bluuebunny/crossref_metadata_2025 huggingface dataset:
The Germanium–Carbon Bond Cleavage Reaction of (Germylmethyl)amine Derivatives. Mechanism and Stereochemistry
Authors: Terunuma Daiyo , Masuo Koujiro , Kizaki Hiroaki , Nohira Hiroyuki
Published: July 2006

A facile cleavage reaction of the germanium–carbon bond of (germylmethyl)amine derivatives to give a germyl anion and an azomethine derivative was developed. The effects of substituents such as phenyl, benzyl, and ethyl groups on the germanium and nitrogen atoms of the (germylmethyl)amine derivatives on the cleavage reaction, were investigated. The mechanism was also investigated based on the stereochemistry of the cleavage reaction using an optically active organogermanium compound.
Preparation and NMR Study of 7,7′-(α,ω-Alkanediyl)bis[theophylline], 1,1′-(α,ω-Alkanediyl)bis[theobromine], and 1,1′-(α,ω-Alkanediyl)bis[3-methyluracil]
Authors: Itahara Toshio , Imamura Kazuhiko
Published: July 2006

The treatment of theophylline, theobromine, and 3-methyluracil with X(CH2)nX (X = Br or I, n = 1—12) in N,N-dimethylformamide containing sodium hydride gave the corresponding 7,7′-(α,ω-alkanediyl)bis[theophylline], 1,1′-(α,ω-alkanediyl)bis[theobromine], and 1,1′-(α,ω-alkanediyl)bis[3-methyluracil]. The interaction of the theophylline, theobromine, and 3-methyluracil rings of these compounds was studied based on their 1H NMR spectra, and stacking of the two purine rings of 7,7′-(α,ω-alkanediyl)bis[theophylline] was observed.
Footprint Catalysis. X. Surface Modification of Molecular Footprint Catalysts and Its Effects on Their Molecular Recognition and Catalysis
Authors: Shimada Toyoshi , Hirose Rie , Morihara Kensaku
Published: July 2006

Trimethylsilylation with hexamethyldisilazane was applied to a surface modification of silica(alumina) gel catalysts, on which surface the “molecular footprint” catalytic cavities had been marked by the authors’ imprinting method. The modification provided for the more stable catalysts than the unmodified catalyst, retaining their molecular-recognition capabilities nearly intact.
Fluorination Reactions at C-5 of 3-O-Benzyl-6-deoxy-1,2-O-isopropylidenehexofuranoses
Authors: Mori Yoko , Morishima Naohiko
Published: July 2006

Fluorination reactions of 2-O-benzyl-6-deoxy-1,2-O-isopropylidene-α-d-gluco-, β-l-ido-, α-d-allo-, and β-l-talo-furanoses (1, 2, 3, and 4) were investigated. The reaction of 1 with diethylaminosulfur trifluoride (DAST) predominantly produced 2-O-benzyl-5,6-dideoxy-5-fluoro-1,2-O-isopropylidene-α-d-glucofuranose with the retention of the configuration at C-5. Both of the fluorides with retained and inverted configurations were obtained in the fluorination of 2 with DAST. In contrast, only the inversion of the configuration occurred when 3 and 4 were reacted with DAST. The reactions of the methanesulfonates of 3 and 4 with tetrabutylammonium fluoride (TBAF) and those of their trifluoromethanesulfonates with tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF) gave the 5-deoxy-5-fluoro derivatives with the inversion of each configuration and the 5,6-unsaturated derivative. However, the reactions of the sulfonates of 1 and 2 overwhelmingly produced the 4,5- and 5,6-eliminated derivatives. For the reaction in which the steric hindrance of the benzyloxyl group at C-3 and the electronic repulsion of ring oxygen to the SN2 displacement with fluoride anion are significant, such as the fluorination of 1 with DAST, the SNi mechansim is reasonable.
Reaction Pathway and Transition State of the Zn-Promoted Barbier-Type Reactions of Benzaldehyde and Benzophenone with Allylic Iodides
Authors: Yamataka Hiroshi , Nishikawa Kazuyoshi , Hanafusa Terukiyo
Published: July 2006

The carbonyl-14C kinetic isotope effects and the substituent effects on the reactivity of the Zn-promoted Barbier-type reaction of allyl iodide (3-iodo-1-propene) with benzaldehyde and benzophenone were determined in THF at 25 °C. The observed normal carbon isotope effects as well as positive Hammett ρ values suggest that the reactions go through a direct nucleophilic addition mechanism. No indication of the occurrence of electron transfer was obtained by enone isomerization and dehalogenation probe experiments. Diastereoselectivity in the reaction of crotyl iodide (1-iodo-2-butene) with benzaldehyde was low and independent of the substituent on aldehyde, consistent with the six-membered cyclic transition state.
An NMR Study on Ion-Pair Structures of Pyridine–Butyllithium Adducts
Authors: Nakamura Norimasa , Yoshino Akihiro , Takahashi Kensuke
Published: July 2006

The 13C and 7Li NMR spectra of the title adducts were observed in THF. In a temperature range from 20 to −80 °C the adducts existed as contact ion pairs in THF. Below −70 °C, the adduct derived from pyridine or 4-phenylpyridine showed three 7Li signals related to three different associated species in solutions. On the other hand, the adduct derived from 2- or 3-phenylpyridine did not give such multiplet signals at −70 °C. The results are related to the interaction between nitrogen and lithium, and the extent of negative-charge migration into the substituent (phenyl ring) in the adduct.
Specific Transport of Copper(II) Ions Across Liquid Membrane by Schiff Base Ligands
Authors: Ameerunisha Sardar , Srinivas Bhamidi , Zacharias Panthappally S
Published: July 2006

Schiff base ligands derived from the condensation of 2-hydroxy-5-methylbenzene-1,3-dicarbaldehyde with substituted anilines are found to be excellent carriers for the specific transport of copper(II) ions through a liquid membrane.
Dissociation Kinetics of 1,5,9-Triazacyclododecane-1,5,9-triacetate and 1,4,8,12-Tetraazacyclopentadecane-1,4,8,12-tetraacetate Complexes of Cerium(III)
Authors: Choi Ki-Young , Kim Ki Sung , Kim Ju Chang
Published: July 2006

The dissociation kinetics of DOTRA=H3dotra (1,5,9-triazacyclododecane-1,5,9-triacetic acid) and PETA = H4peta (1,4,8,12-tetraazacyclopentadecane-1,4,8,12-tetraacetic acid) complexes of Ce(III) ion have been studied in an aqueous solution of 0.1 M (NaClO4) at 25.0 ± 0.1 °C using Cu(II) ions as a scavenger. The dissociation rate constant for the acid-catalyzed pathway decreases in the order, [Ce(peta)]− > [Ce(dotra)] > [Ce(teta)]− > [Ce(nota)] > [Ce(dota)]− according to the present and literature data. The rate constant is significantly affected by internal cavity and chelate ring sizes.
A New α,α′-Diiodination of Ketones Using Iodine-Cerium(IV) Ammonium Nitrate
Authors: Horiuchi C Akira , Takahashi Eiji
Published: July 2006

The direct iodination of some ketones using iodine-cerium(IV) ammonium nitrate in acetic acid or acetonitrile gave the corresponding α,α′-diiodoketones in good yield. In the case of cyclododecanone (4), 3-pentanone (5), and 5-nonanone (6), cis- (meso-) compounds [2,12-diiodocyclododecanone (12), 2,4-diiodo-3-pentanone (13), and 4,6-diiodo-5-nonanone (14)] were obtained preferentially.
The Stability Constants for the 18-Crown-6 Complexes with [2.2]Metacyclophanediazonium Salts
Authors: Tsuge Akihiko , Moriguchi Tetsuji , Mataka Shuntaro , Tashiro Masashi
Published: July 2006

Transannular interaction between two aromatic rings in [2.2]metacyclophanes was estimated by the determination of the stability constants (Ks) for 18-crown-6 complexes with their diazonium salts. It was found out that the Ks is about 10 times as small as that for the corresponding benzenediazonium salt.
One-Step Preparation of α-Chloro-α,β-unsaturated Carbonyl Compounds by the Reaction of Silyl Enol Ethers with TiCl4–LiAlH4–CCl4
Authors: Mitani Michiharu , Kobayashi Yoshinori
Published: July 2006

Reaction of silyl enol ethers in a system composed of TiCl4, LiAlH4, and CCl4, which generates dichlorocarbene, produced α-chloro-α,β-unsaturated carbonyl compounds in an one-step process.
Electrochemical Reduction of Dichlorosilanes in the Presence of 2,3-Dimethylbutadiene
Authors: Kunai Atsutaka , Ueda Takafumi , Toyoda Eiji , Ishikawa Mitsuo
Published: July 2006

Electrolytic reduction of dichloromethylphenyl-, dichlorodiphenyl-, dichlorodi-o-tolyl-, and dichlorodi-p-tolylsilanes in the presence of 2,3-dimethylbutadiene afforded 1-methyl-1-phenyl-, 1,1-diphenyl-, 1,1-di-o-tolyl-, and 1,1-di-p-tolyl-3,4-dimethyl-1-silacyclopent-3-ene, respectively, while the similar reaction of chloromethyldiphenylsilane with 2,3-dimethylbutadiene afforded 1-(methyldiphenylsilyl)- and 1,4-bis(methyldiphenylsilyl)-2,3-dimethyl-2-butene. A reaction mechanism leading to these products has been discussed.
Deprotection of Acetals and Silyl Ethers Using Some π-Acceptors
Authors: Tanemura Kiyoshi , Suzuki Tsuneo , Horaguchi Takaaki
Published: July 2006

Hydrolysis of dodecanal dimethyl acetal and dodecyl silyl ethers in MeCN–H2O was examined using a catalytic amount of π-acceptors such as 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQF4), and chloranil (CA). Cleavage of dodecyl triethylsilyl ether with TCNQ and CA was caused by room light. By application of DDQ-catalyzed deprotection of acetals to hydrolysis of tetrahydropyranyl ethers, the corresponding alcohols were obtained in quantitative yields.
Specific Affinity Labeling of μ Opioid Receptors by S-Activated Enkephalin Analog Containing p-Nitrophenylalanine
Authors: Yasunaga Teruo , Shimohigashi Yasuyuki , Kodama Hiroaki , Miyazaki Masaya , Nagaishi Masaya , Ohno Motonori , Kondo Michio
Published: July 2006

p-Nitrophenylalanine (Phe(p-NO2)) was incorporated in place of Phe4 of [d-Ala2, Leu(CH2S-Npys)5]enkephalin. In the rat brain receptor binding assay, Npys-containing Phe(p-NO2)4- and Phe4-enkephalins exhibited almost unchanged affinities for μ receptors (IC50 = 16—21 nM). However, when the membrane was incubated with each analog, Phe(p-NO2)4-enkephalin (EC50 = 6.90 nM) could label the μ receptors about three times more effectively than Phe4-enkephalin.
Molecular and Crystal Structures of Complexes of Stable Free Radical BDPA with Benzene and Acetone
Authors: Azuma Nagao , Ozawa Takehiro , Yamauchi Jun
Published: July 2006

The crystal structures of two complexes of the 9-(9H-fluoren-9-ylidenephenylmethyl)-9H-fluoren-9-yl stable radical with benzene (BDPA–Bz) and acetone (BDPA–Ac) have been determined by X-ray diffraction at room temperature. They are an isostructure of a monoclinic system with a space group of P21/n. For BDPA–Bz, a = 9.502(2), b = 14.632(2), c = 19.452(2) Å, β = 93.64(1)°, V = 2699(1) Å3, Z = 4, Dx = 1.220 g cm−3. For BDPA-Ac, a = 9.657 (1), b = 14.675(2), c = 18.812(2) Å, β = 95.388(9)°, V = 2654.4(6) Å3, Z = 4, Dx = 1.190 g cm−3. The final R values are 0.043 and 0.062 for 5.47 and 3.93 ratio of the observed reflections versus the parameters for BDPA–Bz and BDPA–Ac, respectively. The BDPA molecules in both crystals have the same propeller shape with an approximated C2 symmetry. The molecular packing of these crystals does not show a one-dimensional stacking, in spite of the magnetic one-dimensionality elucidated by the magnetic susceptibilites. The exchange pathways are discussed based on the McConnell’s spin-density Hamiltonian.
Plasma Reduction of CO2 with H2O for the Formation of Organic Compounds
Authors: Ihara Tatsuhiko , Kiboku Mitsuo , Iriyama Yu
Published: July 2006

The reduction of CO2 with H2O was carried out by means of a microwave plasma reaction in order to obtain organic compounds. The main products obtained in a cold trap were determined to be oxalic acid and H2O2 by an analysis of reversed-phase chromatography using UV and conductivity detectors.
13C NMR and ESR Studies on a Polydiacetylene Having Acetylenic Carbons in the Side Chains
Authors: Hayamizu Kikuko , Okada Shuji , Tsuzuki Seiji , Matsuda Hiro , Masaki Atsushi , Nakanishi Hachiro
Published: July 2006

The 13C NMR spin-lattice relaxation times and ESR spectra were measured for a polydiacetylene obtained by the solid-state polymerization of a tetrayne with n-C14H29 alkyl substituents (14-4A-14). Poly(14-4A-14) has two different side chains. One side chain contains two conjugated acetylenic bonds directly bound to the main backbone conjugated system; the other is an alkyl chain. Although the unpaired electron density of poly(14-4A-14) measured by ESR is less than that in trans-polyacetylene, paramagnetic effects may contribute to the long 13C relaxation times of unsaturated carbons, which provides insight concerning the π-electron structure on the conjugated system.
Thermotropic Liquid Crystals Based on Oligosaccharides. n-Alkyl 1-O-β-d-Cellobiosides
Authors: Ma Yung-Dae , Takada Akihiko , Sugiura Makoto , Fukuda Takeshi , Miyamoto Takeaki , Watanabe Junji
Published: July 2006

n-Alkyl 1-O-β-d-cellobiosides with an alkyl length ranging from 7 to 18 in carbon number m were synthesized, and their thermal properties were studied in comparison with those of the already-known monosaccharide homologues, n-alkyl 1-O-β-d-glucopyranosides. The cellobiosides were found to exhibit a thermotropic mesophase at higher temperatures than the glucopyranosides. Depending on m and thermal history, the cellobiosides showed various textures such as homeotropic, transient bâtonnets, polygonal, and fan-shaped textures. Like in the case of the monosaccharide homologues, the difficulty of aligning the samples prohibited a full classification of the mesophase, but the X-ray diffractograms of the unaligned cellobiosides indicated that their mesophase belongs to smectic A(or less possibly, smectic C). The m dependence of the lamella thickness was much weaker than (about half) that of the monosaccharide homologues. Possible molecular arrangements of the cellobiosides in the mesophase were presented.
Apparent Molar Volumes and Apparent Molar Adiabatic Compressions of Water in Some Alcohols
Authors: Sakurai Masao , Nakamura Kunio , Takenaka Nobuo
Published: July 2006

The ultrasonic velocities in dilute alcoholic solutions of water have been measured in the temperature range from 5 to 45 °C. The solvent alcohols used were methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, and 2-methyl-2-butanol. In addition, the densities of 2-butanol and 2-methyl-1-propanol solutions of water were also measured. The apparent molar volumes and apparent molar adiabatic compressions of water in these alcohols have been evaluated. The limiting partial molar quantities are less than the molar quantities of pure water; this phenomenon is generally more pronounced for lower-chain or branched-chain alcohols. The results are discussed in connection with the hydrogen-bonding interactions, that is, the self-association of the solvent alcohols and the alcohol–water interactions.
Equilibria between Contact and Solvent-Separated Ion Pairs of 1,1-Diphenylethylene Dimer Dianion and Tetraphenylethylene Dianion
Authors: Matsui Hideki , Yoshino Akihiro , Takahashi Kensuke
Published: July 2006

Temperature-dependent 1H NMR chemical shifts of the two title carbanions have been measured in three solvents and with three counter ions. The equilibria between two types of ion pairs of the carbanions have been discussed in terms of solvent, counter ion, and temperature.
Ionization Potentials of Iodide, Bromide, and Thiocyanate Anions in Solvents: Solvent–Solvent Interactions in the Solvation Sphere
Authors: Watanabe Iwao , Tanida Hajime , Maya Keiichi , Ikeda Shigero , Yokoyama Yu
Published: July 2006

The solution-phase ionization potentials of I−, Br−, and SCN− ions in 16 solvents including water have been measured by a photoelectron emission spectroscopic technique. The values obtained as the threshold energy Et for halides are found to be correlated well with the Mayer–Gutmann acceptor number and better with the Riddle–Fowkes modified acceptor number of the solvent indicating that the electronic states of the halides are predominantly stabilized through the Lewis acid–base interaction. The reorganization energies ΔGr of solvent after the photoionization of the halides are obtained from the Et values. The experimental ΔGr values are reproduced by using a simple model which incorporates the dipole–dipole repulsion and the bond formation energies in the first solvation layer. The solvation mechanism of SCN− is somewhat different from those of the halides because its Et depends less on the acceptor number and its ΔGr values in alcohols are about half of those for the halides.
Kinetics and Mechanisms of Photoinduced Electron-Transfer Reaction of Zinc Myoglobin. Intracomplex vs. Intermolecular Quenching Controlled by Conformational Change Associated with Charge and Steric Bulk of Quenchers
Authors: Tsukahara Keiichi , Asami Satoko , Okada Mihoko , Sakurai Takeshi
Published: July 2006

Photoinduced electron transfer (ET) between zinc myoglobin (ZnPPMb) and a variety of quenchers, such as hexacyanoferrate(III) ([Fe(CN)6]3−) and hexaammineruthenium(III) ([Ru(NH3)6]3+) ions, cationic viologens, copper(II) protein (stellacyanin), and metmyoglobins, has been studied in aqueous degassed solutions. The excited triplet state of ZnPPMb (*ZnPPMb) was quenched by [Fe(CN)6]3− in a self-associated complex. Both quenching rate constant and formation constant of the self-associated complex decrease with increasing ionic strengths. The thermal backward ET reaction for this system was not observed; it is most likely that the backward ET step is much faster than the quenching reaction. All of the cationic quenchers examined in this work did not form a self-associated complex with *ZnPPMb, and the intermolecular quenching occurred. The thermal backward ET reaction was observed for these cationic quenchers. Not only photoinduced ET but also thermal backward ET reactions were insensitive to the driving force of the reactions, suggesting that the reactions are controlled by conformational changes in ZnPPMb. The quenching rate constants increase with increasing ionic strength for the cationic quenchers. The effects of poly-l-lysine hydrochloride, sodium poly-l-glutamate, and sodium cyclo-hexaphosphate were also examined. The active site of the *ZnPPMb toward both anionic and cationic quenchers is assumed to be the positively charged site near the heme pocket.
Studies on Bitter Peptides from Casein Hydrolyzate. XIV. Bitter Taste of Synthetic Analogs of Octapeptide, Arg–Gly–Pro–Phe–Pro–Ile–Ile–Val, Corresponding to the C-Terminal Portion of β-Casein
Authors: Nakatani Masaru , Nakata Takashi , Kouge Katsushige , Okai Hideo
Published: July 2006

In order to elucidate the relationship between the chemical structure and bitter taste of the C-terminal portion of β-casein, some analogues, in which the phenylalanine residue was substituted by d-phenylalanine, lysine, glycine, glutamic acid or l-pyrenylalanine, were synthesized. Sensory analyses and CD spectra showed that the location of a hydrophobic amino acid with the l-configuration between the two proline residues should be important for this series of peptides to produce a strong bitterness.
Regioselective Allylation of Ketenes Promoted by SmI2
Authors: Miyoshi Norikazu , Takeuchi Seiji , Ohgo Yoshiaki
Published: July 2006

Ketenes react with various allylic halides mediated by 2 equiv samarium(II) diiodide (SmI2) to the ketenes to afford allylated ketones in good yields. In the reaction with γ-substituted allylic halides, the regioselectivity is influenced by the olefinic geometry of allylic halides. By using γ-substituted (E)-allylic halides, the allylation proceeds on the less hindered site (α-position) of allylic groups predominantly and the tendency was enhanced by the addition of HMPA.
Effects of the Cross-Linking Structure on the Water Sorption Ability of Poly(vinyl carboxylate)
Authors: Matsuguchi Masanobu , Sadaoka Yoshihiko , Shinmoto Masafumi , Sakai Yoshiro
Published: July 2006

Water sorption behavior of four kinds of polymerized vinyl carboxylate, i. e., vinyl benzoate, vinyl methacrylate, vinyl crotonate, and vinyl cinnamate was investigated. The dielectric measurement and quartz crystal microbalance technique were adopted for this purpose. The polymers were hydrophobic and the water sorption ability was enhanced by cross-linking. The dielectric constant of sorbed water was small compared with that of liquid water and the value slightly increased with increasing the amount of sorbed water. The orientation polarization of sorbed water also slightly increased with increasing the amount of sorbed water. It was proved that the cross-linking structure affected the water sorption behavior of the polymer.
pH-Responsive Guest Binding of Polypeptide Containing a Cyclodextrin at the Terminal
Authors: Nagata Yoshitomo , Aso Toshihiro , Kinoshita Takatoshi , Tsujita Yoshiharu , Yoshimizu Hiroaki , Minoura Norihiko
Published: July 2006

Poly(γ-methyl l-glutamate-co-l-glutamic acid) containing a β-cyclodextrin at the terminal (MG/GA-CyD) was prepared and the relationship investigated between the conformation of the polypeptide and inclusion capability of the β-cyclodextrin by circular dichroism and fluorescence spectroscopy in aqueous solution containing 8-anilino-1-naphthalenesulfonate (ANS) as a guest molecule. The terminal β-cyclodextrin of MG/GA-CyD could not include ANS at higher pH, where the polypeptide almost formed a random coil. This was attributed to the terminal β-cyclodextrin being concealed in the random coil of the polypeptide. At low pH, however, random coil-to-α-helix transition of the polypeptide exposed the terminal β-cyclodextrin to the aqueous phase resulting in the ANS-inclusion capability. These results imply that control of the polypeptide conformation leads to conformational switched guest binding of the terminal cyclodextrin.
Highly Twisted t-Butoxycarbonyl Groups in Hexa-t-butyl Benzenehexacarboxylate. The Structural Origin of Steric Hindrance-Induced Dual Fluorescence
Authors: Yasuda Masahide , Kuwamura Goro , Nakazono Takumi , Shima Kensuke , Inoue Yoshihisa , Yamasaki Noritsugu , Tai Akira
Published: July 2006

Comparative X-ray crystallographic analyses of tetra-t-butyl 1,2,4,5-benzenetetracarboxylate (1) and highly congested hexa-t-butyl benzenehexacarboxylate (2) have shown that t-butoxycarbonyl groups in 2 are much more twisted with respect to the benzene ring and bond-elongated in the peripheral positions than those in 1 or hexamethyl benzenehexacarboxylate. Such deformations and the staggered carbonyl orientation, all arising from the steric hindrance, may be responsible for the unusual dual-fluorescence behavior of the sterically congested hexaester 2.
Studies of the Selective O-Alkylation and Dealkylation of Flavonoids. XVI. Demethylation of 2′-Methoxyacetophenones with Anhydrous Aluminum Chloride or Bromide in Acetonitrile
Authors: Kawamura Yasuhiko , Takatsuki Hisanori , Torii Fumihito , Horie Tokunaru
Published: July 2006

Demethylation of 2′-methoxyacetophenones with anhydrous aluminum chloride in acetonitrile was studied to survey its scope and limitations. The mechanism which the reaction proceeds via sterically constrained intermediates was proposed from the substituent effects. Additionally, dealkylation of 2′-benzyloxy-, 2′-ethoxy-, and 2′-isopropoxyacetophenones with two demethylating reagents, hydrochloric acid in acetic acid and anhydrous aluminum bromide in acetonitrile, was studied. It was found that the reactivity was greatly affected by the steric factor between the alkoxyl group and reagent. This behavior may have wide application in selection of protecting groups in organic synthesis.
Molecular Recognition Indicators of Modified Cyclodextrins Using Twisted Intramolecular Charge Transfer Fluorescence
Authors: Hamasaki Keita , Ueno Akihiko , Toda Fujio , Suzuki Iwao , Osa Tetsuo
Published: July 2006

Modified α, β, and γ-cyclodextrins that bear one p-(dimethylamino)benzoyl (DMAB) moiety (DMAB-αCyD, DMAB-βCyD, and DMAB-γCyD, respectively) were synthesized as fluometric molecular recognition indicators. These three modified cyclodextrins show dual fluorescence arising from normal planar and twisted intramolecular charge transfer (TICT) excited states. Among them, the TICT emission was particularly great in the case of DMAB-βCyD. The TICT fluorescence intensity increased for DMAB-αCyD and DMAB-γCyD, and decreased for DMAB-βCyD when the hosts form inclusion complexes with guest molecules, and the variation of the TICT emission intensity was used as a sensitivity parameter. DMAB-αCyD was effective to detect chain compounds while DMAB-γCyD showed high sensitivities to bulky compounds including several steroids. Various guest compounds were detected by DMAB-βCyD, The orders of the sensitivities of the hosts were parallel with those of the binding constants except for the case of DMAB-γCyD. The results demonstrate that these fluorescent CyDs are useful as fluorescent indicators of molecular recognition.
The Reaction Field Energy of a Non-Ideal Dipole
Authors: Abe Takehiro
Published: July 2006

The reaction field energy of a non-ideal dipole directed along the radius vector in a spherical cavity has been formulated and compared with that of a point dipole located in the center of the cavity for two special cases. Thus, the validity of approximation of the point dipole used widely is investigated.
Preparation of Polypyrrole from Pyrrole by Using the Catalytic System of VO(acac)2–AlCl3–O2
Authors: Izumi Seishi , Toshima Naoki
Published: July 2006

Polypyrrole was prepared by the oxidation of pyrrole with molecular oxygen in the presence of bis(acetylacetonato)(oxo)vanadium(IV) (VO(acac)2) and aluminum chloride (AlCl3) as a catalyst. The polymerization of pyrrole at 20 °C at a mole ratio of VO(acac)2/AlCl3 = 1/1 in acetonitrile under 1 atm of oxygen gave polypyrrole, 10−2 S cm−1 in electrocondutivity in 260% yield on the basis of the catalyst charged. The addition of pyridine to the system improved the electroconductivity of the polypyrrole produced. The reaction mechanism is discussed based on the UV-vis spectra of the reaction mixtures, the ESR spectra of the catalytic system, and the oxygen consumption during polymerization.
Characteristics of Iron Phophate as a Catalyst for Partial Oxidation
Authors: Ai Mamoru , Muneyama Etsuhiro , Kunishige Atsuhiro , Ohdan Kyoji
Published: July 2006

The catalytic performances of iron phosphate were compared with those obtained from the phosphates of vanadium and molybdenum in the partial oxidation of various compounds, such as 1-butene, crotonaldehyde, methacrylaldehyde, propinaldehyde, butyraldehyde, isobutyraldehyde, propionic acid, butyric acid, and isobutyric acid. Iron phosphate showed excellent performance for only the oxidative dehydrogenation of isobutyraldehyde and isobutyric acid to form methacrylaldehyde and methacrylic acid, respectively.
Cyclodextrin Precipitates with Naphthalene–Biphenyl Mixed Guests in Aqueous Medium
Authors: Sanemasa Isao , Takahashi Hiroko , Ishibashi Kazunari , Deguchi Toshio
Published: July 2006

Cyclodextrins (β- and γ-CyDs) were precipitated in an aqueous medium at 25 °C in the presence of a naphthalene (N)–biphenyl (B) mixed guest. The N/B molar ratio in the precipitates was found to be governed by SN·KN (SB·KB)−1, where S refers to the solubility of the guest in water and K to the 1 : 1 association constant of the CyD–guest.
The Catalytic Activity of Ionophoric Calix[4]arene Analog
Authors: Okada Yukihiro , Sugitani Yuji , Kasai Yoshinori , Nishimura Jun
Published: July 2006

Calix[4]arene analog (2) having 2-[2-(2-methoxyethoxy)ethoxy]ethyl groups was prepared in 92% yield. Compound 2 showed the extraction of alkali metal ions as an ionophore and the catalytic activity for some SN2 reactions.
Regio- and Stereoselectivity of Cycloadditions of Trifluoromethylated Azomethine Ylide
Authors: Tanaka Kiyoshi , Nagatani Sigeaki , Ohsuga Masaki , Mitsuhashi Keiryo
Published: July 2006

Trifluoromethylated azomethine ylide 1, generated in situ by the conrotatory ring opening of cis-2-benzoyl-1-methyl-3-trifluoromethylaziridine, cycloadded with both electron-deficient and -rich monosubstituted olefins to give exclusively the corresponding 3-substituted pyrrolidines. This high regioselectivity is discussed in connection with the interaction between 1-LUMO and olefin-HOMO.
The Reactions of α-Alkoxy-Substituted Styrenes with Dimethyl Acetylenedicarboxylate and Dimethyl Fumarate Novel Adducts in the Reaction with Dimethyl Fumarate
Authors: Kotsuki Hiyoshizo , Yamaguchi Tadashi , Ohno Keiji , Ichikawa Yoshikatsu , Ochi Masamitsu
Published: July 2006

The reactions of α-trimethylsiloxy-, α-methoxy-, and α-ethoxystyrene with dimethyl acetylenedicarboxylate (DMAD) and dimethyl fumarate (DMFM) have been investigated. With DMAD the 1 : 1 Diels–Alder and the 1 : 2 Diels–Alder ene adducts were obtained, while the reaction with DMFM gave novel open-chain adducts through alkyl group migration and incorporation of the solvent.
Quantum Chemical Rationale on Free-Radical Formation of Irradiated Acrylic Polymers
Authors: Noguchi Akihiro , Kondo Shin-ichi , Kuzuya Masayuki
Published: July 2006

The bond cleavage of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) in their excited states was investigated by means of molecular orbital calculations (AM1 and INDO/S-CI methods) using model molecules. The calculated reaction potentials for the bond cleavages in the excited states showed that the most dissociative bonds are the α-C–H bond for PAA and the C–C bond associated with the decarboxylation for PMAA. β-C–C bond cleavage following the above-mentioned side-bond cleavages seems to be feasible in the higher excited states. The formation of free radicals in the plasma- and γ-irradiations of PAA, PMAA, and their esters could be well explained as reactions in the excited states.
Frontal Chromatography for Nonassociable and Micellar Systems
Authors: Funasaki Noriaki , Hada Sakae , Neya Saburo
Published: July 2006

The continuous flow model of chromatography for computer simulations is developed and applied for nonassociable, dimerizing, and micellar systems. This model is more realistic than the discontinuous flow model, since the former takes into account the infinitesimal flow of the mobile phase. The frontal and zonal chromatograms of sucrose, a nonassociable solute, are determined on a Sephadex G-10 column as a function of the total sucrose concentration. The derivative of the frontal chromatogram at the leading boundary completely overlaps with that at the trailing boundary and has the same shape with the zonal chromatogram. Therefore the number of plate can be calculated from the observed derivative chromatogram. For some dimerizing systems the dimerization constant can be estimated from the concentration dependence of the derivative at the trailing boundary, if an appropriate correction is applied. Some characteristic parameters obtained from the derivative chromatogram of the micellar system provide information on the aggregation pattern. The observed results outlined above can be semiquantitatively predicted by the continuous flow model and by the discontinuous flow model, if the void volume and the number of plate are regarded as adjustable parameters in the latter model.
Synthesis, Crystal Structure, and Properties of Oxygen-Deficient Lanthanum Nickelate LaNiO3−x (0 ≤ x ≤ 0.5)
Authors: Moriga Toshihiro , Usaka Osamu , Imamura Tomomi , Nakabayashi Ichiro , Matsubara Ichiro , Kinouchi Tsuneo , Kikkawa Shinichi , Kanamaru Fumikazu
Published: July 2006

Two kinds of oxygen-deficient phases around LaNiO2.5 were obtained by a low-temperature H2 reduction of perovskite-type LaNiO3. An antiferromagnetic LaNiO2.5 with TN   140 K seems to be stoichiometric and a small amount of excess oxygen leads to a new ferromagnetic phases. A structural refinement has revealed that the former (space group C 2/c) comprised one-dimensionally linked NiO6 octahedra along the c-axis and NiO4 square-planars connecting the octahedra chains. A cooperative Jahn–Teller distortion was observed in both coordination polyhedra, which suggested that LaNiO2.5 has octahedral Ni3+ ions with the low-spin state and square-planar Ni+ ions. Its magnetic property and XPS spectrum support this model. The new ferromagnetism with Tc   230 K could be understood due to a slight canting in the antiferromagnetic interaction between the octahedra and the square-planes.
The Formation Dynamics of Cholesterol Films Prepared by Spontaneous Self-Assembly Method
Authors: Amire Olasoji Abayomi
Published: July 2006

The dynamics of the process of formation of cholesterol films on a solid substrate prepared by the spontaneous self-assembly technique has been investigated. An expression for the coverage in a multilayer system was derived. Application of the equation to cholesterol multilayer film formation kinetics shows that the approach to equilibrium of the self-assembly process obeys first-order rate law. An observed adsorption free energy change of −21.7 ± 0.1 kJ mol−1 was obtained for cholesterol on quartz slide and a mean lifetime of cholesterol on the slide surface during deposition of 78 ± 3 ks at 298.16 K. A mean lifetime for stearic acid adsorbed from hexadecane onto native aluminium oxide surface (data from elsewhere) was found to be 12.4 ± 0.3 ks. The results suggest dynamic processes which strongly depend on the formation constant of the amphiphile for coordination to the substrate.
A Photochemically Prepared O-Bonded Sulfinato Complex of Cobalt(III). Optical Resolution and X-Ray Structure of (2-Aminoethanesulfinato-O,N) [tris(2-aminoethyl)amine]cobalt(III)
Authors: Kojima Masaaki , Shimizu Yasuhiro , Nakajima Kiyohiko , Yoshikawa Yuzo
Published: July 2006

The cis(t-N,O)-[Co{OS(O)CH2CH2NH2-O,N}{N(CH2CH2NH2)3}]2+ (t-N = tertiary amine nitrogen) complex was prepared by photolysis of the corresponding S,N-chelate sulfinato complex. The structure of the linkage-isomerized product was determined by the X-ray method. Optical resolution of the O,N-chelate complex was achieved by SP-Sephadex column chromatography, and the racemization of the complex was studied.
Conversion of Amides, N,N,N′,N′-Tetramethylurea, and Esters to the Corresponding Selenoxo Compounds by Treatment with Bis(trimethylsilyl) Selenide and BF3·OEt2
Authors: Takikawa Yuji , Watanabe Hiroyuki , Sasaki Ryuji , Shimada Kazuaki
Published: July 2006

The reactions of amides and N,N,N′,N′-tetramethylurea with (Me3Si)2Se in the presence of BF3·OEt2 afforded the corresponding slelenoxo compounds in good yields. On the other hand, selenation of ethyl and butyl benzoates in a similar manner gave benzoin and 2,3,5,6-tetraphenyl-1,4-diselenin via selenoesters. The trapping of selenoesters was also achieved by 2,3-dimethyl-1,3-butadiene to afford [4+2] cycloadducts.
Production of CN(B2Σ+) Radicals in the Dissociative Excitation of BrCN and ICN by Metastable Ar and Kr Atoms in a Flowing Afterglow
Authors: Kanda Kazuhiro , Suzuki Kaoru , Kondow Tamotsu , Ito Haruhiko , Kuchitsu Kozo
Published: July 2006

The dynamics of dissociative excitation of BrCN or ICN producing CN(B2Σ+) radicals by Ar(3P2) or Kr(3P2) was investigated by using the flowing afterglow method. The observed vibrational distributions of CN(B) are consistent with the reported reaction mechanism for the CN(B) formation initiated by the transfer of the excitation energy of the metastable atom to the cyanide molecule.
Community-Based Substance Abuse Training
Authors: Bonder Bette R. , Hulisz Darrell , Marsh Sybil , Bonaguro John
Published: July 2006

Elementary school staff requested and were provided with strategies for helping students and a resource guide to services for students living with substance-abusing adults.
Training School Nurses
Authors: Castleman Joan B. , Novak Maureen A. , Sposetti Venita J.
Published: July 2006

This field project focused on training school nurses to do screening and brief interventions for tobacco use. Needed resources were organized in a kit.
Modeling the Psychology of Consumer and Firm Behavior with Behavioral Economics
Authors: Ho Teck H. , Lim Noah , Camerer Colin F.
Published: July 2006

Marketing is an applied science that tries to explain and influence how firms and consumers behave in markets. Marketing models are usually applications of standard economic theories, which rely on strong assumptions of rationality of consumers and firms. Behavioral economics explores the implications of the limits of rationality, with the goal of making economic theories more plausible by explaining and predicting behavior more accurately while maintaining formal power. This article reviews six behavioral economics models that are useful to marketing. Three models generalize standard preference structures to allow for sensitivity to reference points and loss aversion, social preferences toward outcomes of others, and preference for instant gratification. The other three models generalize the concept of game-theoretic equilibrium, allowing decision makers to make mistakes, encounter limits on the depth of strategic thinking, and equilibrate by learning from feedback. The authors also discuss a specific marketing application for each of these six models. The goal of this article is to encourage marketing researchers to apply these models. Doing so will raise technical challenges for modelers and will require thoughtful input from psychologists who study consumer behavior. Consequently, such models could create a common language both for modelers who prize formality and for psychologists who prize realism.
Rebuilding the Boat While Staying Afloat: The Modeling Challenge for Behavioral Economics
Authors: Prelec Drazen
Published: July 2006

The author comments on the article by Ho, Lim, and Camerer (2006) , which showcases the potential of the new behavioral economics approach to marketing with six theoretical “case studies.” Each case study describes a new model of consumer behavior or competitive marketing interactions. The author raises two general questions about such models. The first question is whether behavioral economics is, in reality, a new form of theoretical psychology, competing with existing psychological models and theories and subject to the same vulnerability to evidence as applies to psychological theory. The author argues that behavioral economists are ambivalent about this point, sometimes claiming psychological realism or plausibility as a necessary modeling requirement and other times introducing assumptions for modeling convenience. The second question is whether the impact of behavioral economics on marketing will be experienced more strongly through the development of new quantitative models or through the exploration of qualitative lessons stimulated by behavioral violations of rationality. It is argued that behavioral economics not only contributes new modeling instruments but, through its documentation of rationality violations or “anomalies,” can provide a rich source of intuitions and insights into consumer psychology as well.
Things that Go Bump in the Mind: How Behavioral Economics Could Invigorate Marketing
Authors: Johnson Eric J.
Published: July 2006

In their article, Ho, Lim, and Camerer (2006) lead by example. They identify principles from behavioral economics, and rather than simply exhort their readers to pay attention, they actually produce impressive demonstrations of how these principles can be applied to substantive marketing problems. It is easy to argue that these ideas are important, but it is more difficult to demonstrate that importance. Implicitly, Ho, Lim, and Camerer send a message of encouragement: Behaviorally realistic assumptions are not problems to be ignored; they are opportunities. Formal models can capture psychologically realistic concerns. Together, they should be the grist for the next generation of marketing mills.
How “Psychological” Should Economic and Marketing Models Be?
Authors: Ho Teck H. , Lim Noah , Camerer Colin F.
Published: July 2006

The authors discuss the potential of making the recently developed behavioral economics models even more “psychological” by (1) increasing their context specificity, (2) allowing different people to have different model parameters, and (3) capturing the underlying psychological processes more explicitly. They show that some of these models already make room for understanding context specificity and heterogeneity, and they discuss new ways to enrich the models along those two dimensions. The task of adding process details is more challenging in simple mathematical forms because these models must serve as building blocks for aggregate market models.
Leveraging Missing Ratings to Improve Online Recommendation Systems
Authors: Ying Yuanping , Feinberg Fred , Wedel Michel
Published: July 2006

“Product recommendation systems” are backbones of the Internet economy, leveraging customers' prior product ratings to generate subsequent suggestions. A key feature of recommendation data is that few customers rate more than a handful of items. Extant models take missing recommendation rating data to be missing completely at random, implicitly presuming that they lack meaningful patterns or utility in improving ratings accuracy. For the widely studied EachMovie data, the authors find that missing data are strongly nonignorable. Recommendation quality is improved substantially by jointly modeling “selection” and “ratings,” both whether and how an item is rated. Accounting for missing ratings and various sources of heterogeneity offers a rich portrait of which items are rated well, which are rated at all, and how these processes are intertwined, while reducing holdout error by 10% or more. The authors discuss ways to implement the proposed framework within existing recommendation systems and its implications for marketers.
When Will a Brand Scandal Spill Over, and how Should Competitors Respond?
Authors: Roehm Michelle L. , Tybout Alice M.
Published: July 2006

Three experiments identify conditions under which a brand scandal spills over and negatively affects attitudes and beliefs about the product category and about competing brands. The research also examines factors that may enhance or reduce the likelihood of spillover effects and strategies for responding to scandal spillover.
Is Happiness Shared Doubled and Sadness Shared Halved? Social Influence on Enjoyment of Hedonic Experiences
Authors: Raghunathan Rajagopal , Corfman Kim
Published: July 2006

Because many hedonic stimuli (e.g., movies, vacations, food) are often consumed in the company of other people, it is important to know how social influence affects the enjoyment of shared experiences. Extrapolation from informational and normative influences suggests that enjoyment is enhanced when others offer positive opinions and diminished when they offer negative opinions about shared stimuli. In this article, the authors propose an alternative model. Building on the need to belong and the need for accuracy, the authors predict that enjoyment from sharing stimuli depends on consumers' perceived interpersonal agreements about the shared stimuli, such that congruence of opinions enhances and incongruence of opinions diminishes the enjoyment of the shared experience. The results from three experiments support the authors' predictions and indicate that under some circumstances, social influence can operate in opposite directions on judgments of shared stimuli and on the enjoyment of sharing them.
A Comparison of Criteria to Design Efficient Choice Experiments
Authors: Kessels Roselinde , Goos Peter , Vandebroek Martina
Published: July 2006

To date, no attempt has been made to design efficient choice experiments by means of the G- and V-optimality criteria. These criteria are known to make precise response predictions, which is exactly what choice experiments aim to do. In this article, the authors elaborate on the G- and V-optimality criteria for the multinomial logit model and compare their prediction performances with those of the D- and A-optimality criteria. They make use of Bayesian design methods that integrate the optimality criteria over a prior distribution of likely parameter values. They employ a modified Fedorov algorithm to generate the optimal choice designs. They also discuss other aspects of the designs, such as level overlap, utility balance, estimation performance, and computational effectiveness.
Models for Heterogeneous Variable Selection
Authors: Gilbride Timothy J. , Allenby Greg M. , Brazell Jeff D.
Published: July 2006

Preference heterogeneity is a major research stream in marketing aimed at quantifying and understanding the diversity of demand for product attributes and attribute levels. In experimental settings, in which consumers are presented with simple descriptions of product offerings, continuous distributions of heterogeneity, such as the multivariate normal, provide a useful representation of preference. However, in more complex cases in which respondents have value for only a few of the benefits associated with an offering or cognitive constraints that result in selective attention to a subset of the information available, continuous distributions of heterogeneity do not reflect the possibility that a subset of the variables has nonzero effect sizes for different respondents. Identifying which attributes are used in a brand choice decision is closely related to the statistical procedure of variable selection. This article extends variable selection methods to accommodate heterogeneity across consumers and data contexts, conditions frequently encountered in marketing studies. The authors apply the methods to a discrete-choice conjoint study in which data are collected in both full-profile and partial-profile formats.
Forward-Looking Bidding in Online Auctions
Authors: Zeithammer Robert
Published: July 2006

At Internet auction sites, such as eBay, nearly identical goods are often sold in a sequence of auctions, separated by small amounts of time. Upcoming auctions are announced several days in advance, so buyers can benefit from forward-looking strategies that take this information into account. This article develops a model of such bidding, provides empirical evidence of the model's relevance to actual behavior on eBay, and discusses the general implications of forward-looking bidding for sequential, auction-driven marketplaces.
The Periodicity of Pricing
Authors: Bronnenberg Bart J. , Mela Carl F. , Boulding William
Published: July 2006

Retail pricing data combine multiple decisions (e.g., regular pricing and discounting) that are possibly made by multiple decision makers (e.g., retailers and manufacturers). For example, temporary price reductions (high-frequency price changes) can be used to price discriminate in the short run, whereas regular price adjustments (low-frequency price changes) might reflect changes in long-term costs or demand. Time disaggregation cannot disentangle these factors, because frequency aggregation exists even when data are analyzed at the lowest possible level of temporal aggregation. Because little is known about the nature of pricing interactions across various planning cycles, this article develops several empirical generalizations about the role of periodicity in pricing. Using week-store stockkeeping-unit-level price data in 35 grocery categories, the authors find that (1) cross-brand correlation in prices occurs at multiple planning horizons, and the planning horizon of the predominant interaction does not typically coincide with the sampling rate of the data; (2) aggregating pricing interactions across frequencies obscures distinct and different interactions; (3) pricing interactions are related to category- and brand-specific factors, such as mean interpurchase times; (4) regular price changes explain most of the variation in prices; and (5) periodicity can affect inferences about the nature of competition within a category. The authors conclude by discussing several practical marketing applications for which marketing decisions across frequencies have relevance.