bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Behaviour of the Lithiated Nickel Oxide Crystal
Authors: Yoneyama Hiroshi , Tamura Hideo 
Published: July 2006

Abstract
The electrochemical properties of lithiated nickel oxide were studied using a single-crystal (100) face and a sintered body. The I–V curves of the Fe2+/Fe3+ system on the single-crystal electrode were almost the same as those on the sintered-body electrode when the electric resistivities of the crystals were equal. However, a high amount of charge was obtained at the sintered-body electrode compared with the single-crystal electrode when the crystals were oxidized anodically. The effect on these reaction rates of the space charge depletion layer formed on the electrode surface will be discussed. The dependence of the reaction rates on the electric resistivity of the crystal can be understood to a certain extent through this discussion.
Normal Vibrations and Far-infrared Spectra of Ammonium Chloride and Ammonium Chloride-d4 Crystals
Authors: Fukushima Kunio , Yamamoto Hiroko 
Published: July 2006

Abstract
The normal coordinate treatment of optically active lattice vibrations of ammonium chloride and ammonium chloride-d4 at low temperature was made in order to elucidate the nature of the vibrations and obtain force constants in the potential in the crystals by the method of least squares. Using the constants, the optically active lattice vibrations of a crystal model for ammonium chloride and ammonium chloride-d4 at room temperature were calculated. The far-infrared spectra obtained and the Raman and infrared spectra in literature were discussed.
Cotton Effect Induced in Optically Inactive Molecules and Molecular Complexes by Optically Active Environment. I. Pyrene, TCNNQ, and Their Molecular Complex in Acetylcellulose Film
Authors: I’Haya Yasumasa J , Yunoki Toru 
Published: July 2006

Abstract
Ultraviolet absorption spectra, induced optical rotatory dispersion and circular dichroism of pyrene, TCNNQ, and their molecular complex were measured in acetylcellulose film and solution. The Cotton effect corresponding to each absorption maximum of these systems appeared. A perturbation of excited states of these molecules and their complex due to an asymmetric environment of acetylcellulose might be of paramount importance in producing a non-zero rotational strength in the corresponding molecular absorption region. The second charge-transfer band was clearly detected in the differential optical rotatory dispersion spectrum of the TCNNQ-pyrene molecular complex embedded in an acetylcellulose film. The method was shown to be promising in detecting very weak and closely overlapped transitions in various molecules.
Activity Coefficients for the System Glycylglycine–Urea–Water
Authors: Uedaira Hatsuho 
Published: July 2006

Abstract
Activity coefficients for the ternary system glycylglycine-urea-water were measured by the isopiestic vapor pressure method at 25°C. The activity coefficients of glycylglycine were lowered by urea. The lowering increased with increasing concentration of urea and with decreasing concentration of the amino acid. It was dependent on amino acid concentration to a greater extent than in the system α-amino-n-butyric acid–urea–water. The activity coefficients of urea were also decreased by glycylglycine. The free energy of the transfer of glycylglycine from water to urea solutions in various concentrations was calculated. The values obtained were combined with enthalpy data to yield −3.9 e. u. as the entropy value for the transfer from water to 6 m urea solution. Results have been interpreted to support the existence of interaction between urea and glycylglycine.
Formation Constants of Some Bivalent Metal Chelates of N-Phenylbutyrohydroxamic Acid
Authors: Shukla J P , Tandon S G 
Published: July 2006

Abstract
The formation constants for the metal chelates of Mn(II), Ni(II), Zn(II), and Cu(II) with N-phenylbutyrohydroxamic acid have been determined in 50 volume per cent dioxane-water mixture following the Bjerrum-Calvin pH titration technique and maintaining the titration medium at a constant salt background (0.1 m KClO4) and a temperature 25±0.1°C. The formation constants found are logK1=9.68(Cu), 6.85(Zn), 6.67(Ni), 5.25(Mn), and logK2=8.58(Cu), 5.52(Zn), 5.21(Ni), and 4.09(Mn), the stability order being Mn&lt;Ni&lt;Cu&gt;Zn.
Studies of Ruthenium Complexes. III. Kinetics of Isotopic Ligand-Exchange Reactions of Halogenopentaammineruthenium(III) Complexes in Aqueous Solution
Authors: Shinohara Tetsuo , Yamada Takato , Takebayashi Noriyuki , Hiraki Shun-ichi , Ohyoshi Akira 
Published: July 2006

Abstract
Kinetic studies of isotopic ligand-exchange reactions, [Ru(NH3)5X]2++X*−=[Ru(NH3)5X*]2++X−, where X=Cl, Br, and I, have been made in aqueous solutions. The effects of the hydrogen- and halide-ion concentrations, and of the ionic strength of the aqueous solution on the exchange rate had not been observed under certain definite experimental conditions. The rate constants were determined to be 3.15×10−4 sec−1 for the chloro-pentaammine 3.63×10−4 sec−1 for the bromopentaammine, and 1.1×10−4 sec−1 for the iodopentaammine at 80°C. The energies of activation were 20 kcal/mol (chloropentaammine), 23 kcal/mol (bromopentaamine), and 30 kcal/mol (iodopentaammine). The reactions proceed through the following two steps:
[Ru(NH3)5X]2++H2O→[Ru(NH3)5H2O]3++X−
[Ru(NH3)5H2O]3++X*−→[Ru(NH3)5X*]2++H2O
The first step is regarded as the rate-determining one.
A Kinetic Study of the Monomer-dimer Reaction in Propionic Acid by Means of Ultrasonic Absorption Measurements
Authors: Tatsumoto Nobuhide , Sano Takayuki , Yasunaga Tatsuya 
Published: July 2006

Abstract
Second ultrasonic absorptions with relaxation frequencies of 26, 36, 53, and 70 MHz could be observed in 0.27, 0.47, 1.0, and 2.0 m cyclohexane solutions respectively of propionic acid at 20°C. The consideration of the variations in the sound absorption, the sound velocity, and the chemical shift with the concentration leads us to the conclusion that the relaxation is attributable to the perturbation of the equilibrium between the open dimer and the monomer of propionic acid. The backward rate constant in this reaction is estimated to be about 109 sec−1M−1.
Brominations of Aliphatic Ketones by Copper(II) Bromide in Organic Solvents. II. The Reaction of Acetone with Copper(II) Bromide in N,N-Dimethylformamide
Authors: Kojima Yoshitane , Usui Kimiko , Kawaguchi Shinichi 
Published: July 2006

Abstract
Because of a long induction period, the reaction between acetone and copper(II) bromide does not occur readily in pure DMF. However, in the presence of an acid, it proceeds readily. The initial rate is proportional to the product of the concentration of acetone and perchloric acid, but independent of the concentration of copper(II) bromide. The acid-catalyzed bromination of acetone by bromine has also been studied in DMF and found to obey the same second-order rate law as that in water. Both bromination reactions of acetone in DMF by copper(II) bromide and bromine were interpreted to be controlled by the enolization process of acetone.
Effects of Substituents on the Smiles Rearrangement of O-s-Triazmyl-2-aminophenoIs
Authors: Maeno Norio , Itagaki Takeshi , Uno Seiichi , Matsui Kohji 
Published: July 2006

Abstract
Several 4- or 5-substituted O-(s-triazinyl)-2-aminophenols were synthesized, and the kinetics of the Smiles rearrangement of these compounds have been studied spectrophotometrically in methanol, ethanol, and 2-propanol in order to make clear the effects of substituents on the rearrangement. Substituents in the s-triazine nucleus were found to affect the progress of the reaction to a great extent by changing the positive character of the triazine-ring carbon. On the other hand, a substituent in the aminophenol moiety affects both the nucleophilic reactivity of the attacking amino group and the stability of the leaving phenoxide anion or the reactivity of the s-triazinyl group, but the effect on the amino group was found to be predominant, the effect of a substituent in the aminophenol moiety was smaller than that of the substituents in the s-triazine nucleus.
Syntheses of Isoprenoids from Isoprene. III. The Dimerizations of Dimethylcyclopropanes
Authors: Tanaka Juntaro , Katagiri Takao , Takabe Kunihiko , Sakamoto Tadashi 
Published: July 2006

Abstract
1,1-Dimethylcyclopropane(I) was found to dimerize selectively by the action of boron trifluoride etherate. In the products, compound (III), which had been presumed, and the reaction intermediates (VII and VIII) were identified. The reaction mechanism was discussed. 1,2-Dimethylcyclopropane(VI) gave the same products.
Syntheses and Reactions of Functional Polymers. LXVI. Activation of Carboxylic Acid by Means of Polymers Containing Hydroxamic Acid Residue and N-Hydroxysuccinimide Residue
Authors: Narita Mitsuaki , Teramoto Takero , Okawara Makoto 
Published: July 2006

Abstract
In order to achieve solid-phase acyl activation of carboxylic acid, the syntheses and reactions of polymers containing hydroxamic acid and N-hydroxysuccinimide residues were investigated. A polymer containing hydroxamic acid residue was obtained by the modification of cross-linked copolymer of p-nitrophenyl acrylate with styrene, and one containing N-hydroxysuccinimide residue was prepared by copolymerization of N-acetoxymaleimide with styrene followed by hydrolysis. These N-hydroxy polymers were allowed to react with N-protected amino acids by means of the dicyclohexylcarbodiimide method giving the activated polymer ester. While the polymer containing hydroxamic acid residue was inferior to that containing N-hydroxysuccinimide residue in activation of carboxylic acid, amino acid esters of the latter were active enough to react with another amino acid to yield dipeptides almost quantitatively without racemization.
Oxidative Dimerization of Pyrrole Derivatives. II. The Formation and Structure of Dimers of 3-Alkoxycarbonyl-substituted Pyrryls
Authors: Tomita Kuniyuki , Yoshida Norio 
Published: July 2006

Abstract
Oxidation of 3-alkoxycarbonyl-substituted pyrrolic compounds with aqueous potassium ferricyanide in the presence of potassium hydroxide afforded 2,2′- and 5,5′-bispyrrolenine derivatives, which were in equilibrium with each other in solution via radical intermediates. The substituent effects on the dimer formation will also be discussed in connection with the characters of the intermediate pyrryl radicals.
Syntheses and Reactions of Metal Organics. VII. Reactions of n-Butoxytitanium Chlorides with Saturated Cyclic Ethers
Authors: Yoshino Norio , Yoshino Takeshi 
Published: July 2006

Abstract
The reactions of n-butoxytitanium chloride, TiCln(OnBu)4−n (n=0,1,2,3,4), with 1,4-dioxane, tetrahydrofuran, and tetrahydropyran have been studied. No adducts have been isolated when n=0,1,but the compounds TiCl2-(OnBu)2·O(CH2CH2)2O, TiCl2(OnBu)2·C4H8O, TiCl2(OnBu)2·C5H10O, TiCl3(OnBu)·O(CH2CH2)2O, TiCl3(OnBu)·2C4H8O, TiCl3(OnBu)·2C5H10O, TiCl4·O(CH2CH2)2O, TiCl4·2C4H8O and TiCl4·2C5H10O have been isolated when n=2,3,4. Possible structures for these adducts were discussed on the basis of elemental analysis, IR spectra, NMR spectra, and molecular weights. The adducts undergo hydrolysis very quickly with moisture.
Linear Conjugated Systems Bearing Aromatic Terminal Groups. IX. Syntheses and Elctronic Spectra of α,ω-Di-1-anthrylpolyenes
Authors: Takeuchi Yasuhira , Akiyama Shuzo , Nakagawa Masazumi 
Published: July 2006

Abstract
Syntheses of α,ω-di-1-anthrylpolyenes have been carried out by the Wittig reaction for information on the role of aromatic terminal groups on the electronic spectral regularity of α,ω-diarylpolyenes. The reaction of phosphoranes derived from 1-anthrylmethyl-, 3-(l-anthryl)propenyl-, and 5-(1-anthryl)-pentadienyltriphenylphosphonium bromides with 1-formylanthracene, 3-(1-anthyrl)propenal, 5-(1-anthryl)pentadienal, and muconic aldehyde afforded a series of di-1-anthrylpolyenes (I1−6) by a proper combination of the phosphorane and the aldehyde moiety. Owing to the broading of absorption bands in the long wavelength region, no discussion could be made on the electronic spectral regularity.
Thiocyanoacetate. IV. The Reaction of Ethyl Thiocyanoacetate with Aromatic Aldehydes in the Presence of Thioureas
Authors: Kambe Satoshi , Hayashi Toshio 
Published: July 2006

Abstract
Ethyl thiocyanoacetate (1) reacts with anomatic aldehydes in the presence of N,N′-dialkylthiourea to give arylidene N,N′-dialkyl-N-thiocarbamoyl thiocyanoacetamides (3). On the other hand, the treatment of the ester (1) with benzaldehyde in the presence of thiourea or N-methylthiourea under the same conditions affords 5-benzylidene-2-imino-4-thiazolidinone (5a) or 5-benzylidene-3-methylthiazolidine-2,4-dione (6a).
An MO-Theoretical Study of the Decomposition of Hydroperoxides by Sulfonium Compounds and Some Nucleophiles
Authors: Ohkubo Katsutoshi , Kanaeda Hirokazu 
Published: July 2006

Abstract
The decomposition reactions of hydroperoxides (ROOH) by sulfonium compounds or some nucleophiles (sulfides, phosphites, and transition metal ions) were treated by the extended Hückel method, augmented by the use of d-orbitals. We obtained serveral findings. First, ROOH was more reactive to nucleophiles and was energetically more stable than (ROOH)2. Second, the order of the ability for the ROOH decomposition, sulfonium compounds&gt;&gt;sulfides&gt;phosphites\gtrsimthiophene, was in good agreement with that of the AO populations of the nonbonding lone pair orbitals of the above compounds. Third, the distinguished ability of the sulfonium compound may be attributed to the contribution of the partially-occupied sulfur d-orbitals, in particular, the lowest unoccupied dz2-orbital; in the ROOH decomposition, these orbitals interact with the lowest unoccupied antibonding pσ-orbital of the O–O in ROOH at the Oβ atom in the direction of the O–O axis. Finally, it was concluded that the sulfur d-orbitals contribute to the long-range interaction (S–Oβ&gt;3.0 Å) between ROOH and sulfonium compounds.
An MO Approach to the Interpretation of Organic Mass Spectra. I. Relative Bond Energy of the Molecule Ion by the Extended Hückel Method
Authors: Ogata Michihiko , Ichikawa Hiroshi 
Published: July 2006

Abstract
A method of comparing the relative bond energies is applied to the interpretation of the simple cleavage and the McLafferty rearrangement reactions in organic mass spectrometry. A qualitative correlation between the relative bond energy and the charge density at the highest occupied orbital is found. The behavior of the highest occupied and some lower vacant orbitals is discussed.
Competitive Adsorption of Polyvinylpyrrolidone with n-Alkyl Alcohols at the Mercury/Solution Interface
Authors: Yoshida Tadashi , Ohsaka Tetsuya , Iida Yasuo 
Published: July 2006

Abstract
Competitive adsorption of polyvinylpyrrolidone (PVP, \barM=10000) with n-hexanol, n-pentanol, or n-butanol was examined by observation of the differential capacity at the mercury interface in 1 n sulfuric acid. Adsorption of PVP coexistent with alcohol hardly differed from the single adsorption1) controlled by its diffusion. The competitive adsorption curve of C (differential capacity) vs. t1⁄2 (adsorption time) was expected from the sum of the individual capacity depressions by the single adsorption at −0.5 or −0.6 V (SCE) and the expected curve of C vs. t1⁄2 was compared with the curve observed. The competitive behavior of alcohol coexistent with PVP was examined by the relation “θAlccom (coverage of coexistent alcohol) vs. t1⁄2” at −0.5 or −0.6 V (SCE), where θAlccom was estimated from the difference between the differential capacities with and without PVP, in view of the fact that behavior of PVP is nearly independent of the coexistent alcohol. The results are discussed in terms of four types of models assumed for the competitive behavior of coexistent alcohols with different adsorbability. It is considered that the alcohol is replaced with PVP as soon as the latter reaches the interface by diffusion, the adsorption equilibrium of an alcohol being achieved immediately. The relation θAlccom=(1−θpvp)θAlc holds in the case of n-butanol coxistent with PVP, where θPVP, θAlc, and θAlccom are coverages due to the single adsorption of PVP and butanol and to the competitive adsorption of butanol, respectively. The tendency of alcohol to be replaced with PVP is inversely proportional to its adsorption coefficient. n-Butanol was most sensitive to the coexistence of PVP.
Studies on Intermolecular Complex Formation. II. Crystal Structure of Cytosine-N-Benzoylglycine Complx Monohydrate
Authors: Tamura Chihiro , Hata Tadashi , Sato Sadao , Sakurai Noriko 
Published: July 2006

Abstract
Many intermolecular complexes between N-acylamino acids and nucleotide bases have been found by means of X-ray powder diffractometry. Among these, the crystal structure of N-benzoylglycine cytosine complex monohydrate has been determined by the direct method. The crystal data are: a=18.71,b=7.11,c=18.37 Å, and β=144.0°. The space group is P21⁄c; Dobsd=1.37; Dcalcd=1.35 g/cm3. The final R factor was 0.131. In the crystal, a cytosinyl cation and a N-benzoylglycyl anion are joined by two NH···O hydrogen bonds, of which the shorter one is 2.652 Å long. Such a complex formation may exist in vivo.
The Adsorption of Polyvinylpyrrolidone at the Mercury/Solution Interface
Authors: Yoshida Tadashi , Ohsaka Tetsuya , Tanaka Shoji 
Published: July 2006

Abstract
The adsorption of polyvinylpyrrolidone (PVP), known as a water-soluble polymer, at the electrolyte/DME interface was examined by observing the differential capacity vs. the time relation, under conditions where the adsorption process was mainly controlled by diffusion. In the case of a relatively low bulk concentration and a short adsorption time, the adsorption rate of PVP at−500 mV(SCE) was controlled almost wholly by the diffusion of the adsorbate to the DME. The relation between the time required to attain the saturated adsorption and the bulk concentration was explained approximately by the Koryta equation, based on the linear diffusion. PVP showed no tendency to form multi-layers within the range of bulk concentrations and adsorption times observed. The maximum surface concentration of PVP decreased almost linearly with the increase in its mean molecular weight. The number of constitutive segments adsorbed per unit of area to form a monolayer at the interface was almost constant, independent of the mean molecular weight. The activation energy for the diffusion was found to be ca. 4.7 kcal/mol. On the basis of the results obtained, the configuration of PVP adsorbed at the interface was discussed.
Bond Alternation in Tropone as Studied by Gas Electron Diffraction
Authors: Ogasawara Makoto , Iijima Takao , Kimura Masao 
Published: July 2006

Abstract
Assuming a planar conformation with C2v symmetry, and using the estimated mean amplitudes of vibration, the bond alternation in tropone was confirmed. The average C–C and C=C distances were determined by the least-squares method to be 1.454±0.010 and 1.362±0.013 Å respectively; moreover, two probable sets of the structure parameters were obtained. On the basis of conformational arguments regarding the structures of related compounds, the following set of the bond lengths was preferred: C–H, 1.098±0.016 Å; C1–O, 1.225±0.012 Å; C1–C2, 1.445±0.012 Å; C2–C3, 1.364±0.012 Å; C3–C4, 1.462±0.012 Å; and C4–C5, 1.342±0.018 Å.
Behavior of Oxygen Species on the Nickel Oxide Catalyst Surface
Authors: Chaudhri Safee , Kera Yoshiya , Hirota Kozo 
Published: July 2006

Abstract
The 18O-oxidation of carbon monoxide was studied on nickel oxide catalysts, and the oxygen exchangeability with the oxide during the reaction was determined. The activities of three oxide samples, obtained under different preparation conditions, were compared. The samples were prepared at 350, 600, and 850°C; they are denoted as NiO-I, NiO-II, and NiO-III respectively. In the case of NiO-I, two kinds of oxygen species, weakly and strongly bound to the surface, were observed. Above 120°C, not only weakly but also strongly bound surface oxygen become reactive; however, the binding energy distribution was quite broad. Similar observations were made in the case of NiO-II, with a similar change above 170°C and with a sharp energy distribution. In contrast, for NiO-III, only a small percentage of the monolayer of the surface oxygen became active and exchangeable below 200°C, but above 250°C about three layers became activated. Models are proposed for the surface state of these oxides on the basis of the behavior of the surface oxygen.
Monolayers of Poly(methyl acrylate) Saponified Partially in Homogeneous and Heterogeneous Systems
Authors: Hironaka Seiichiro , Meguro Kenjiro 
Published: July 2006

Abstract
Poly (methyl acrylate) prepared by radical polymerization of methyl acrylate was saponified partially in acetone-water mixtures (5 : 2 and 100 : 1 by volume), using sodium hydroxide as the catalyst. Saponification in an acetone-water mixture of a 5 : 2 ratio by volume proceeded in a homogeneous state, but the reaction solution of a 100 :1 ratio by volume was in a white-turbid state, in which saponification proceeded in a heterogeneous state. The properties of the monolayers of polymers saponified in different states were studied at the air/water interface by measuring the surface pressure. The limiting areas obtained on distilled water for each polymer saponified in these two systems decreased linearly with an increase in the degree of saponification. However, the monolayers of polymer saponified in a homogeneous system were more stable on sodium chloride solution than those obtained in a heterogeneous system, and gave the limiting areas on solutions above 5% corresponding with the theoretical values calculated from the areas per methyl acrylate and acrylic acid residue and the degree of saponification. This can be explained by the fact that some of the hydrophilic parts of the saponified polymers submerged into the water phase were squeezed out onto the water surface by the salting out effect. On the other hand, those values obtained in a heterogeneous system neither corresponded to the theoretical values nor gave reproducible areas at high concentrations. These facts may be due to the differences in the states of the saponified polymers.
The Vibrational Assignment and Force Constants of Halogenomethylsilanes and Their Germanium Analogues: ClCH2SiH3, ClCH2SiD3, BrCH2SiH3, BrCH2SiD3, CICH2GeH3, and CICH2GeD3
Authors: Ohno Keiichi , Murata Hiromu 
Published: July 2006

Abstract
The infrared spectra of ClCH2SiH3, ClCH2SiD3, BrCH2SiH3, BrCH2SiD3, ClCH2GeH3, and ClCH2GeD3for both the gaseous and solid states in the 250–4000 cm−1 region have been obtained. All the fundamental vibrations except for the skeletal bending and YH3(–D3) (Y=Si, Ge) torsional vibrations have been observed and assigned. The normal vibration calculation has been carried out using a modified Urey-Bradley force field. The transferability of the force constants has also been investigated.
The Diffuse Reflection Spectra of 1-Arylazo-2-naphthols Deposited on Various Synthetic Fibers
Authors: Matsunaga Yoshio , Miyajima Nobuhiko 
Published: July 2006

Abstract
The diffuse reflection spectra of sixteen 1-arylazo-2-naphthols deposited on polypropylene, polyacrylonitrile, polyethylene terephthalate, and Nylon-6,6 were recorded in the range from 350 to 700 nm. The spectra indicate the coexistence of the azo and hydrazone tautomers in these systems. By a comparison with the absorption spectra of the compounds dissolved in n-hexane, acetonitrile, methyl benzoate, and formamide, it was concluded that the nature of the fibers is the major factor determining the tautomeric equilibria. The effect of moisture on the spectra was found to be rather small except in the cases of the p-OH and p-MeO derivatives deposited on polyacrylonitrile.