bluuebunny/crossref_metadata_2025_split huggingface dataset:
Thermoosmosis and Transported Entropy of Water across Hydrocarbonsulfonic Acid-Type Cation-Exchange Membranes
Authors: Suzuki Takashi , Iwano Keiko , Kiyono Ryotaro , Tasaka Masayasu 
Published: July 2006

Abstract
Solvent transport across hydrocarbonsulfonic acid-type cation-exchange membranes was measured for aqueous electrolyte solutions under a temperature difference and an osmotic pressure difference. The hydrocarbonsulfonic acid-type cation-exchange membranes, Aciplex® K-181, Aciplex® K-182, and Neosepta® C66-5T with the H+, Li+, Na+, K+, NH4+, CH3NH3+, (CH3)2NH2+, (CH3)3NH+, (CH3)4N+, (C2H5)4N+, (n-C3H7)4N+, and (n-C4H9)4N+ forms were used. The direction of thermoosmosis across the membranes with the H+ and the Na+ forms was from the cold side to the hot side, as observed for various anion-exchange membranes. However, the direction was from the hot side to the cold side for the membranes with the ammonium and the alkylated ammonium ion forms, except for Neosepta® C66-5T with the (CH3)4N+, (C2H5)4N+, and (n-C3H7)4N+ forms. This is why the entropy of the water in the membranes will increase with increasing the number of hydrogens combining with the nitrogen of the alkylated ammonium counterions, because they are exchangeable with the hydrogens of water molecules in the membranes. Thermoosmosis across the membranes with the (n-C3H7)4N+ and the (n-C4H9)4N+ forms will also occur toward the cold side, because the hydrophobic interaction between the hydrophobic alkyl groups of the counterions and the membrane matrix is very strong and the membranes act as a hydrophobic polyethylene membrane.
Pressure Effect on the Inter- and Intramolecular Vibrations of Pyrazine Crystal
Authors: Maehara Masayoshi , Kawano Hiroshi , Nibu Yoshinori , Shimada Hiroko , Shimada Ryoichi 
Published: July 2006

Abstract
The effect of pressure on the Raman active inter- and intramolecular vibrations of the pyrazine crystal was studied under hydrostatic pressure up to 5 GPa. The frequency shift of the intermolecular vibrations and the discontinuous variation of the bandwidth of the ν2 and ν1 intramolecular vibrations induced by pressure at constant temperature indicate that the pyrazine crystal undergoes phase transition (change of the molecular orientation in the crystal) under about 1 GPa. The pressure-induced frequency shift of the intramolecular vibrations was calculated using an intermolecular potential of the atom–atom type. The calculation also suggests the occurrence of the phase transition of the crystal.
Raman Spectroscopic Study on the Temperature Dependence of the Uncoupled O–D Stretching Band from HDO Molecules in Concentrated Aqueous Zn(ClO4)2 Solutions
Authors: Kameda Yasuo , Sugawara Ikuko , Kijima Ken-ichi , Usuki Takeshi , Uemura Osamu 
Published: July 2006

Abstract
Polarized Raman spectra of the uncoupled O–D stretching vibrational bands in concentrated aqueous Zn(ClO4)2 solutions have been recorded in the temperature range of 26—95 °C. Observed isotropic and anisotropic spectra have been analyzed by a double-difference method, in conjunction with a least squares fitting procedure, to deduce Raman band components arisen by HDO molecules in the first hydration shell of the constituent ions in the solution. Two band components centered near 2420 and 2640 cm−1 were assigned to the O–D stretching vibrational mode of HDO molecules coordinated to Zn2+ and ClO4−, respectively. These frequencies agree with the infrared double-difference results. Further, it has been found that the relative integrated intensity of the ion-perturbed O–D bands is quite different from that of the ‘bulk’ HDO molecules. The temperature dependence of peak parameters such as the frequency and peak area for Zn2+ and ClO4−-perturbed bands is very small in the temperature range of 26—95 °C, in contrast to a pronounced collapse of the band from bulk HDO molecules at elevated temperatures. This suggests that the local structure around these ions in the solution changes little in the temperature range examined in this study.
Simulation of the Valence X-Ray Photoelectron Spectra of 16 Polymers by the Semiempirical HAM/3 MO Method Using the Model Molecules
Authors: Endo Kazunaka , Inoue Chiaki , Kaneda Yasuo , Aida Masayuki , Kobayashi Naoya , Chong Delano P 
Published: July 2006

Abstract
The HAM/3 method was used to provide a better assignment of the valence X-ray photoelectron spectra of 16 polymers involving nitrogen, oxygen, fluorine, a glucose unit, and a benzene nucleus using the monomer, dimer or trimer model molecules without consideration of the contraction factor of the energy scale. The calculated Al Kα photoelectron spectra were obtained using Gaussian functions of a fixed approximate linewidth, 0.10 Ik and Ik = I′k − WD, where I′k is the vertical ionization potential of each MO and WD is an approximate shift to account for the work function of the sample and other energy (polarization energy and so on) effects. We assumed that WD corresponds to the shift that we must apply before we can compare the calculated spectrum for the single model molecule with the observed spectrum for the solid. The approximate linewidth corresponds to the experimental result that the inner valence spectra are broader. The theoretical spectra showed good agreement with the spectra of the polymers observed between 0—40 eV.
Silica Gel-Bonded Cationic Polyelectrolyte with Ferron as Counterion. Application to Preconcentration or Elimination of Trace Metals
Authors: Prasad Bhim Bali , Sundd Sonu 
Published: July 2006

Abstract
An integral N-based cationic polymer, poly[N-xylylene N,N′-dicyclohexylethylenediammonium dibromide], was immobilized through hydrogen bonding on the surface of silica gel. The chelating ligand, 7-iodo-8-hydroxyquinolino 5-sulfonic acid (Ferron), was subsequently attached to the matrix by ion-exchange method; this renders an extremely stable stationary phase, free from leaching complications, under electrostatic (salt) bond interactions. Analytical characteristics of this sorbent were studied. The optimum sorption conditions for Cu2+, Cd2+, Zn2+, Pb2+, Co2+, Ni2+, and Fe3+ under static and dynamic (column) methods were ascertained. The chelator was found to be selective for the retention of Cu2+, Pb2+, and Fe3+ from multi-element mixtures. The relatively fast kinetics of the sorbent with the time required to reach half of the maximum sorption (t1/2 value 2 min) and the percentage attainment of equilibrium in 2 min (P2 min value &gt; 50%) for most of the heavy metals, excluding Ni2+, reveal the suitability of the chelating resin in column operation, especially in single column ion-chromatography. The specific applications of the sorbent in purification of supporting electrolyte/buffers required for voltammetric detection are also explored.
Molecular Structure of Nitro- and Nitrito-Copper Complexes as Reaction Intermediates in Electrochemical Reduction of Nitrite to Dinitrogen Oxide
Authors: Komeda Nobutoshi , Nagao Hirotaka , Kushi Yoshinori , Adachi Gin-ya , Suzuki Masatatsu , Uehara Akira , Tanaka Koji 
Published: July 2006

Abstract
Copper-nitrito and -nitro isomers, [Cu(ONO)(tpa)]PF6 and [Cu(NO2)(tpa)]PF6 (tpa = tris[(2-pyridyl)methyl]amine) were isolated and the molecular structures were determined by X-ray analysis. [Cu(ONO)(tpa)]PF6 (C18H18N5O2PF6Cu) crystallizes in the monoclinic space group P21/a with a = 13.374(2), b = 14.033(2), c = 13.455(2) Å, β = 119.10(1)°, V = 2206.5(6) Å3, and Z = 4. [Cu(NO2)(tpa)]PF6 (C18H18N5O2PF6Cu) crystallizes in the orthorhombic space group I/ba2 with a = 16.718(3), b = 17.554(3), c = 14.785(3) Å, V = 4338(1) Å3, and Z = 8. Those nitrito- and nitro-complexes exist as an equilibrium mixture in solutions. Electrochemical reduction of NO2− in the presence of [Cu(H2O)(tpa)](ClO4)2 at −0.4 V in H2O (pH 7.0) catalytically produced N2O with concomitant evolution of a small amount of NO via the nitro and nitrito adducts.
Extraction Behavior of Di-μ-oxo-bis[oxomolybdenum(V)] with 2-Methyl-5-octyloxymethyl-8-quinolinol
Authors: Feng Yuqi , Imura Hisanori , Ohashi Kousaburo 
Published: July 2006

Abstract
Binuclear oxomolybdenum(V), Mo2O42+, was quantitatively extracted with 0.01 mol dm−3 2-methyl-5-octyloxymethyl-8-quinolinol (HMO8Q) in chloroform at pH 2.3 and isobutyl methyl ketone at pH 1.0—3.9. To elucidate the extraction equilibrium, the effect of the pH as well as the HMO8Q and molybdenum(V) concentration on the distribution ratio of Mo2O42+ was studied. The extracted complex was found to be Mo2O4(MO8Q)2; the extraction constants (Kex) were determined to be 100.15 and 101.57 in benzene and chloroform, respectively. These values were lower than Kex = 103.26 obtained in the Mo2O42+-5-octyloxymethyl-8-quinolinol–chloroform system, suggesting a steric effect of the methyl group at the 2-position. In the presence of trioctylphosphine oxide (TOPO) a great enhancement of molybdenum(V) extraction was found and could be ascribed to the formation of an adduct, Mo2O4(MO8Q)2(TOPO).
Synthesis and Properties of Linear-Type S-Bridged RhIIINiIIRhIII Trinuclear Complexes with 2-Aminoethanethiolate (aet) or l-Cysteinate (l-cys). Crystal Structure of [Ni{Rh(aet)3}2](NO3)2
Authors: Konno Takumi , Okamoto Ken-ichi 
Published: July 2006

Abstract
The reaction of fac(S)-[Rh(aet)3] with Ni2+ at room temperature gave a linear-type S-bridged RhIIINiIIRhIII trinuclear complex, [Ni{Rh(aet)3}2]2+ (1). A similar reaction of ΔLll-fac(S)-[Rh(l-cys-N,S)3]3− with Ni2+ produced the corresponding trinuclear complex with l-cys ligands, ΔLllΔLll-[Ni{Rh(l-cys-N,S)3}2]4− (ΔLllΔLll-2), retaining the ΔLll configuration of the starting complex. The crystal structure of 1(NO3)2 was determined by X-ray diffraction. [Ni{Rh(aet)3}2](NO3)2·2H2O, chemical formula C12H40N8S6O8NiRh2, crystallizes in the triclinic space group with a = 12.249(3), b = 13.366(4), c = 10.260(2) Å, α = 108.76(1), β = 102.46(1), γ = 101.21(1)°, V = 1488.7(7) Å3, Z = 2, and R = 0.024. In 1 the central NiII atom is situated in a distorted octahedral geometry, coordinated by six thiolato sulfur atoms from the two octahedral fac(S)-[Rh(aet)3] units. The two fac(S)-[Rh(aet)3] units have the same absolute configuration to form the racemic (ΔΔ/ΛΛ) isomer. The optically active ΔΔ and ΛΛ isomers of 1 were derived from ΔΔΔΔ- and ΛΛΛΛ-[{Rh(aet)3}4Zn3(HO)]5+ respectively, by adding excess Ni2+. The electronic absorption spectral behavior of 1 indicated that the intermolecular exchange of the fac(S)-[Rh(aet)3] units occurs in solution, which results in the formation of the ΔΛ (meso) isomer from a 1 : 1 mixture of the ΔΔ and ΛΛ isomers. The chemical properties of the present RhIIINiIIRhIII complexes are discussed in comparison with those of the corresponding CoIIINiIICoIII and RhIIICoIIIRhIII complexes.
Synthesis and Photochromic Properties of Fulgides with a t-Butyl Substituent on the Furyl- or Thienylmethylidene Moiety
Authors: Kiji Jitsuo , Okano Tamon , Kitamura Hitoshi , Yokoyama Yasushi , Kubota Shuji , Kurita Yukio 
Published: July 2006

Abstract
2,6,6-Trimethyl-5-(2,5-dimethyl-3-furyl and -3-thienyl)-3-heptyn-2,5-diols were carbonylated in benzene in the presence of 1 : 1 — Pd(OAc)2/I2 as the catalyst. The reaction at 90 °C under 80 atm of carbon monoxide for 5 h directly gave both E and Z isomers of t-butyl-substituted furyl- or thienyl fulgides. The former had been reported impossible to synthesize by the Stobbe condensation. Similarly, furyl- and thienylfulgides with an isopropyl group were synthesized by this method. The fulgides were isolated by column chromatography in 37—75% yields. Coloring quantum yields of t-butyl-furyl- and -thienylfulgides are 0.79 and 0.73, respectively, which are the greatest in each series of fulgides with the same heteroaromatic ring.
Triethylborane-Induced Radical Cyclization of 1-Allyloxy-2-halosilacyclopentane. Stereoselective Synthesis of 1,3,6-Triols Starting from Silacyclobutane
Authors: Matsumoto Kozo , Miura Katsukiyo , Oshima Koichiro , Utimoto Kiitiro 
Published: July 2006

Abstract
1-Allyloxy-2-bromo-1-phenylsilacyclopentane was synthesized by a ring-enlargement reaction of 1-allyloxy-1-phenylsilacyclobutane with LiCHBr2. The treatment of 1-allyloxy-2-bromo-1-phenylsilacyclopentane with n-Bu3SnH in the presence of a catalytic amount of Et3B provided 2-oxa-1-silabicyclo[3.3.0]octane, which was converted into 1,3,6-triol by an oxidative cleavage of silicon–carbon bonds with H2O2. An intermolecular radical addition of 2-iodosilacyclopentane to acetylenic compounds afforded the corresponding iodoalkenes.
Synthesis, Properties, and Structures of 1,2 : 5,6-Bis(ethylenedithio)pyracylene and Its Radical Cation Salts
Authors: Tani Hiroyuki 
Published: July 2006

Abstract
1,2 : 5,6-Bis(ethylenedithio)pyracylene (2) was synthesized as an example of molecular design for a polyaromatic condensed-type donor with two ethylenedithio groups at the periphery. The redox potential of 2 indicates that this heterocycle is a reversible two-stage redox system with low oxidation potentials, which enhances the donor ability. This donor was readily oxidized to afford single crystal radical cation salts with hexafluorophosphate (PF6−) and triiodide (I3−) by electrocrystallization. The crystal structures of the radical cation salts, (2)3(PF6)2 and (2)2I3, show segregated stacks of donors and anions. The I3 salt presents a two-dimensional sheet along the ab plane similar to I3 salt of bis(ethylenedithio)tetrathiafulvalene.
Solvent Effects on the Solvolysis of p-Nitrobenzyl and 3,5-Bis(trifluoromethyl)benzyl p-Toluenesulfonates
Authors: Fujio Mizue , Susuki Toshihiro , Goto Mutsuo , Tsuji Yutaka , Yatsugi Ken-ichi , Kim Sung Hong , Ahmed Gamal Abdel-Wahab , Tsuno Yuho 
Published: July 2006

Abstract
Solvolysis rates of p-nitrobenzyl and 3,5-bis(trifluoromethyl)benzyl p-toluenesulfonates were determined in a wide variety of solvents. The solvent effects were analyzed based on the Winstein–Grunwald equation. The solvent effect on these deactivated benzyl solvolyses failed to give a single linear correlation with the 2-adamantyl YOTs parameter. The lower response to the solvent polarity and the pattern of dispersion for respective binary solvent series can be interpreted in terms of nucleophilic solvent assistance. The application of the equation gave a low m value of 0.4 and a large l of close to unity for both derivatives. Furthermore, the l value is also comparable to that for ethyl p-toluenesulfonate and even close to that for the methyl derivative, which has generally been defined as the standard SN2 substrate.
Spectroscopic Study of Intracluster Proton Transfer in Small Size Hydrogen-Bonding Clusters of Phenol
Authors: Mikami Naohiko 
Published: July 2006

Abstract
Spectroscopic studies of the hydrogen-bonding clusters of phenol were reviewed with an emphasis of the characterization of the cluster structures involving the proton transfer processes. Two experimental methods which were newly developed for the spectroscopy of the size selected clusters and their ions were described. Trapped ion photodissociation spectroscopy revealed that chromophore alternation occurs in the cluster cations with various proton-accepting molecules, such as NH3 and H2O. The infrared spectroscopy combined with the ionization detection was applied to the spectra of the OH vibrations which characterized the neutral clusters of phenol with water. The spectroscopic evidence of the ion-pair form of the neutral cluster is presented and the possibility of the intracluster acid-base reaction is discussed.
Photovoltaic Properties of Triphenodioxazine and Dichlorotriphenodioxazine
Authors: Yoshida Sadamu , Kozawa Kozo , Uchida Tokiko 
Published: July 2006

Abstract
Photovoltaic behaviors of evaporated thin films of triphenodioxazine (TPDO) and 6,13-dichlorotriphenodioxazine (DClTPDO) were investigated with sandwich-type cells, the configurations of which were Ag/TPDO/Al and Al/DClTPDO/indium–tin oxide (ITO). The action spectra of the short-circuit photocurrent suggest that only the photons absorbed by pigments near the Ag/TPDO interface or the DClTPDO/ITO interface are effective to produce carriers for external circuits. These results mean that Schottky barriers are formed at these interfaces, and that both pigment layers act as n-type semiconductors. Observed effects of oxygen and/or hydrogen gas on the dark conductivity of these pigment films also reflect the n-type semiconducting behavior. The observed electrical behaviors are consistent with the proposed band structures for these two cells, which are estimated from the spectroscopic data.
Semiconductor Photocatalysis: Size Control of Surface-Capped CdS Nanocrystallites and the Quantum Size Effect in Their Photocatalysis
Authors: Yanagida Shozo , Ogata Tomoyuki , Shindo Akihiro , Hosokawa Hiroji , Mori Hirotaro , Sakata Takao , Wada Yuji 
Published: July 2006

Abstract
Size-controlled CdS nanocrystallites were prepared by using thiophenol or hexanethiol as a capping reagent by controlling the ratio of Cd2+ to bis(trimethylsilyl) sulfide (S(TMS)2) as a source of the sulfide ion in reversed micelles. Their solubility and photocatalysis were examined. A series of size-controlled phenyl-capped CdS nanocrystallites catalyze the photoreduction of aromatic ketones in the presence of triethylamine as an electron donor under visible-light irradiation. The photocatalytic activity is affected by the particle size, i.e., the reducing power of the photogenerated electron on CdS nanocrystallites toward the ketones increases with decreasing the particle size. The enhancement of photocatalytic activity observed by reducing the particle size should be ascribed to not only a negative shift of the conduction band edge, but also suppression of the formation of surface defects.
NMR Study on the Electrochemically Generated Triphenylmethyl Anion
Authors: Okano Mitsutoshi , Kugita Tsuyoshi , Ohtani Daijiro , Hamano Hiroshi 
Published: July 2006

Abstract
The 13C and 1H NMR spectra of the triphenylmethyl anion, which had been generated by an electrochemical reduction of triphenylmethane in dimethylformamide at −40 °C, were successfully obtained. An anion having a tetrabutylammonium counter cation had 13C chemical shifts similar to those for an anion with a lithium counter cation. An examination of the 1H NMR spectra revealed that the reaction is a one-electron reaction. Experiments conducted under temperature control showed that the anion is fairly stable below −20 °C. Decomposition of the anion above −20 °C was suggested to be hydrogen abstraction from the β-position of a tetrabutylammonium cation by a triphenylmethyl anion (Hofmann decomposition of the ammonium cation).
Collinear Quantum Calculation of Transition-State Spectrum for the K + NaCl Reaction
Authors: Takayanagi Toshiyuki 
Published: July 2006

Abstract
The laser-induced reaction, K + NaCl + hν → KCl + Na*, has been studied quantum-mechanically, with consideration of only collinear geometries. Laser-dressed equations are numerically solved by the R-matrix propagation method. Quantum reaction probabilities are dominated by many resonances corresponding to the vibrational states of the reaction complex formed in the reaction. The results obtained are compared with surface hopping trajectory calculations. The trajectory surface hopping model fails in predicting the translational energy dependence of the reaction probabilities but a Landau–Zener model is qualitatively correct in the calculation of the laser wavelength dependence of the reaction probabilities. These results suggest that the dynamics of the laser-induced reaction can be divided into two independent processes; the ground state reaction K + NaCl → KCl + Na and the non-adiabatic transition from the laser-dressed ground state to the excited state.
A Voltage-Modified Trajectory Simulation for a State-Selected CH3I Supersonic Beam in an Electrostatic Hexapole Field
Authors: Che Dock-Chil , Ogawa Tetsuya , Ohoyama Hiroshi , Kasai Toshio , Kuwata Keiji 
Published: July 2006

Abstract
The |JKM &gt; state selection of a seeded CH3I/Ar supersonic beam has been achieved using a 2-m electrostatic hexapole field. Several |JKM &gt; states were better resolved than the previous one in a CH3Cl/He supersonic beam. A voltage-modified trajectory simulation was carried out for fitting the observed focusing curve, in which the first-order approximation of the Stark effect was corrected in terms of the hexapole voltage in an empirical formula. A better agreement was found on the peak positions of the focusing curve, and the relative heights of the three peaks suggest that CH3I molecules in the present beam populate among the |JKM &gt; states in a statistical way with a rotational temperature of 3 K.
Conductometric and Volumetric Studies on the Inonization, Hydration, Aggregation, and Coagulation of AOT in Dodecane
Authors: Manabe Masahiro , Ito Tetsuya , Kawamura Hideo , Kinugasa Takumi , Sasaki Yasushi 
Published: July 2006

Abstract
For the sodium l,2-bis(2-ethylhexyloxycarbonyl)ethanesulfonate (AOT)/water/dodecane system, the conductivity (κ) of the solution as well as the partial molar volume of water was determined at 25 °C as a function of the water concentration (CW) at a given concentration of AOT (CA). The value of (κ) increased stepwise through 2 peaks before water-phase separation. Each step was assigned as follows. Upon the initial additions of water at all of the CA’s studied (CA &lt; 0.2 mol kg−1 (dodecane)), κ remained zero, indicating the formation of unionized hydrate, AOT(H2O)2. The critical composition of the solution for reversed micelle formation was estimated to be CA = ca. 0.02 and CW = ca. 0.04 mol kg−1 (dodecane). After hydrate formation, micelles were formed in equilibrium with the hydrate, at which point κ increased abruptly to the 1st peak. Coagulation of the micelles occurred above another critical composition (CA = 0.120 and CW = 0.612 mol kg−1), at which point κ increased with a steep slope up to the 2nd peak. The partial molar volume of water in the same system also indicated the formation of AOT(H2O)2.
Thermochemical Aspects of Partition. A Study on The Novel Hydrophobic Parameters of Multiply-Substituted Benzoic Acids
Authors: Nakamura Katsuhiko , Da Yong-Zhong , Jikihara Takahiro , Fujiwara Hideaki 
Published: July 2006

Abstract
The thermochemical aspects of partition have been measured for multiply-substituted benzoic acids with the intention of disclosing the mode of change of the proposed novel hydrophobic parameters on multiple substitution in the phenyl ring. The substituent hydrophobic parameter (π) has been separated into two terms of enthalpic and entropic nature (πH and πS). It is necessary to take into account the effect of solvation around the hydrogen-bond-participating groups, such as OH, OCH3, and NO2, besides the benzoic CO2H in interpreting the substituent dependency of π, πH and πS. Some Hammett sigma parameters, such as σo(→OH) and σo(→OCH3), which mean the ortho substituent effect to the functional OH and OCH3 groups, respectively, act in a compensating manner to πH and πS, resulting in a vanishing effect on π. These trends are in good conformity with the enthalpy–entropy compensation rule in chemical thermodynamics.