave-induced reaction.     

Quantitative determination of bitter principles in specimens of Ganoderma lucidum using high-performance liquid chromatography and its application to the evaluation of ganoderma products

For quantitative determination of 19 triterpene constituents, including six ganoderma alcohols (1-6) and 13 ganoderma acids (7-19), in the products of Ganoderma lucidum, an analytical system was developed using high-performance liquid chromatography with an ODS column. The mobile phase was a linear gradient of 1% AcOH/H(2)O-CH(3)CN and 2% AcOH/H(2)O-CH(3)CN, and the elution profile was monitored at 243 and 250 nm for ganoderma alcohols and acids, respectively. The relative standard deviations of this method were less than 2.35% and 2.18% (n=5) for intraday and interday assays, and the recoveries were 90.9-100.8% and 93.4-103.9% for constituents of alcohol and acid groups, respectively. This system was applied to a quantitative determination of the constituents in 10 different products of G. lucidum: six usual umbrella forms of the fruiting bodies, three antlered forms of the fruiting bodies and spores, and eight specimens from the same G. lucidum strain, which was parasitized on logs from different plants or different fungus beds. The analytical results indicated that the quantity and composition of these triterpenes differed appreciably among various specimens, but the relative ratio of the alcohols and acids was not significantly different when the same strain of G. lucidum was used.     

Giant meso-meso-linked porphyrin arrays of micrometer molecular length and their fabrication

On the basis of the Ag(I)-promoted coupling reaction of zinc(II)-5,15-bis(3,5-dioctyloxyphenyl)porphyrin Z1, chain elongation has been attempted by using a stepwise doubling approach, which provides Z2, Z4, Z8, Z16, Z32, Z64, Z128, Z256, Z384, and Z512. The porphyrin arrays up to Z128 are sufficiently soluble in CHCl3 and THF despite their very long molecular lengths and rodlike structures, while the arrays over Z128 show a significant drop in solubility and stability. The discrete porphyrin arrays thus isolated were characterized by means of (1)H NMR spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, UV/Vis spectroscopy, gel-permeation chromatography (GPC), cyclic voltammetry (CV), single-crystal X-ray crystallography, scanning tunneling microscopy (STM), and atomic force microscopy (AFM). Contrary to expected linear conformations of the arrays Z n (where n is the number of porphyrins), the single molecular images of Z128, Z256, and Z512 revealed largely bent structures; this finding indicates the substantial conformational flexibility of Z n. We also exploited an effective synthetic route by means of which Z n can be fabricated with a thiol-protected aryl group to provide Z n S(2) through Z n Br(2), by bromination with N-bromosuccinimide and subsequent Pd-catalyzed Suzuki-Miyaura arylation. Finally, the reaction of Z256 provided Z512, Z768, and Z1024. Collectively, this work provides an important milestone in the preparation of sub-microscale discrete organic molecules and the fabrication of molecular-based materials, hence significantly contributing to device applications.     

Hypoxanthine sensor based on an amorphous silicon field-effect transistor

The pH response of an a-ISFET with xanthine oxidase immobilized on a ca. 20-μm thick poly(vinyl butyral) membrane over the gate insulator, is used to detect the uric acid produced by enzyme-catalyzed oxidation of hypoxanthine. The pH sensitivity between pH 5.0 and 10.0 is ca 48 mV/pH at 32°C in 10 mM phosphate buffer. The change in the output gate voltage 1 min after sample injection, is linearly related to the logarithm of the hypoxanthine concentration in the range 0.02–0.1 mM. The optimum buffer pH is 7.5. The system can be used for 2 weeks with 30% loss of enzymatic activity.     

Separation of vanadium isotopes by ion-exchange chromatography

Cation-exchange displacement chromatography of VO2+ was carried out for studying vanadium isotope effects in carboxylate ligand-exchange systems. The heavier isotope 51V was enriched in the carboxylate complex solution. The isotope separation coefficients epsilon(= alpha-1) for 50V/51V were 2.2 x 10(-4) and 2.4 x 10(-4) for citrate and lactate systems at 298 K, respectively. These values are much larger than those obtained in a previous study on the malate system. The existence of binuclear complexes of VO2+ may create the conditions for larger isotope fractionation. From the viewpoint of the process development of isotope separation, the heights equivalent to a theoretical plate of these processes were analyzed and found to be very small in each system due to the homogeneous, small and highly porous resin used. Citrate may be better than the other tested systems for the vanadium isotope separation.     

Partial molar volumes and adiabatic compressibilities ofN-acetyl-DL-serinamide andN-acetyl-L-threonmamide in dilute aqueous solutions

Densities and sound velocities in dilute aqueous solutions ofN-acetyl-DL-serinamide andN-acetyl-L-threoninamide were measured at 5, 15, 25, 35, and 45°C. Partial molar volumes and partial molar adiabatic compressibilities of these amino acid derivatives at infinite dilution were determined. The partial molar quantities for the parent amino acids, serine and threonine, were also determined and compared with the acetyl amide derivatives. The contribution of the side chain of theN-acetyl amino acid amide or amino acid to the partial molar quantities were estimated from the difference between the partial molar quantities for the solute studied and those for the corresponding species,N-acetyl-glycinamide or glycine, without the side chain.     

Novel and efficient synthesis of 4-dimethylamino-2-glycosylaminoquinazolines by cyclodesulfurization of glycosyl thioureas with dimethylcyanamide

4-dimethylamino-2-glycosylaminoquinazoline derivatives were synthesized by cyclodesulfurization of N-aryl-N'-glycosyl thioureas with dimethylcyanamide in the presence of silver triflate in good yields.     

Novel synthesis of benzalacetone analogues of naphth[a]azulenes by intramolecular tropylium ion-mediated furan ring-opening reaction and X-ray investigation of a naphth[1,2-a]azulene derivative

[reaction: see text] Benzalacetone analogues of naphth[1,2-a]azulene (8), naphth[2,1-a]azulene (13), and naphth[2,3-a]azulene (18) were synthesized from 2-(5-methyl-2-furyl)-1-tropylionaphthalene (7), 1-(5-methyl-2-furyl)-2-tropylionaphthalene (12), and 2-(5-methy-2-furyl)-3-tropylionaphthalene (17), respectively. The synthetic method is based on furan ring-opening reaction by the intramolecular electrophilic attack of a tropylium ion. Single-crystal X-ray work on the naphth[1,2-a]azulene derivative (8) revealed that its tetracyclic system exhibited deformation from planarity similar to that of benzo[c]phenanthrene (tetrahelicene). A centrosymmetric associated dimer structure, just like the molecules of carboxylic acids but via C=O...H-C hydrogen bonds, was found in the crystal. Reduction of bond-length alternation in the seven-membered ring was also found.     

Synthesis of novel cation-ordered compounds with fluorite-related structure prepared by oxidation of Sn-Ta-O pyrochlore

Pyrochlore-type oxide, Sn^II_1.64(Ta_1.88Sn^IV_0.12)O_6.58 was oxidized for exploring novel metastable phases. Two novel Sn^IV_0.82(Ta_0.94Sn^IV_0.06)O_4.11 phases with a fluorite-related structure, which was obtained as a pure phase, and with a rutile-related structure appearing as an impurity for the fluorite-related phase were successfully obtained similar to the previous Sn-Nb-O system. The ordered arrangement of respective cations of Sn and (0.94Ta+0.06Sn) in the precursor Sn^II_1.64(Ta_1.88Sn^IV_0.12)O_6.58 was left in the both oxidized Sn^IV_0.82(Ta_0.94Sn^IV_0.06)O_4.11 phases. In contrast to the previous Sn-Nb-O system, the cation-ordered α-PbO₂-related Sn^IV_0.82(Ta_0.94Sn^IV_0.06)O_4.11 could not be obtained in the present conditions. Such a difference between the Sn-Ta-O and Sn-Nb-O systems was interpreted by larger energy barrier of the transformation from the fluorite-related phase to α-PbO₂-related phase in Sn-Ta-O system than in Sn-Nb-O system.     

Studies on the tacticity of polyacrylonitrile. III. NMR spectra of stereoisomers of 2,4,6-tricyanoheptane as model compounds of polyacrylonitrile

The three stereoisomers of 2,4,6-tricyanoheptane were separated and their NMR spectra were studied as the three-unit model compounds of polyacrylonitrile. The chemical shifts and coupling constants obtained from the NMR spectra were compared to those of the two-units model compounds. The geminal protons for the isotactic methylene are not equivalent, but the difference of the chemical shifts is smaller than that in the meso two-unit model. The racemic methylene signals appear at higher field than the meso methylene in the heterotactic three-unit model as in the case of the racemic and the meso two-unit models. The signals of the methinic protons in triads appear in the order: isotactic CH, heterotactic CH, and syndiotactic CH from the high field. From the observed values of the vicinal coupling constants, the chain conformations of the model compounds are also discussed.