bluuebunny/crossref_metadata_2025 huggingface dataset:
Structure of and Tetrahedral Character of the Boron Atom in 9-[2-(1-Ethylthiopentyl)phenyl]-9-borabicyclo[3.3.1]nonane
Authors: Toyota Shinji , Oki Michinori
Published: July 2006

Structure of the title compound was determined by the X-ray analysis. The sulfur atom intramolecularly coordinates to the boron atom with a distance of 2.071 Å and the relation between the butyl group at the benzylic position and the S-ethyl group is nearly anti. The observed dynamic behavior in the compound is discussed on the basis of the structure and the results of some NMR experiments. Other structural features and the tetrahedral character of the boron atom are also reported.
Molecular and Crystal Structure of 3,5,5-Trimethyl-2-(2-methyl-2-nitropropyl)-2-cyclohexen-1-one Possessing Molecular Asymmetry
Authors: Azuma Nagao , Ozawa Takehiro , Yamawaki Kunihiko , Tamura Rui
Published: July 2006

The crystal structure of an aliphatic nitro compound with atropisomerism, C13H21NO3, has been determined by X-ray diffraction at ambient temperature. The monoclinic structure (P21/c, Z = 8) was refined by the full-matrix least-squares method to a final R = 0.040 for 2394 observed unique reflections. Two crystallographically independent molecules consist of a pair of atropisomers. The intramolecular O···H–C type hydrogen bonds (O···C(methyl): 3.21–3.54 Å) and the contact between the nitro oxygen and ethylenic carbon atoms (O···C: 3.24 and 3.36 Å) may be responsible for this isomerism.
Kinetics of Oxidation of Aniline and Xylidines by the Tetrahydroxoargentate(III) Ion
Authors: Kumar Anil , Panwar Ashok
Published: July 2006

The reactions of [Ag(OH)4]− with aniline and xylidines have been investigated. The stopped-flow experiments reveal kinetically distinguishable steps involving initial complexation of the substrate with the silver(III) species which is followed by its decomposition. The latter process obeys first-order kinetics and takes place with a rate constant of about 0.8 s−1 through intramolecular electron transfer from substrate to the silver(III) center. Azobenzene and p-benzoquinone have been identified as the main products of the reaction of [Ag(OH)4]− and aniline. An increase in concentration of aniline enhances the yield of azobenzene which accounts for approximately 65% of the consumed aniline. This effect has been interpreted by the increased effective complexation between aniline and [Ag(OH)4]− at higher concentrations. The stoichiometry of the reaction is found to vary with a change in the concentration of aniline. At higher concentrations it comes out to be 1 : 2 for [Ag(OH)4]− : aniline. A mechanism of this reaction is worked out.
Effect of a Combination of Drawing and Heat Treatment on the Tensile Properties of Poly[1,3,4-oxadiazole-2,5-diyl- 1,4-phenyleneimino(chloroterephthaloyl)imino-1,4-phenylene] Film
Authors: Hirai Kan , Amemiya Yoshiaki , Sano Youichiro , Kojima Kyouhei
Published: July 2006

Poly[1,3,4-oxadiazole-2,5-diyl-1,4-phenyleneimino(chloroterephthaloyl)imino-1,4-phenylene] (PBO-ClT) was prepared by the low-temperature solution polycondensation of 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole with 2-chloroterephthaloyl dichloride in the presence of lithium carbonate as an acid accepter in 1-methyl-2-pyrrolidinone (NMP). The value of the inherent viscosity of PBO-ClT was 1.79 dl g−1 in sulfuric acid (0.5 g/100 ml, 25 °C). PBO-ClT was easily dissolved in NMP and N,N-dimethylacetamide (DMA). The solubility of PBO-ClT, chloro-substituted polymer, was larger than that of poly(1,3,4-oxadiazole-2,5-diyl-1,4-phenyleneiminoterephthaloylimino-1,4-phenylene) in these organic solvents. In order to enhance the tensile properties of PBO-ClT films cast from NMP solutions, the films were drawn and heat-treated under various conditions. The films were drawn in a DMA/water mixture (80 : 20, v/v, 70 °C) and subsequently heat-treated (the temperature was raised from room temp to 300 °C at a heating rate of 12—15 °C min−1). The values of the tensile strength, tensile modulus, and breaking energy of the drawn and heat-treated films were 1.30 GPa, 22.8 GPa, and 37.3 MJ m−3, respectively. These values were changed into 1.02 GPa, 18.5 GPa, and 26.9 MJ m−3 after 2 h of heat-aging at 350 °C in air. These results showed the high-temperature durability of the drawn and heat-treated materials.
Orientational Opacity Functions for the CN(A) and CN(B) Radical Formations in the Ar(3P) + CF3CN Reaction
Authors: Che Dock-Chil , Kasai Toshio , Ohoyama Hiroshi , Kuwata Keiji
Published: July 2006

Using the oriented molecular beam, the orientational dependence of the CN(A) and of the CN(B) radical formation has been reinvestigated to obtain orientational opacity functions for the Ar(3P) + CF3CN reaction. The steric model with the Legendre polynomial expansion gave the best-fit functions which have two reactive sites on CF3CN. One site locates at the CN end and the other one near the C–F bonds. It was found that the CF3 end attack is the least favorable for both CN formations. These results substantiate the relationship between the shape of the 2e and 7a1 molecular orbitals of CF3CN and the orientational opacity functions.
Preparation and Characterization of Nitrosylruthenium(III) Complexes Containing Diethylenetriamine
Authors: Asanuma Risa , Tomizawa Hiroshi , Urushiyama Akio , Miki Eiichi , Mizumachi Kunihiko , Ishimori Tatsujiro
Published: July 2006

Some kinds of {RuII-NO+}-type complexes containing a diethylenetriamine ligand were prepared from hydrous RuX3·NO (X = Cl or Br) and diethylenetriamine. Among them, the crystal and molecular structures for trans-mer-[RuCl2(dien)NO]PF6 (1) and mer-[RuBr3(Hdien)NO]Br·H2O (2) (dien = diethylenetriamine) were determined by X-ray diffraction. The crystal of 1 was monoclinic, space group P21/a with a = 21.296(4), b = 6.602(2), c = 10.079(2) Å, β = 97.12(2)°, Z = 4, and final R = 0.0307, and the crystal of 2 was orthorhombic, space group P212121 with a = 11.988(4), b = 17.234(9), c = 7.141(2) Å, Z = 4, and final R = 0.0825. In 1, the two chloro ligands were in the trans arrangement and the dien was in the meridional arrangement as a tridentate ligand. In 2, the three bromo ligands were in the meridionalarrangement with the Hdien coordinated to the ruthenium through one terminal and central nitrogen atoms as a bidentate ligand, and the remaining uncoordinated terminal moiety was –NH3+. The trans-strengthening effect that is expected to be caused by the NO was not observed for the Ru–N(dien) bond. The synthesized complexes were also characterized by IR and NMR spectra.
Analytical Study on Separation of Vanadium(V), Niobium(V), and Tantalum(V)
Authors: Kakade Sharad Mahadeo , Shinde Vijay Malhar
Published: July 2006

A simple and rapid method for extractive separation of vanadium(V), niobium(V), and tantalum(V) from halide media has been worked out using triphenylphosphine oxide in toluene as an extractant. The optimum conditions for extraction and separation have been evaluated from critical study of various variable factors. The log–log plots are used to ascertain probable extractable species. The method is applicable to the analysis of standard alloy samples and synthetic mixtures. The results are reproducible and accurate.
X-Ray Crystal Structures and Unusual Magnetic Properties of Alkoxo-Bridged Copper(II) Complexes with 2-Dialkylaminoethanol and 1-Dialkylamino-2-propanol
Authors: Mikuriya Masahiro , Yamamoto Masato , Mori Wasuke
Published: July 2006

A series of alkoxo-bridged copper(II) complexes with 2-dialkylaminoethanol and 1-dialkylamino-2-propanol, [Cu2(R2NCH2CH2O)2(NCS)2] and [Cu2{R2NCH2CH(CH3)O}2(NCS)2] (R = CH3, C2H5, n-C3H7, i-C3H7), have been prepared and characterized by infrared and electronic spectroscopies, and temperature dependence of magnetic susceptibilities. The crystal structures of [Cu2{i-C3H7)2NCH2CH2O}2(NCS)2] and [Cu2{R2NCH2CH(CH3)O}2(NCS)2] (R = CH3, C2H5, n-C3H7, i-C3H7) have been determined by X-ray crystallography. The compounds are polymeric with copper atoms alternately bridged by two alkoxo oxygen atoms and two thiocyanate ions, except for [Cu2{(i-C3H7)2NCH2CH(CH3)O}2(NCS)2] which is a discrete alkoxo-bridged dinuclear molecule. The unusual magnetic properties are discussed in relation to the crystal structures.
New Synthetic Methods and Reagents for Complex Carbohydrates. VIII. Stereoselective α- and β-Mannopyranoside Formation from Glycosyl Dimethylphosphinothioates with the C-2 Axial Benzyloxyl Group
Authors: Yamanoi Takashi , Nakamura Kazumi , Takeyama Hiroshi , Yanagihara Kenji , Inazu Toshiyuki
Published: July 2006

The reactions of mannopyranosyl dimethylphosphinothioates and alcohols using silver perchlorate as an activator in the presence of molecular sieves 4A in benzene at room temperature gave the 1,2-trans-α-mannopyranosides in good yields. On the other hand, 1,2-cis-β-mannopyranosides could be obtained from the dimethylphosphinothioates by the combined use of iodine and 5 mol% triphenylmethyl perchlorate as an activating system. The syntheses of the derivatives of αMan(1→6)[αMan(1→3)]Man and βMan(1→4)GlcNAc units of glycoproteins by these methods are described.
Photocontrolled Uptake and Release of Photochromic Haptens by Monoclonal Antibodies. Evidence of Photoisomerization Inside the Hapten-Binding Site
Authors: Harada Masataka , Sisido Masahiko , Hirose Jyunzo , Nakanishi Mamoru
Published: July 2006

Monoclonal antibodies against a tetrapeptide carrying a photochromic azobenzene moiety (Glu–azoAla–Gly–Gly, azoAla = l–p–phenylazophenylalanine) were prepared under conditions where the azobenzene moiety was in the trans form. The binding of the hapten peptide to the antibody was investigated by fluorescence quenching of the antibodies by the hapten peptide. The results indicated that the antibodies bind the hapten peptide when the azobenzene moiety is in the trans form, but release the peptide in the cis form. The mechanism of photoreversible binding and release was studied using a pulsed laser light. Photoisomerization of the hapten peptide was found to occur inside the binding site, indicating that the latter is flexible enough to allow the trans–cis photoisomerization within a few ten picoseconds.
Intramolecular Photocycloaddition of (E)-3-(4-Methoxyphenyl)-3-pentenyl 6-Cyano-9-phenanthrenecarboxylate. Temperature and Solvent Effects
Authors: Tanaka Noriyuki , Yamazaki Hiroyuki , Sakuragi Hirochika , Tokumaru Katsumi
Published: July 2006

(E)-3-(4-Methoxyphenyl)-3-pentenyl 6-cyano-9-phenanthrenecarboxylate as well as the corresponding 9-phenanthrenecarboxylate exhibited exciplex emission and gave [2+2] photocycloadducts of the double bond with the phenanthrene 9,10 bond (a cyclobutane) and with the ester carbonyl group (an oxetane). The involvement of plural exciplex intermediates for these phenomena was proposed on the basis of the temperature and solvent dependence of quantum efficiencies of fluorescence and cycloadditions as well as of the effects of quenchers of exciplex intermediates.
Synthesis and Cation-Binding Properties of Dihydroxycrownophanes and Their Derivatives
Authors: Inokuma Seiichi , Sakai Shigefumi , Katoh Reiko , Nishimura Jun
Published: July 2006

Dihydroxycrownophanes (2a—c) were conveniently synthesized by intramolecular [2 + 2] photocycloaddition, and their derivatives with two cation-ligating side chains (3a—6a) were also readily prepared by the reaction of 2a—c and the corresponding halides in the presence of NaH. All of the crown compounds obtained were used as ionophores in single extraction experiments of heavy metal cations including transition metal cations in a H2O–CH2Cl2 system. Although 3a did not extract any alkaline earth metal cation at pH 7.0, it showed high affinity toward Pb2+ even under acidic conditions (pH 4.7). Crownophanes (4a—c) having two 2-pyridylmethyl ligands efficiently extracted Ag+ with excellent selectivity.
Synthesis of Glucose-Sensitive Insulin-Releasing Protein Devices
Authors: Chung Dong-June , Ito Yoshihiro , Imanishi Yukio
Published: July 2006

A glucose-sensitive insulin-releasing protein device was synthesized by connecting insulin to glucose oxidase (GOD) through a disulfide linkage. Insulin was released from the device by reductive cleavage of the disulfide linkage with electrons generated upon oxidation of glucose by GOD. Some protein devices containing different amounts of insulin were synthesized by varying the feed concentration in the synthetic process. The amount of released insulin increased with the increase of insulin content in the protein device. Although using urea enhanced the amount of insulin coupled to GOD, the efficiency of insulin release did not increase. The fluorescence quenching of the protein device containing fluorescence-labelled insulin with acrylamide showed that insulin was incorporated into the interior domain of the GOD molecule by addition of urea.
Synthesis of Highly Acidic Catalysts of Tungsten Oxide Supported on Tin Oxide, Titanium Oxide, and Iron Oxide
Authors: Hino Makoto , Arata Kazushi
Published: July 2006

Solid superacid catalysts, which were active for the skeletal isomerization and cracking of isopentane, were obtained by impregnating hydroxides or amorphous oxides of Sn, Ti, and Fe with ammonium metatungstate and then calcining in air; the maximum activity was observed with calcination at 1000 °C for the material of Sn and 700 °C for those of Ti and Fe (11—13 wt% W).
Crystal and Molecular Structures of Allocinnamic Acid
Authors: Lee Ho-Hi , Senda Hitoshi , Kuwae Akio , Hanai Kazuhiko
Published: July 2006

Crystals of allocinnamic acid having a melting point of 68 °C are monoclinic: space group P21/n with a = 10.157(4), b = 9.798(2), c = 15.770(4) Å, β = 91.35(3)°, and Z = 8. The structure was solved by direct method and refined to a final R value of 0.059 for 3832 reflections [I > 3σ(I)]. There are two independent molecules (A, B) in the asymmetric unit. The two molecules are hydrogen bonded through carboxylic acid groups [O1A···O2B 2.643(5) Å, O2A···O1B 2.629(5) Å]. Geometric differences between the two molecules are found in the torsion angle around the C(phenyl)–C(olefin) bond and the olefinic C=C bond length. In the high-resolution solid-state 13C NMR spectra resonances for the C2, C3, and C4 carbons are observed as doublet features in accordance with the conformational variations observed in X-ray crystallography.
Assignments of the Deoxyribose Vibrations: Isotopic Thymidine
Authors: Tsuboi Masamichi , Ueda Toyotoshi , Ushizawa Koichi , Sasatake Yasuhiro , Ono Akira , Kainosho Masatsune , Ishido Yoshiharu
Published: July 2006

Raman spectrum of thymidine-13C5, in which five C atoms of the deoxyribose moiety are uniformly substituted with 13C atoms, has been examined in the crystalline state with 488.0 nm excitation. Some of the Raman bands were observed at appreciably shifted frequencies from those of the corresponding Raman bands of the natural thymidine, and they were assigned to some vibrations involving deoxyribose motions.
Zeolite-Assisted Oxidation of Sulfides with Sodium Bromite Trihydrate in Aprotic Solvents
Authors: Hirano Masao , Kudo Hiroyuki , Morimoto Takashi
Published: July 2006

The title oxidation of a variety of sulfides was effectively performed in dichloromethane in the presence of H+-exchanged zeolite F-9, affording the corresponding sulfoxides in good yields under mild and neutral conditions.
Support of Ultrafine Palladium Particles upon a Glassy Carbon Substrate by a Chemical Method
Authors: Takasu Yoshio , Ohashi Norio , Onoue Satoshi , Kameyama Kohichi , Yahikozawa Kiyochika
Published: July 2006

Isolated ultrafine palladium particles prepared by a gas-evaporation method have been chemically supported on a flat glassy carbon substrate using a silane coupling agent. The modification of the ultrafine palladium particles with the silane coupling agent was confirmed by FT-IR spectroscopy and transmission electron microscopy (TEM). The supported palladium particles did electrochemical sorption–desorption of hydrogen in an acidic solution.
Kinetic Studies of the Catalytic Oxygen Exchange of Chromate Ions with Water by Periodate Ions
Authors: Okumura Akiko , Kitani Mie , Murata Michiyo
Published: July 2006

The oxygen exchange reaction between chromate ions and water is catalyzed by the addition of a small amount of periodate ions. The catalytic reaction has been studied by using 18O tracer work (0 °C, pH = 8—12, [Cr(VI)] = 0.075 mol dm−3, [I(VII)] = 10−5 mol dm−3) and an 17O NMR line broadening technique(30 °C, pH = 4—6, [Cr(VI)] = 1 mol dm−3, [I(VII)] = 0.043 mol dm−3). The catalytic process has been interpreted in terms of the reversible condensation of chromate ions with periodate ions to form chromatoperiodate ions. The rate law is given as: Rc = k1[HCrO4−][H4IO6−] + k2[HCrO4−][H3IO62−] + k3[CrO42−][H4IO6−] + k4[CrO42−][H3IO62−], where Rc is defined as the increase in the rate of the oxygen exchange of chromate upon the addition of periodate ions. The catalytic rates were analyzed according to the rate law to obtain the values of the rate constants (k1−k4); k1, k2, and k3 are on the order of magnitude of 103—104 mol−1 dm3 s−1, and k4 = 5 mol−1 dm3 s−1 at 0 °C. For the reaction between H3IO62− and CrO42−, the energy and entropy of activation were obtained to be 26 kJ mol−1 and −143 J K−1 mol−1, respectively.
Charge-Transfer Complexation in Aqueous Polyelectrolyte Solution. I. Complexation between Dimethoxyanthracenesulfonate Ion and Anthraquinonesulfonate Ion
Authors: Itaya Tomoyuki , Kawabata Yoshiya , Ochiai Hiroshi , Ueda Kazuyoshi , Imamura Akira
Published: July 2006

Absorption and fluorescence spectroscopic studies on the charge-transfer (CT) complexation between 9,10-dimethoxyanthracene-2-sulfonate ion (DMACS−) and 9,10-anthraquinone-2-sulfonate ion (AQS−) in aqueous solution were performed in the presence of poly(allylammonium chloride) (PAAH+Cl−), as well as in its absence. No spectroscopic indication of the CT complex was recognized by mixing Na+DMACS− (1 × 10−4 M) with Na+AQS− (1 × 10−4 M), but the addition of PAAH+Cl− to the mixed solution brought about the CT complexation. On the other hand, in the absence of PAAH+Cl−, DMACS− and AQS− also form the CT complex when their concentrations become ca. 1 × 10−3 M. Therefore, the CT complexation between DMACS− and AQS− in PAAH+Cl− solution can be attributed to a close proximity of DMACS−–AQS− pairs, which results from the electrostatic binding of them by the polyions. The continuous variation method for the CT band indicated that a 1 : 2 (DMACS− : AQS−) complex and a 1 : 1 complex were preferentially formed in the presence and absence of PAAH+Cl−, respectively. The above results show that the high electrostatic potential of PAAH+ affects the complexation, especially the stoichiometry.
Catalytic Conversion of Alkyl Acetate into Alkene and Acetic Acid over Iron(III) Ion-Exchanged H-Mordenite
Authors: Ichikawa Tsuneki , Hosokawa Hideyuki , Yoshida Hiroshi
Published: July 2006

The iron(III) ion in H-mordenite was found to act as a very strong oxidizing agent. It accelerates the conversion of alkyl acetate into alkene and acetic acid by withdrawing an electron from the coordinated alkyl acetate. It also oxidizes water into proton and oxygen, and benzene into benzene radical cation.
Reaction Pathway and Selective Hydrogenation on Catalyst Derived from Oxidation Treatment of Mg2Cu Alloy
Authors: Chikamatsu Nobuyasu , Tagawa Tomohiko , Goto Shigeo
Published: July 2006

A catalyst derived from oxidation treatment of Mg2Cu alloy was studied in a gas-phase continuous-flow reactor under atmospheric pressure to investigate the specific selectivity for hydrogenation. In order to propose the reaction pathways for hydrogenation of long chain unsaturated ester, reactivities of characteristic functional groups were tested.

The reactions of ester and aldehyde groups showed higher selectivity to alcohols than to paraffins. We concluded from competitive reactions of two reactants that hydrogenation of unsaturated bond group was inhibited by the adsorption of ester or aldehyde group.

The effect of partial pressure on each reaction rate was summarized into the Langmuir equation. The main route to unsaturated alcohol and reasons for the increased selectivity to alcohol are discussed.
Pressure Effect on the Inter- and Intramolecular Vibrations of Hexachlorobenzene Crystal
Authors: Sadakuni Gouki , Maehara Masayoshi , Kawano Hiroshi , Nibu Yoshinori , Shimada Hiroko , Shimada Ryoichi
Published: July 2006

The effect of pressure on the Raman active inter- and intramolecular vibrations of the hexachlorobenzene crystal was studied under hydrostatic pressure up to 5.5 GPa. The Raman frequencies of the inter- and intramolecular vibrations increased monotonically and some bands due to the degenerate intramolecular vibrations were resolved into doublets with increasing pressure. The pressure-induced frequency shift and factor group splitting of the bands due to the intramolecular vibrations were calculated using an intermolecular potential of the atom–atom type. These results show that (1) no phase transition takes place in the crystal under pressure up to 5.5 GPa, (2) the observed pressure-induced frequency shift is mainly caused by the repulsive force between chlorine atoms belonging to the adjacent molecules, and (3) the observed splitting of the bands due to the degenerate intramolecular vibrations is caused by the different intermolecular force acting to the a and b vibrational modes.
N-Nitroso and C-Nitro Derivatives from Di-(2-pyridyl)amine and Butyl Nitrite
Authors: Giumanini Angelo G , Poiana Marco , Verardo Giancarlo , Strazzolini Paolo , Tolazzi Marilena , Cerioni Giovanni
Published: July 2006

The reaction between di-(2-pyridyl)amine and butyl nitrite produced N-nitrosodi-(2-pyridyl)amine, (5-nitro-2-pyridyl)-2-pyridylamine and (3-nitro-2-pyridyl)-2-pyridylamine of which the likely conformations are evinced from spectral data. Structural elucidation of N-nitrosodi-(2-pyridyl)amine in the solid state by X-ray diffraction excluded any substantial contribution of the rings to resonance structures.
Further Investigations on Polar Substituent Effects on the NMR Chemical Shifts of N-Acylanilines and Related Compounds. Correlation Analytical Approach and Solvent Effects
Authors: Yuzuri Tomoaki , Suezawa Hiroko , Hirota Minoru
Published: July 2006

The 1H, 13C, and 15N chemical shifts of various substituted anilides of the carboxylic and sulfonic acids ZNHC6H4Y (Z = C6H5CO, CH3CO, CF3CO, and CH3SO2) and related compounds were correlated with σ and related substituent constants. The ρ-values from the Hammett type plots of the chemical shifts were shown to provide some important information concerning the polarization of the amide chromophore. The solvent effect on ρ showed the fact that the local π-polarization of an amide is strengthened in polar or hydrogen-donating solvents.
Synthesis and Reactions of Monosilylated 1,3,5-Hexatriyne and 1,3,5,7-Octatetrayne. Total Synthesis of Caryoynencins
Authors: Yamaguchi Masahiko , Park Hyeon-Joo , Hirama Masahiro , Torisu Kazuhiko , Nakamura Shigeo , Minami Toru , Nishihara Hiroshi , Hiraoka Tetsuo
Published: July 2006

Selective monodesilylation of 1,8-bis(t-butyldiphenylsilyl)-1,3,5,7-octatetrayne and 1,6-bis(t-butyldiphenylsilyl)-1,3,5-hexatriyne with lithiated phenylacetylene gave unstable 1-(t-butyldiphenylsilyl)-1,3,5,7-octatetrayne and 1-(t-butyldiphenylsilyl)-1,3,5-hexatriyne, respectively. The terminal acetylenes on lithiation added to aldehydes and a ketone giving polyynols in high yields. The reaction was applied to the synthesis of polyyne antibiotics, caryoynencins. Polymerization of the terminal octatetrayne on an ITO-coated glass plate gave a film, which showed conductivity of 10−4 S cm−1 when doped with SO3.
Implications of a Transition State in a Diels–Alder Reaction in Supercritical Carbon Dioxide
Authors: Ikushima Yutaka , Saito Norio , Sato Osamu , Arai Masahiko
Published: July 2006

For the Diels–Alder reaction between isoprene and methyl acrylate in supercritical carbon dioxide at 323 K, the solubility parameter of the activated complex was determined as a function of the pressure, ranging from 7 to 20 MPa, in order to study the nature of the complex and the effect of the solvent on the reaction. The relation between the solubility parameter and the ET(30)-scale was examined as well.
Electrocrystallization of Quinhydrone
Authors: Awano Hiroshi , Sakai Shoji , Kuriyama Takashi , Ohba Yoshihiro
Published: July 2006

Quinhydrone crystals were deposited at 2.0 V vs. Ag onto SnO2-coated glass substrates from aqueous solutions of hydroquinone in the presence of NaCl, HCl, or NaOH. The crystals were observed with backscattered image SEM, and characterized with X-ray diffraction and IR spectroscopy. In situ visible absorption spectra were measured and a mechanism of deposition is discussed.
Practical Synthesis of Palladium Bis(trifluoromethanesulfonate) and Its Application to the Synthesis of Palladium Complexes
Authors: Murata Shizuaki , Ido Yoshiyuki
Published: July 2006

Palladium bis(trifluoromethanesulfonate) is usually prepared from the reaction of palladium dinitrate or diacetate and trifluoromethanesulfonic acid. Reactions of palladium bis(trifluoromethanesulfonate) with various ligands (L and/or X−) give corresponding palladium(II) complexes, such as [Pd(CF3SO3)2L2] and [PdX2L2].
Preparation of Linear Oligoaniline Derivatives Using Titanium Alkoxide as a Condensing Agent
Authors: Ochi Miyoko , Furusho Hitoshi , Tanaka Jun
Published: July 2006

Linear oligoaniline derivatives were prepared by the reaction of aromatic amines and phenols using various titanium alkoxides as condensing agents. The oligomers obtained were silver white microscopic crystals. Titanium alkoxides used were titanium alkoxide or titanium alkoxide aryloxide and the latter showed high dehydration condensation activity in comparison with the usual titanium alkoxides.
One-Pot Synthesis of Ethyl 3-(2-Hydroxyalkyl)aminoalkanoates by Ring Opening of 1,3-Oxazolidines Using Reformatsky Reagent
Authors: Nishiyama Tomihiro , Kishi Hiroshi , Kitano Kouji , Yamada Fukiko
Published: July 2006

Oxazolidines, obtained by the condensation of aldehydes with 2-anilino-1-alkanols, react with the Reformatsky reagent derived from ethyl bromoacetate under mild reaction conditions to afford ethyl 3-(2-hydroxyalkyl)aminoalkanoates.
A NEW METHOD OF ESTIMATING CATAPHORETIC VELOCITY IN A CONCENTRATED SUSPENSION
Authors: Komagata Sakuji
Published: July 2006

The results of the weight method coinside well with those of U-tube method. Although there are many points to be improved in the present apparatus, the author believes that the method is of some value, as it is, for the reason that there are few methods for the measurement of cataphoretic velocity in a heavily concentrated suspension. The author has designed the apparatus operating automatically under the same principle, results of which will be reported in a near future.
THE RELATION BETWEEN KOLBE’S REACTION AND HYDROGEN ION CONCENTRATION. THE MECHANISM OF KOLBE’S REACTION
Authors: Matsuda Hamilton Ryoichi
Published: July 2006

(1) The relation between ethane and oxidizing substances in the solutions formed by the electrolyses of acetate solutions is discussed.

(2) It is demonstrated that acetyl peroxide is first formed at the anode, and that ethane is one of its decomposition products.

(3) The presence of hydrogen peroxide in the solutions after electrolysis is attributed to the following hydrolyses of acetyl peroxide: (CH_3·COO)_2+H_2O &=CH_3·COOH+CH_3·COOOH,

CH_3·COOOH+H_2O &=CH_3·COOH+H_3O_2. (4) It is discussed how the formation of hydrogen peroxide is related to the pH value of the solution on the one hand and to the concentration of the solution on the other.

(5) The relation existing between the ethane and the hydrogen peroxide formations is also discussed.

(6) It is concluded that the facts observed in the experiments so far carried out by the writer can well be explained by assuming the intermediate formation of acetyl peroxide.
THE ACTIVITY COEFFICIENT OF ZINC SULPHATE FROM ELECTROMOTIVE FORCE MEASUREMENTS
Authors: Masaki Kosaku , Ikkatai Takuo
Published: July 2006

1. Electromotive forces of the cell, Zn–Hg (sat amalgam) |ZnSO4(m), Hg2SO4(s)| Hg, were measured at 25°C. in the range of the concentrations of 0.0004321 to 3 molal.

2. The electromotive force of higher dilutions is quite abnormal owing to the solubility of mercurous sulphate.

3. The mean activity coefficients of zinc sulphate for more concentrated parts were calculated by using the Cowperthwaite and LaMer’s data about dilute solutions. The potential E0 of the cell, when ion activities of zinc sulphate are hypothetically one molal, was found to be 1.37475 volt at 25°C.
STUDIES ON REACTIONS BETWEEN GAS AND SOLID. IV. AZOTATION OF CALCIUM CARBIDE AND THE EFFECT OF TEMPERATURE ON ITS VELOCITY
Authors: Aono Takeo
Published: July 2006

The effect of temperature elevation to the velocity of azotation of powdered calcium carbide (with 1% CaF2) has experimentally been determined.

1. At a constant temperature lower than about 950°C., the following relation was found:

(Remark: Graphics omitted.)

where nt means the degree of azotation (in %) after a time t, and n∞ the final and maximum value of nt; k5 and t′ are constants.

2. At a constant temperature between about 1000 and 1060°C., the common monomolecular course was found, namely: n_t=n_∞{1-e^-k^′_4(t+t^′)}where k4′ being a velocity constant.

3. At any temperature there is a maximum in the velocity; the time and the degree of azotation at the maximum point increase with rising temperatures. The following approximate relation was found between them.

(Remark: Graphics omitted.)

where Y is the degree of azotation at the maximum of the velocity, T the absolute temperature, and A and B constants.

4. From the temperature coefficient of the velocity constant, the apparent heat of activation for a powdered technical carbide (with 1% CaF2) was calculated to be about 58.6 Cal./mol. at temperatures between 1000° and 1060°C., and about 33 Cal./mol. above 1080°C.
STUDIES ON REACTION BETWEEN GAS AND SOLID. VI. AZOTATION OF CALCIUM CARBIDE AND THE EFFECT OF CATALYSERS ON ITS VELOCITY
Authors: Aono Takeo
Published: July 2006

The effects of some catalytic substances to the velocity of azotation of both powdered and “granular” carbide were experimentally determined.

1. There is an optimum quantity of calcium fluoride to be added to the carbide to get the highest velocity of azotation, the quantity of which is a function of both carbide and reaction temperature.

2. The added substances not only have some influence upon the velocity, but also change the characteristics of the velocity curves of azotation.

3. Carbon and carbon containing substances or those which sets carbon free from carbide show strong catalytic action to the azotation of calcium carbide. The opinion that the nascent carbon must be acting as a catalyser is supported.
ON THE COPPER AGE IN ANCIENT CHINA
Authors: D\={o}no Tsurumatsu
Published: July 2006

(1) Three specimens of ancient Chinese spear-heads which are said unearthed from. Yin site ((Remark: Graphics omitted.)) were analysed, and it was found that they consist mainly of copper added with certain quantities of lead and contain no significant amount of tin.

(2) From the chemical studies, all these spear-heads are by no means of bronze and they are regarded as the first pure copper implements ever discovered in China.

(3) The prevailing opinion which negates the existence of the pure copper age in ancient China must thus be abandoned, and the existence of the copper age in China must be admitted.

(4) It is supposed that if these specimens were actually manufactured in Yin dynasty ((Remark: Graphics omitted.)), the pure copper age in China existed at about Yin dynasty ((Remark: Graphics omitted.)), and the beginning of the bronze age followed that age.
CONCENTRATION CELL WITH TERNARY ELECTROLYTE
Authors: Masaki Kosaku
Published: July 2006

(1) The electromotive forces of the concentration cells with ternary electrolytes were studied by the three methods.

(a) At anion reversible cell with mercury electrode.

(b) At anion reversible cell with silver electrode.

(c) At the cation reversible cell with amalgam electrode.

(2) Several equations were theoretically obtained to calculate the electromotive forces of the cells above mentioned.

(3) Mobilities at 30°C. and activity coefficients of chlorine, zinc, calcium, barium, strontium and magnesium ions were calculated.

(4) We had a very good agreement between measured electromotive forces and calculated ones in the very dilute solutions.
SOME EXPERIMENTS WITH PEROWSKITE (CaO·TiO2) AND TITANITE (CaO·TiO2·SiO2)
Authors: Iwasé Keizô , Fukusima Masaji
Published: July 2006

In the experimental study of the equilibrium of the system consisting of calcium silicate, CaO·SiO2, and titanium dioxide, TiO2, calcium titanate, a compound belonging to the other system has often been found in the crystallized mass of a compound CaO·TiO2·SiO2, calcium titanium silicate, and hence thorough investigation of the crystallization of calcium titanate and calcium titanium silicate was carried out before the determination of the equilibrium of the above mentioned system. These two compounds were synthesized from their components and their X-ray patterns were taken by the Debye–Scherrer method, and using these photographs as the standard, the condition has been fully determined in which these two compounds separate out from the melt. Microscopic study with a reflected light has also been applied for the identification of these two compounds. The stabilities of these two compounds were also investigated by several methods. Finally, the melting point of calcium titanium silicate was determined by the cooling curve method in which supercooling of the melt was prevented by seeding.
GLUCOSULFATASE. V
Authors: Soda Tokuro , Egami Fujio
Published: July 2006

1. Glucosulfatase is a simply hydrolysing enzyme.

2. It is almost perfectly adsorbed by kaolin.

3. It can not be adsorbed by BaSO4, aluminium hydroxide gel and charcoal. These adsorbents can be used for the purification of the enzyme. Thus a perfectly clear enzyme solution is obtainable. A solid preparation of very active glucosulfatase was obtained. Its purity (G-Sulf) is 11.6 while the original value was 1.0.

4. The enzyme action is inhibited by: glucose, galactose, MgCO3, inorganic sulphate and phosphate.

5. Glucosulfatase always contains phenosulfatase but they are not one and the same enzyme.
HETEROGENEOUS CHEMICAL REACTIONS IN THE SILENT ELECTRIC DISCHARGE. IX
Authors: Miyamoto Susumu
Published: July 2006

The chemical reactions in the silent electric discharge were studied when hydrogen reacted on the following inorganic solid substances.

(1) Potassium sulphite. Reaction products:—hydrogen sulphide potassium hydroxide.

(2) Cadmium bromide. Reaction products:—metallic cadmium and hydrogen bromide.

(3) Potassium perchlorate. Reaction products:—potassium chloride and water.

(4) Mercuric cyanide. Reaction products:—metallic mercury and hydrogen cyanide.

(5) Mercuric thiocyanate. Reaction products:—mercuric sulphide, metallic mercury, hydrogen cyanide, hydrogen sulphide, and thiocyanic acid.

(6) Silver cyanide. Reaction products:—metallic silver and hydrogen cyanide.

(7) Sodium thiocyanate. Reaction products:—sodium sulphide, hydrogen sulphide, and hydrogen cyanide.

(8) Lead thiocyanate. Reaction products:—lead sulphide, hydrogen sulphide, and hydrogen cyanide.

(9) Potassium cyanide. It was proved that potassium cyanide was hardly reduced under the conditions of this experiment.

The writer wishes to express his appreciation of a grant from the Imperial Academy towards the expenses of this research.
REACTIONS BETWEEN ETHYLENE CHLORIDE AND CHLORINE
Authors: Hamai Senzo
Published: July 2006

(1) In the reaction between chlorine and ethylene chloride in the liquid phase 1,1,2,-trichlorethane is the principal product and in the gaseous phase the formation of hexachlorethane predominates.

(2) The reaction between gaseous chlorine and liquid ethylene chloride seems to occur mainly on the liquid gas interface.

(3) Hydrogen chloride gas dissolved in the mixture catalytically accelerates the reaction.

(4) There seems to exist an induction period in the reaction between ethylene chloride and chlorine possibly owing to catalytic acceleration by either hydrogen chloride or substituted product or both in later stage.

(5) In the gaseous reaction between chlorine and ethylene chloride the formation of hexachlorethane predominates especially when chlorine exists largely in excess to ethylene chloride vapour.

(6) A suggestion is made as to the method of study on chemical reactions, especially on chlorination reaction (substitution).
Administrative deficiency citations and quality of care in nursing homes
Authors: Castle Nicholas G , Longest Beaufort B
Published: July 2006

In this investigation, we examine deficiency citations for administration in nursing homes. Administration is defined as the top managers in each facility, consisting of the nursing home administrator and director of nursing. We examine the association between deficiency citations for administration (indicating poor administration practices) and quality of care. Regulators, as well as consumers, are interested in this association. Data used came from the 1996-2004 Online Survey, Certification And Recording (OSCAR) data, representing approximately 17,000 facilities per year. We find that 5% of facilities received a deficiency citation for administration, and lower facility quality is associated with these administration deficiency citations.
Mobile phone-based surveillance of cardiac patients at home
Authors: Scherr D , Zweiker R , Kollmann A , Kastner P , Schreier G , Fruhwald F M
Published: July 2006

We tested the reliability, acceptability and feasibility of a home-monitoring system for cardiac patients. Each participant was equipped with a mobile phone, an automatic blood pressure device and a digital weight scale. In total, 20 patients (14 patients with chronic heart failure, six patients with hypertension; mean age 50 years, standard deviation [SD] 14) were monitored for 90 days each. They were asked to measure their blood pressure, pulse and body weight every day, and to transfer the data together with the dosage of medication to the telemonitoring server using wireless Internet technology in the mobile phone. The physician in charge received email alerts when reported data fell outside pre-defined limits. The patients' compliance with the system was high. During a cumulative monitoring period of 1735 days, there were 2040 data transfer sessions, a mean of 102 per patient (SD 43). The mean percentage of successful data transfers was 83% (SD 22). The stability of the telemonitoring system was 98%, meaning that patient data transfer was almost always possible. The accessibility of the secure web server for physicians was above 99%. The web-based home-monitoring system was reliable and easy to handle for both patients and health care professionals. It may be a useful tool for patients with heart failure as well as hypertensive patients.
Equity of access to health care. Evidence from NHS Direct in the UK
Authors: Knowles Emma , Munro James , O'Cathain Alicia , Nicholl Jon
Published: July 2006

In the UK National Health Service (NHS), NHS Direct, the national 24-h telephone helpline, has been available in England and Wales since 2000 and has been termed a 'single gateway' to health care. We conducted a population survey of 15,004 people in areas covered by the service, which included questions about NHS Direct use and socio-economic characteristics. After removing undeliverable questionnaires, the survey response rate was 60% (8750/14,516). In all, a quarter of respondents had ever used NHS Direct (26%, 95% confidence interval 25–27), ranging from 32% of the population in Preston/Chorley (888/2794) and Newcastle and North Tyneside (515/1621) to 17% (2215/8536) in Sheffield, which had introduced the service 20 months later. Logistic regression showed that those from poorer socioeconomic groups or with communication difficulties were less likely to have used the service than others. Overcoming this apparent bias against those likely to have the greatest need is an unsolved problem not confined to telemedicine.
A systematic review of the literature on home monitoring for patients with heart failure
Authors: Martínez Andrés , Everss Estrella , Rojo-Álvarez José Luis , Figal Domingo Pascual , García-Alberola Arcadio
Published: July 2006

We conducted a systematic review of the literature for assessing the value of home monitoring for heart failure (HF) patients. The abstracts of 383 articles were read. We excluded those in which either no home monitoring was done or only the technical aspects of the telemedicine application were described. Forty-two studies met the selection criteria. We classified the results into feasibility (technical and institutional) and impact (on the clinical process, on patient health, on accessibility and acceptability of the health system, and on the economy). Evaluating the articles showed that home monitoring in HF patients is viable, given that: (1) it appears to be technically effective for following the patient remotely; (2) it appears to be easy to use, and it is widely accepted by patients and health professionals; and (3) it appears to be economically viable. Furthermore, home monitoring of HF patients has been shown to have a positive impact on: (1) the clinical process, supported by a significant improvement of patient follow-up by adjustment of treatment, diet or behaviour, as well as hospital readmissions and emergency visits reduction; (2) the patient's health, supported by a relevant improvement in quality of life, a reduction of days in hospital, and a decrease in mortality; and (3) costs resulting from the use of health resources.
Pharmacologic Expulsive Treatment of Ureteral Calculi
Authors: Beach Michele A , Mauro Laurie S
Published: July 2006

Objective:

TO evaluate the role of nifedipine and the α1-adrenoreceptor antagonists tamsulosin, terazosin, and doxazosin in the expulsive treatment of ureteral calculi.

Data Sources:

Literature was searched via MEDLINE (1966–February 2006) with subsequent bibliographic review. MeSH headings included ureteral calculi, nifedipine, doxazosin, and adrenergic α-antagonists. Key terms were ureteral calculi, nifedipine, tamsulosin, terazosin, and doxazosin.

Study Selection and Data Extraction:

Trials evaluating nifedipine, tamsulosin, terazosin, and doxazosin for expulsion of ureteral stones were reviewed. All were published in English-language, peer-reviewed journals.

Data Synthesis:

Several trials have evaluated the effects of nifedipine and tamsulosin on ureteral stone passage rates and mean time to stone passage in stones no larger than 15 mm. In 28 day trials, the rates of ureteral stone passage were 35–70% in the control groups compared with 77.1–80% in patients treated with nifedipine and 79.3–100% in patients treated with tamsulosin. Average number of days to stone passage in the control groups was 4.6–20, and the time to stone passage was only 5–9.3 days in patients receiving nifedipine and 2.7–7.9 days in those receiving tamsulosin. The stone passage rates and time to stone passage appeared to be similar in one trial that compared tamsulosin with terazosin and doxazosin. Limited data suggest that these agents may have a role as adjuncts to shock wave lithotripsy. Adverse drug reactions were uncommon.

Conclusions:

Nifedipine, tamsulosin, terazosin, and doxazosin are safe and effective options in enhancing ureteral stone expulsion in selected patients with uncomplicated presentations.
Specification of Optic Nerve Oligodendrocyte Precursors by Retinal Ganglion Cell Axons
Authors: Gao Limin , Miller Robert H.
Published: July 2006

Cell fate commitment in the developing CNS frequently depends on localized cell–cell interactions. In the avian visual system the optic nerve oligodendrocytes are derived from founder cells located at the floor of the third ventricle. Here we show that the induction of these founder cells is directly dependent on signaling from the retinal ganglion cell (RGC) axons. The appearance of oligodendrocyte precursor cells (OPCs) correlates with the projection of RGC axons, and early eye removal dramatically reduces the number of OPCs.In vitrosignaling from retinal neurites induces OPCs in responsive tissue. Retinal axon induction of OPCs is dependent onsonic hedgehog(Shh) and neuregulin signaling, and the inhibition of either signal reduces OPC inductionin vivoandin vitro. The dependence of OPCs on retinal axonal cues appears to be a common phenomenon, becauseocular retardation(orJ) mice lacking optic nerve have dramatically reduced OPCs in the midline of the third ventricle.
Abnormal Categorization and Perceptual Learning in Patients with Hippocampal Damage
Authors: Graham Kim S. , Scahill Victoria L. , Hornberger Michael , Barense Morgan D. , Lee Andy C. H. , Bussey Timothy J. , Saksida Lisa M.
Published: July 2006

Prevailing theory holds that the medial temporal lobe (MTL) subserves declarative memory exclusively, whereas nondeclarative memory is independent of this brain region. Recent studies in patients with amnesia, however, have shown that performance on declarative memory tasks may not always be dependent on a single MTL memory system, instead highlighting the critical role of anatomically distinct structures in processing different stimulus types. In particular, the hippocampus has been implicated in spatial memory, whereas perirhinal cortex seems critical for object memory. To assess whether stimulus type would also be a key dimension in nondeclarative memory, patients with selective hippocampal lesions were tested on simple categorization and perceptual learning of faces and virtual reality scenes. The patients demonstrated preserved categorization and perceptual learning of faces but abnormal performance when the stimuli to be discriminated were virtual reality scenes. These findings imply that stimulus type may be a more critical predictor of performance on memory tasks (declarative and nondeclarative) than previously thought. They also suggest that reports of good nondeclarative memory after MTL damage may, in some cases, simply reflect the use of stimuli that fail to tap the processes dependent on structures in this region, such as spatial processing in the case of the hippocampus.
A Simple Account of Cyclopean Edge Responses in Macaque V2
Authors: Bredfeldt Christine E. , Cumming Bruce G.
Published: July 2006

It has been shown recently that neurons in V2 respond selectively to the edges of figures defined only by disparity (cyclopean edges). These responses are orientation selective, often preferring similar orientations for cyclopean and luminance contours, suggesting that they may support a cue-invariant representation of contours. Here, we investigate the extent to which processing of purely local visual information (in the vicinity of the receptive field) might explain such results, using the most impoverished stimulus possible containing a cyclopean edge (a circular patch of random dots divided into two regions by a single edge). Many V2 cells responded better to the cyclopean edge than to uniform disparities, and most of these were at least broadly selective for the orientation of the cyclopean edge. Two characteristics argue against a cue-invariant contour representation: (1) the cyclopean edge response was frequently abolished by small changes to the component disparities; and (2) although V2 cells frequently responded to both signs of a cyclopean edge (defined by which side of the edge is in front), they did so at different edge locations. These characteristics are consistent with a simple feedforward scheme in which V2 neurons receive inputs from several V1 subunits with different disparity selectivity. We also found a correlation between the preferred orientations for cyclopean edges and contrast stimuli, suggesting that this feedforward wiring is not random. These characteristics suggest that V2 responses to cyclopean edges may be useful in supporting a cue-invariant contour representation higher in the visual pathway.