bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydrates of Organic Compounds. XV. The Formation of Clathrate-Like Hydrates of Tetraisopentylammonium Alkanoates and Alkanedioates
Authors: Nakayama Haruo , Nakamura Kayoko , Haga Yukio , Sugiura Y\={o}ji
Published: July 2006

The solid-liquid phase diagrams of binary mixtures of water with tetraisopentylammonium alkanoates, [(i-C5H11)4N]CnH2n+1COO (n=0–9), and with bis(tetraisopentylammonium) alkanedioates, [(i-C5H11)4N]2-[OOC(CH2)nCOO] (n=0–10), were examined in order to confirm the formation of clathrate-like hydrates. The results are summarized as follows: (1) For all the compounds examined the formation of a clathrate-like hydrate is newly confirmed; (2) the melting points of these hydrates are fairly high (lie between 10 and 28°C); (3) typical hydrates formed by the alkanoates have hydration numbers around 38 and those formed by the alkanedioates around 80; and (4) hydrates with hydration numbers around 14 and larger than 40 are also found for the alkanoate hydrates and around 30 and larger than 80 for the alkanedioate hydrates. The effects of the alkyl chain length of the alkanoate anion and of the methylene chain length of the alkanedioate anion on the stability of the hydrates are not marked, suggesting that a hydrogen-bonded framework of water molecules around a (i-C5H11)4N+ cation is fairly stable.
Back Biting Reactions during the Catalytic Decomposition of Polyethylene
Authors: Ishihara Yumiko , Nanbu Hidesaburo , Saido Katsuhiko , Ikemura Tadashi , Takesue Tomoyuki
Published: July 2006

Isobutane and isopentane were selectively obtained by polyethylene catalytic decomposition using the NaY-type zeolite catalyst. Back biting reactions are thus essential to gas formation during the catalytic decomposition of polyethylene. Chain-end secondary carbonium ions cause back biting reactions involving intramolecular rearrnagement to form the C9 fraction. Isobutane and isopentane are then produced by decomposition of the gasification precursor C9 fraction.
Cis-Trans Isomerism among the Octahedral Diaquabis(N,N- or N,N′-dialkylethylenediamine)nickel(II) Complexes and Their Thermal Reaction Products
Authors: Ihara Yoshinori , Satake Yasuhiro , Suzuki Masatatsu , Uehara Akira
Published: July 2006

The thermochemical changes in coordination structure of diaquabis(N,N- or N,N′,-dialkylethylenediamine)nickel(II) complexes ([Ni(H2O)2(diamine)2]X2·nH2O) were reinvestigated by means of TG-DTA and electronic spectroscopy at room and elevated temperatures, where diamine is N,N (or N,N′-dimethylethylenediamine (NN- or NN′-dmen) or N,N-(or N,N′)-diethylethylenediamine (NN- or NN′-deen); X is Cl−, Br−, I−, or NO3−; n is 0, 1, 2, or 3. The diaqua complexes prepared were all trans except for cis-[Ni(H2O)2(NN-dmen)2]I2. The trans complexes with the symmetric (N,N′-dialkylsubstituted) diamines brought about a deaquation-anation upon heating, retaining the original trans configuration, while those with the asymmetric (N,N-dialkylsubstituted) diamines transformed into the cis complexes. In the case of the NN-dmen complexes, cis-halogenoaqua species were isolated as a stable intermediate during the thermal reactions. The complex nitrates changed to trans-dinitrato or cis-mononitrato species depending upon the diamines. The effects of the N-substituents in the diamines and of the anions on the patterns of thermal reactions were also discussed.
Conductivity of N-Methylpyridinium Iodide and Its Methyl Substituted Derivatives in Water–Ethanol Mixture
Authors: Swain Ranjan Kumar , Behera B
Published: July 2006

The conductivity of N-methylpyridinium iodide (NMPI) and its methyl substituted derivatives at 2-, 3-, and 4-positions in water–ethanol solvent mixtures is reported at 25°C. The conductivity data are analyzed by the Shedlovsky method to get both Λ0 and KA, the association constant, simultaneously. The Λ0 values decrease or increase with increase or decrease of the viscosity of the solvent mixtures. The values of Λ0 and K are in the order of H>3->4->2-. The Walden product Λ0η for these iodide salts behaves in a manner as is expected for highly hydrogen bonded water-alcohol mixtures. A mole fraction of 0.15 to 0.2 in ethanol indicates maximum interaction between water and ethanol. The values of Λ0 and KA indicate greater solvation and hence less ion-ion interaction in case of NMPI and 3-CH3 salts than 2- and 4-CH3 salts.
Thermospray Ionization Mass Spectrometry of Polydimethylsiloxane Antifoams
Authors: Nishimura Toshihide , Aoki Yukimi , Hiyama Yukio , Sonoda Akio
Published: July 2006

Mass Spectrometric characterization of several polydimethylsiloxane (PDSI) antifoams has been studied using a thermospray (TSP) ionization technique. The PDSI antifoams dissolved into an eluent were flow-injected to a TSP interface without column separation. A selective formation of PDSI ammonium adduct ions directly reflecting their molecular weight distributions was observed in the mass region up to 3500 daltons. Both cyclic PDSIs and fatty acid esters were detected for a water-dilutable antifoam and their relative abundances and species were characteristic to a particular formulation of antifoam emulsion. Thus TSP mass spectrometric technique seems suitable and useful for analysis of an aqueous antifoam sample to identify both its molecular weight distribution of PDSIs and a type of antifoam formulations used in various fields such as food and pharmaceutical industries.
Asymmetric Transformation of (RS)-1,2,3,4-Tetrahydro-3-isoquinolinecarboxylic Acid via Salt Formation with (1S)-10-Camphorsulfonic Acid
Authors: Shiraiwa Tadashi , Furukawa Tsuyoshi , Tsuchida Tamotsu , Sakata Shinji , Sunami Michio , Kurokawa Hidemoto
Published: July 2006

Asymmetric transformation of (RS)-1,2,3,4-tetrahydro-3-isoquinolinecarboxylic acid [(RS)-TIC] by use of (1S)-10-camphorsulfonic acid [(S)-CS] as a resolving agent gave a salt of (S)-TIC with (S)-CS with 90% optical purity in hexanoic acid. The TIC obtained from the salt was purified to give optically pure (S)-TIC in 80% yield based on the starting (RS)-TIC.
A Convenient Synthesis of Sulfones by the Oxone Oxidation of Sulfides in an Aprotic Solvent in the Presence of Clay Minerals
Authors: Hirano Masao , Tomaru Jun-ichirou , Morimoto Takashi
Published: July 2006

The title oxidation in dichloromethane in the presence of “wet”-montmorillonite and -kaolin afforded the corresponding sulfones in excellent to almost quantitative yield under neutral and mild conditions.
Absorption and Fluorescence Spectra of 1-Methyl-2(1H)-pyridinimines and 2-Methylaminopyridine–Acetic Acid Complex
Authors: Fujimoto Akira , Inuzuka Kozo
Published: July 2006

Upon the addition of acetic acid to 2-methylaminopyridine in isooctane, weak absorption and fluorescence bands appeared near 350 and 465 nm at the tail of the main bands, respectively. These new bands were attributed, on the basis of the spectral results of 1-methyl-, 1,3-dimethyl-, 1,4-dimethyl-, 1,5-dimethyl-, and 1,6-dimethyl-2(1H)-pyridinimines, and 1-methyl-2-methylimino-1,2-dihydropyridine, to have originated from 2(1H)-pyridinimine moiety (iminoform tautomer) in the 2-methylaminopyridine-acetic acid complex. In addition, the fluorescence quantum yields of the 1-methyl-2(1H)-pyridinimines in isooctane were shown to be very small.
Partial Oxidation of [Octakis(dodecyloxy)phthalocyaninato]zinc(II) with 2,3-Dichloro-5,6-dicyano-p-benzoquinone
Authors: Kasuga Kuninobu , Nakao Tadahiro , Mihara Takuya , Sogabe Kunihisa
Published: July 2006

While an organic oxidant such as 2,3-dichloro-5,6-dicyano-p-benzoquinone oxidized [Zn{Pc(OC12H25)8}] in a chloroform solution, it did not oxidize H2Pc(OC12H25)8 and [Cu{Pc(OC12H25)8}]. Oxidation was confirmed by the electronic and ESR spectra, as well as cyclic voltammograms. The electrical conductivity of the zinc(II) complex increased 105 times in partial oxidation.
Anisochrony in Rotatable Ligands and Symmetry Non-Equivalence Characterized by Subduction of Coset Representations
Authors: Fujita Shinsaku
Published: July 2006

A general method of characterizing symmetry equivalence and non-equivalence in a molecule is developed on the basis of the one-one correspondence between an orbit and a coset representation. This method provides us with a theoretical foundation to understand anisochrony in rotatable ligands. A given molecule is regarded as a combination of a three-dimensional skeleton and ligands. The ligand is referred to as a segment or a fragment according to its environment. Thus, the fragment is defined as a ligand-in-isolation; and the segment denotes a ligand built into a molecule. The symmetry of the ligand as a fragment is restricted to the local symmetry. This restriction is examined by using methyl and methylene ligands as examples. A methyl fragment has a homospheric C3v(/Cs) orbit that consists of three hydrogen atoms. On the other hand, a methylene fragment has an enantiospheric Cs(/C1) orbit that contains two hydrogen atoms. Such an orbit is incorporated into various molecules to afford restricted orbits, which are characterized by subduction of coset representations. The restricted orbits are discussed in terms of global and local orbits. This discussion provides a general approach to rationalize various types of anisochronies.
Extraordinary Coordination of Acetonitrile to Square-Planar, 1,4,8,11-Tetraazacyclotetradecanenickel(II) and (1R,4R,8S,11S)-1,4,8,11-Tetramethyl-l,4,8,11-tetraazacyclotetradecanenickel(II) Cations
Authors: Yokoyama Takashi , Iwamoto Etsuro , Kumamaru Takahiro
Published: July 2006

Coordination of dipolar aprotic solvents to the square-planar complexes of nickel(II) was investigated in nitrobenzene (NB) spectrophotometrically. Compared with N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), it was observed that acetonitrile (AN) was strongly coordinated to [NiL]2+ (L=1,4,8,11-tetramethyl-1,4,8,ll-tetraazacyclotetradecane). The stepwise coordination constants KNiS1 and KNiS2 (mol−1 dm3) for (1R,4R,8S,11S)-[NiL]2+ were found to be (1.6, 0.5), (1.0, 0.1), (3.4, 6.7), and (0.4, 1.9) for DMSO, DMF, AN, and benzonitrile, respectively. The KNiS2 values for nitriles are larger than the KNiS1 values, showing that nitriles are coordinated to the metal ion through π-back donation.
Silica-Supported Boron Phosphate Catalyst Prepared by Chemical Vapor Deposition
Authors: Sato Satoshi , Hasegawa Mitsuharu , Sodesawa Toshiaki , Nozaki Fumio
Published: July 2006

A silica-supported boron phosphate (BPO4) catalyst was prepared by chemical vapor deposition (CVD) using mixtures of boron triethoxide and phosphoryl trimethoxide. Both the amount and the P/B ratio of deposited BPO4 were changed with the CVD temperature and time. At the optimum CVD temperature of 300°C, the amount of deposited BPO4 was linearly increased with the CVD time. When alkoxide mixtures with the desired P/B ratio were used as CVD sources at 300°C, the expected P/B ratios were available. At CVD temperatures below 300°C, neither a sufficient amount nor a desired P/B ratio was given. On the other hand, above 325°C, the deposition was suppressed by blocking the micropore of silica, especially for long-time CVD operation, owing to the too fast deposition. Although the resulting surface compound was amorphous, it was revealed to have microstructures of BPO4 by means of a 31P NMR measurement. The amorphous BPO4 dispersed highly on silica exhibited a high catalytic efficiency for the isomerization of 1-butene and a simultaneous oligomerization of 1-butane in comparison with a catalyst prepared by the conventional impregnation method.
Application of the SPE Method to Organic Electrochemistry. XI Influence of the Solvent on the Electrooxidation of Cinnamyl Alcohol on Mn, Pt–Nafion
Authors: Chen Zhen , Mizoe Toshiyuki , Ogumi Zempachi , Takehara Zen-ichiro
Published: July 2006

The influence of organic solvents on the electrooxidation of cinnamyl alcohol on Mn, Pt–Nafion has been investigated. Though tetrahydrofuran (THF) gave a high current efficiency (90%), carbon tetrachloride gave a low current efficiency (<20%). The importance of a co-solvent for the SPE electrolyzer was proposed and substrate transport to the active site located at the interface platinum/ionic cluster region was enhanced by solvents miscible with water. Though THF behaved as a good co-solvent, carbon tetrachloride did not. A composite electrode deposited with platinum on both surfaces of Nafion was applied to oxidation. The cell voltage was as low as 2 V.
Photocatalysis on Native and Platinum-Loaded TiO2 and ZnO Catalysts —Origin of Different Reactivities on Wet and Dry Metal Oxides—
Authors: Anpo Masakazu , Chiba Katsuichi , Tomonari Masanori , Coluccia Salvatore , Che Michel , Fox Marye Anne
Published: July 2006

Substantial differences in photocatalytic reactivity were observed on powdered TiO2 and ZnO, both Pt-loaded and unloaded, in the photocatalytic hydrogenation of CH3C≡CH and C3H6 in the presence of H2O. Similar reactivity was observed, however, in the photocatalytic oxidation of i-C4H8 and C3H6 by O2 on these same catalysts. Photoluminescence of TiO2 and ZnO in the presence and the absence of H2O and/or O2 indicate that H2O causes a downward band bending to increase the efficiency of recombination of photogenerated electrons and holes, with a greater effect being observed on ZnO than on TiO2. These results, together with the direct detection of reaction intermediates by ESR, are rationalized by differences in the yields of the photogenerated intermediates, i. e., H (formed from trapped electrons) and OH (formed from trapped holes). The steady state concentrations of these intermediates depend on the degree of the positively-charged adducts on the surfaces of these oxides. The addition of O2 causes an upward band bending of the oxide and suppresses recombination of photo-generated electrons and holes, by formation of negatively-charged surface adducts. With similar degrees of band bending, TiO2 and ZnO produce almost the same photocatalytic reactivities as are observed for these oxides as dry systems.
Conversion of Hydroxyl Groups in Alcohols to Other Functional Groups with N-Hydroxy-2-thiopyridone, and Its Application to Dialkylamines and Thiols
Authors: Togo Hideo , Fujii Misa , Yokoyama Masataka
Published: July 2006

The radical decarboxylation reaction of N-alkoxyoxalyloxy-2-thiopyridone which was prepared by the reaction of alcohol, oxalyl chloride, and N-hydroxy-2-thiopyridone was studied both in the absence and presence of olefinic compounds. The same reactions with olefinic and acetylenic alcohols gave the corresponding lactone derivatives. On the other hand the unsymmetrical alkyl 2-pyridyl disulfides were obtained by the same reaction with aliphatic thiols.
Selective Deoxygenation of Various N–O Bonds Catalyzed by Rhodium Carbonyl Clusters in the Presence of H2O and CO and Their Heterogenization Using Amino-Substituted Polystyrenes
Authors: Kaneda Kiyotomi , Fujita Kazuo , Takemoto Tetsuya , Imanaka Toshinobu
Published: July 2006

Catalytic deoxygenation of various N–O bonds using rhodium carbonyl compounds under a water gas shift reaction was studied. A catalyst system of Rh6(CO)16 and N,N,N′,N′-tetramethyl-1,3-propanediamine was found to have high activities for the following deoxygenations: 1) conversion of nitrobenzenes to anilines, 2) aliphatic nitro compounds to nitriles, 3) oximes to nitriles, 4) hydroxylamines to amines, and 5) amine oxides to amines. The above-mentioned rhodium catalyst system was heterogenized by using amino-substituted polystyrenes. Rh6 and Rh14 carbonyl clusters of [Rh6(CO)15H]−, [Rh6(CO)15]2−, and [Rh14(CO)25]4−, were formed on the polymer surface. The characteristic features of the catalysis of the polymer-bound rhodium cluster complexes are described in relation to the corresponding homogeneous ones.
Synthesis of α,ω-Diamino Acids via Amidocarbonylation Reaction: Novel Synthesis of Lysine, Ornithine, and Their Analogs
Authors: Amino Yusuke , Izawa Kunisuke
Published: July 2006

α,ω-Diamino acid derivatives, such as lysine and ornithine, were synthesized via amidocarbonylation (cobalt-catalyzed formation of N-acyl α-amino acid from aldehyde, amide and carbon monoxide) of ω-(phthalimido)alkanals in good yield. The phthalimido group was proved to be intact under the conditions of amidocarbonylation. The hydroformylation-amidocarbonylation of N-phthaloyl-β,γ- and N-phthaloyl-γ,δ-unsaturated amines proceeds very nicely to give α,ω-diamino acid derivatives with good selectivity. Selective deprotection of α-N-acyl-ω-N-phthaloyl α,ω-diamino acids was achieved using hydrazine for the N-phthaloyl group and aminoacylase for the N-acetyl group to afford the optically active α,ω-diamino acid, respectively.
A Study of the Reduction of Chelated Palladium on Mercury Electrode
Authors: Lai C K , Wang Y Y , Wan C C
Published: July 2006

This paper investigates the reduction kinetics and mechanism of Pd(II)–ethylenediamine with cyclic voltammetry and normal pulse polarography techniques. The results indicate that the reduction is an irreversible process. The major kinetic parameters and diffusion coefficients of Pd(II)–ethylenediamine and other Pd(II)–aliphatic diamine complexes are reported. The influences of concentrations, pH values, and ligand structures on the reduction of Pd(II) complex are also discussed. The electrochemical reaction orders with respect to ethylenediamine and Pd(II)–ethylenediamine are found to be 0 and 1, respectively and these reaction orders demonstrate an undissociated complex reduction mechanism. Finally the iodide effect on normal pulse polarography is studied. The increase in current when iodide is added implies that the reduction is via the outer sphere path way.
Chemical Shift Standards in High-Resolution Solid-State NMR (1) 13C, 29Si, and 1H Nuclei
Authors: Hayashi Shigenobu , Hayamizu Kikuko
Published: July 2006

The resonance frequencies of 13C, 29Si, and 1H nuclei in pure tetramethylsilane have been measured accurately by spinning the liquid sample at the magic angle, which are free from the effects of the bulk magnetic susceptibility and the solvent. Using the above resonance positions, the chemical shifts of several second shift-standard materials have been determined with much improved accuracy and precision.
The Reaction of Diphenyl(trimethylsilylmethyl)phosphine with Carbonyl Compounds in the Presence of Fluorides
Authors: Kawashima Takayuki , Mitsuda Noriaki , Inamoto Naoki
Published: July 2006

Diphenyl(trimethylsilylmethyl)phosphine (1) was allowed to react with benzophenone in the presence of CsF in N,N-dimethylformamide to give a mixture of methyldiphenylphosphine (2), (2,2-diphenyl-2-trimethylsiloxyethyl)diphenylphosphine (3) and (2-hydroxy-2,2-diphenylethyl)diphenylphosphine (4) in good yield. The use of about 10 mol% of CsF gave 3 with fairly good selectivity. The reaction with benzaldehyde gave a similar result, but only protodesilylation occurred in the reaction with enolizable carbonyl compounds.
Synthesis of Lateral Root-Inducing Compounds Using an Efficient Coupling Reaction of Chiral Triflates
Authors: Kotsuki Hiyoshizo , Miyazaki Aya , Ochi Masamitsu , Sims James J
Published: July 2006

Lateral root-inducing compounds, isolated from the bacterium Erwinia quercina, have been synthesized by using a coupling reaction of chiral triflates derived from l- or d- tartrates and their biological activities examined.
Photoinduced Intramolecular Cyclization Reaction of 2-(2-Alkenoyl)-3-isopropylthio-1,4-benzoquinones to Heterocyclic Compounds
Authors: Iwamoto Hidetoshi , Takuwa Akio
Published: July 2006

Irradiation of 2-acryloyl- and 2-(1-cycloalkenylcarbonyl)-3-isopropylthio-1,4-benzoquinones in benzene gave tricyclic and tetracyclic compounds in good yields, respectively.
Indium-Induced Reaction of Phenacyl Iodide. Deiodinative Dimerization to β,γ-Epoxy Ketone and Aldol Condensation with Aldehydes
Authors: Araki Shuki , Butsugan Yasuo
Published: July 2006

The reaction of phenacyl iodide with indium metal gave 3,4-epoxy-1,3-diphenyl-1-butanone which, on treatment with silica gel, gave 2,4-diphenylfuran and 2,4-diphenyl-4-oxobutanal. Metallic indium as well as indium(I) iodide were found to mediate the aldol condensation between α-halo ketone and aldehyde.
Organophosphorus Chemistry. XV. The Reaction of 10-Dicyanomethylene-9(10H)-phenanthrenone with Alkyl Phosphites
Authors: Abdou Wafaa M , Ganoub Neven A F , Mahran Mohamed R
Published: July 2006

The titled compound 5a reacts with trialkyl phosphites and dialkyl phosphonates to give, in each case, two conformers (A+B) of the corresponding phosphonate 8 and 9. The yields of the two isomers were estimated on the basis of 31P NMR data. Besides, structures 8 and 9 were supported by analytical and spectroscopic measurements of the major isomer 8A and 9A. The rotational isomers were assigned in terms of the Newman projection and NMR data. Relative ratios were studied in the light of dynamic NMR spectroscopy.
Electrical Conductivity of Black Phosphorus-Germanium Compound
Authors: Maruyama Yusei , Inabe Tamotsu , He Lin , Terui Toshifumi , Oshima Kokichi
Published: July 2006

Single crystals of a new material, black phosphorus doped with germanium, have been prepared by a bismuth-flux method. Germanium atoms are incorporated into the black phosphorus in 2 to 4 atomic percent. The resistivity is reduced by two to three orders (ρ=6×10−3 Ω cm) compared with the pure black phosphorus, and its temperature dependence is metallic at low temperatures. There is no magnetoresistance up to 12 T at 0.6 K in striking contrast to the pure black phosphorus which shows negative magnetoresistance in this region. The crystal lattice constants decrease with germanium doping, especially in the interlayer direction. These facts indicate the enhanced three dimensionality with germanium doping.
Cobalt(III)-tren Complexes of 3-Formylcamphor
Authors: Nakano Yoshiharu , Yoshikawa Yuzo , Masuhara Shigeo , Sato Shoichi
Published: July 2006

3-Formylcamphor Co(III) complexes of a tripod-like ligand, tren, were prepared and the two possible geometrical isomers were separated successfully. The crystal structure of one of them was determined by X-ray diffraction. A red plate-like crystal was monoclinic, space group P21, a=12.401 (2), b=9.9400 (7), c=10.932 (1) Å, β=108.44 (1)°, and Z=2. The structure was refined to R=0.047 on 2818 reflections. The geometrical isomers were compared sepectroscopically.
Preparations, Properties, and Crystal Structures of trans-[Rh(CN)2(NH3)4]Cl·H2O and trans-[Rh(CN)2(en)2]Cl
Authors: Yoshida Kiyohiko , Kitada Takayuki , Odano Naomi , Kashiwagi Mayumi , Harada Kazumasa , Urushiyama Akio , Nakahara Masayoshi
Published: July 2006

Syntheses of the title new complex compounds of Rh(III) were successful. Single, sharp IR peaks of ν (C≡N) were observed at 2130 cm−1 (trans-[Rh(CH)2(NH3)4]Cl·H2O) and 2170 cm−1 (trans-[RH(CN)2(en)2]Cl), respectively. The values of the ligand field tetragonal parameter Dt were estimated to be −366 and −377 cm−1, respectively, based on the 1Ega (D4h)←1A1g Aig transition (37100 cm−1: trans-[Rh(CN)2(NH3)4]+; 37000 cm−1: trans-[Rh(CN)2(en)2]+). The X-ray crystal data are: for trans-[Rh(CN)2(NH3)4]Cl·H2O, orthorhombic, Cmcm, a=7.961(3), b=17.295(2), c=7.436(3) Å, Dc=1.79, Dm=1.79 g cm−3, Z=4; for trans-[Rh(CN)2(en)2]Cl, monoclinic, P21⁄n, a=9.665(4), b=9.107(3), c=6.779(3) Å, β=109.68(2)°, Dc=1.85, Dm=1.83 g cm−3, Z=2. The N≡C–Rh–C≡N sequence of trans[Rh(CN)2(NH3)4]+ lies in a line of m2m Symmetry in the crystal. The central Rh atom of trans-[Rh(CN)2(en)2]+ occupies the special position of inversion symmetry. The important geometrical data of the complexes are Rh–N=2.07(1), Rh–C=2.02(3) Å, N–Rh–N=88.0(5)° (trans-[Rh(CN)2(NH3)4]+) and Rh–N=2.080(3), 2.072(3), Rh–C=2.047(4) Å, N–Rh–N (within chelate ring)=82.7(1)° (trans-[Rh(CN)2(en)2]+).
Effect of Chloride Ion on Lead Signal Appearance in the Co-Existence of Iron in Electrothermal Graphite Furnace Atomic Absorption Spectrometry
Authors: Imai Shoji , Ichinoseki Masayoshi , Nishiyama Yasuko , Hayashi Yasuhisa
Published: July 2006

The atomic absorption signals for lead were measured in various chloride matrices at a charring temperature of 700 K. A typical double-peak signal was observed with iron(III) chloride, while a single peak was observed with iron(III) nitrate. At a charring temperature of 1440 K, the first peak disappeared and only the second peak remained; the atomization temperature of the latter was in agreement with that in the iron matrix. The larger content of the chloride ion increased the first peak absorption and decreased the second peak absorption without any shift of the peak temperatures, showing that one species for the second peak was converted to the same species for the first peak by the addition of a chloride ion. The appearance temperature of the first peak signal in the X−–Fe3+ matrix system increased in the order Cl−<Br−<I−. It was concluded that the appearance of the first peak is caused by the dissociation of lead halide.
Electronic Properties of One-Dimensional Iodine Complex. Benzo[b]phenothiazine–I2.5
Authors: Someno Taro , Hoshizaki Taketoshi , Kozawa Kozo , Uchida Tokiko , Hayashi Hakuro , Sugano Tadashi , Kinoshita Minoru
Published: July 2006

One-dimensional metallic conductance was observed along the c axis of a single crystal of benzo[b]phenothiazine–iodine complex, (B[b]PT)2(I3−)(I)2, the crystal structure of which was preliminarily determined by X-ray analysis. Its metal-insulator transition was observed around 235 K, and the sign of the carriers seemed to be positive above 250 K. From the reflection spectra, with polarized light parallel to the c axis, a plasma-edge-like dispersion was observed in near IR region. Several parameters were evaluated by assuming a tight binding band model. The EPR spectra of this complex consist of only one broad signal (peak-to-peak width at room temperature 250×10−4 T) in the temperature range from 4 K to 296 K (g=1.998±0.002).
Photoreduction and Emission of Solid Europium(III) Chloride in KBr by Laser Irradiation at 308 nm
Authors: Yamada Yasuhiro , Ohno Shin-ichi
Published: July 2006

The emission and transient absorption spectra of solid europium irradiated with laser light at 308 nm were measured. EuCl3·6H2O in a KBr disk was photoreduced to form excited Eu2+, and the emission from excited Eu2+ was observed directly after a reduction of Eu3+. Since Eu2+ was not stabilized in the KBr disk sample, it oxidized rapidly to form Eu3+. From a discussion concerning the temperature dependence of the rate constants of the reduction and deexcitation, it is shown that the reduction rate increases at higher temperature.
Interactions between an Anionic Porphyrin and Cationic Surfactants in Water
Authors: Tominaga Toshihiro , Endoh Satoshi , Ishimaru Hiroaki
Published: July 2006

Interactions between decyl-, dodecyl-, and tetradecyltrimethylammonium bromide (DeTAB, DTAB, and TTAB) and an anionic porphyrin, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphine (H2TPPS4−), have been studied in water at 298.2 K. Precipitate formation constants between the surfactant cations and the H2TPPS4− anion have been obtained. The precipitates were resolubilized by a further addition of the surfactants at concentrations close to the critical micelle concentrations (cmc) in DeTAB, and below the cmc’s in DTAB and TTAB solutions. Surface tension and conductance measurements show that the effects of H2TPPS4− on the cmc’s are very small. The fluorescence of H2TPPS4− is quenched in both water and sodium dodecyl sulfate solutions by the methylviologen cation, but not in cationic surfactant solutions. The diffusion coefficients were measured in a system containing H2TPPS4− and TTAB; the results show the existence of large premicellar aggregates.
Preparation of Metallosilicates with ZSM-5 Type Structure by Atom-Planting Method
Authors: Yamagishi Kouji , Namba Seitaro , Yashima Tatsuaki
Published: July 2006

Aluminosilicates, gallosilicates, and indosilicates with the ZSM-5 type structure were prepared by the “Atom-Planting method”. The introduction of metal cations into the framework of highly siliceous ZSM-5 zeolites was confirmed by IR and unit cell volume measurements. The acidic properties of these metallosilicates were examined by pyridine-IR and NH3-temperature programmed desorption spectroscopies. The increasing order of the acid strengths of the metallosilicates is indosilicate<gallosilicate<aluminosilicate.
The Carboxylation of Active Methylene Compounds with Carbon Dioxide in the Presence of Diphenylcarbodiimide and Potassium Carbonate
Authors: Chiba Koji , Tagaya Hideyuki , Karasu Masa , Ono Tsuyoyuki , Hashimoto Kazumi , Moriwaki Yasusi
Published: July 2006

Active methylene compounds were effectively carboxylated with carbon dioxide in the presence of diphenylcarbodiimide (DPC) as a biotin model and potassium carbonate. Fluorene was carboxylated even under a nitrogen atmosphere in the presence of DPC, indicating that a carbonate ion was the carbon source. The reaction occurred even in the presence of water. It was considered that reaction intermediates are stable to water and that the concentration of the carbonate ion is important for carboxylation.
Thermal Reactions of 6-Methyl-5-[(substituted hydrazono)methyl]- 2,4(1H,3H)-pyrimidinediones with Electron-Deficient Olefins and Acetylene
Authors: Noguchi Michihiko , Kiriki Yasutoshi , Tsuruoka Takashi , Mizui Takahiro , Kajigaeshi Shoji
Published: July 2006

The thermal reactions of some 6-methyl-5-[(substituted hydrazino)methyl]-2,4(1H,3H)-pyrimidinediones (1) were investigated. The 1,5-hydrogen shift in 1 gave 5,6-dihydro-5,6-bis(methylene)-2,4(1H,3H)-pyrimidinedione intermediates, while the 1,2-hydrogen shift in 1 gave azomethine imine intermediates. These reaction profiles depend on the substituents of hydrazone moieties.
Bismuth Trichloride as a New Efficient Catalyst in the Aldol Reaction and the Michael Reaction
Authors: Wada Makoto , Takeichi Eiji , Matsumoto Takashi
Published: July 2006

In the presence of a catalytic amount of bismuth(III) trichloride (5 mol%), silyl enol ethers react with aldehydes at room temperature in dichloromethane to give the corresponding aldols in good yields. Silyl enol ethers also have been found to react with α,β-unsaturated ketones at room temperature in dichloromethane to afford the corresponding 1,5-dicarbonyl compounds, the Michael adducts in good yields. The intermediate adducts of the aldol reaction (the silyl ethers) and the Michael reaction (the silyl enol ethers) were also obtained in good yields.
Antibiotic use in Cystic Fibrosis
Authors: Kelly H. William , Lovato Carol
Published: July 2006

Chronic pulmonary infections contribute significantly to the morbidity and mortality of patients with CF. The primary pathogens are Pseudomonas aeruginosa (PA) and Staphylococcus aureus. Hemophilus influenzae has been isolated from a significant number of patients also. A number of the β-lactam and aminoglycoside antibiotics reportedly have altered pharmacokinetic variables in CF. Therapy of acute pulmonary deterioration consists of intravenous antibiotics for two weeks. Antibiotic selection is based on culture and sensitivity results. Currently, the combination of a broad-spectrum penicillin and an aminoglycoside seems to provide the best results. Prophylactic antibiotics are effective if the primary isolates are sensitive to the agents used. Chronic PA infections are problematic because effective oral agents are not available. Aerosolized antibiotics do not improve results over adequate systemic therapy for acute exacerbations. Questions regarding optimal dosages, frequency, and duration of therapy remain.
Rasburicase for the Management of Tumor Lysis Syndrome in Neonates
Authors: McNutt Deborah M , Holdsworth Mark T , Wong Craig , Hanrahan Jeffery D , Winter Stuart S
Published: July 2006

Objective:

TO describe the management of tumor lysis syndrome (TLS) with rasburicase in 2 patients who presented with cancer within the first month of life and compare and contrast both cases with respect to their underlying renal physiology, management, and eventual outcome.

Case Summary:

TLS developed in 2 neonates born at 38 weeks' gestational age; both were managed in part with rasburicase. One patient was a 21 -day-old infant who received 2 days of induction chemotherapy for the treatment of congenital Stage IV-S neuroblastoma. With a single 0.2 mg/kg dose of rasburicase, the serum urate level normalized and the infant completed therapy without incident. The second patient was a 4-day-old neonate with congenital precursor-B cell acute lymphoblastic leukemia who presented with spontaneous TLS complicated by renal dysfunction. Despite several doses of intravenous rasburicase (2 doses of 0.1 mg/kg and 4 doses of 0.2 mg/kg), as well as aggressive supportive therapy, the infant died of complications arising from uncontrolled TLS.

Discussion:

Neonates may be at particular risk for TLS given their immature renal function and its predisposition toward metabolic derangements. While rasburicase has the potential to provide a rapid reversal of TLS in this patient population, when TLS is complicated by pre-existing acute renal failure, additional interventions and alternative anti-tumor strategies may be necessary for a successful outcome. When managing TLS in infancy, clinicians must consider the relative degree of renal immaturity and its predisposition toward metabolic derangements.

Conclusions:

Rasburicase appears to be well tolerated and effective in lowering serum urate concentrations in the treatment of therapy-related TLS in neonates. However, in instances of spontaneous TLS complicated by the normally low glomerular filtration rate in the newborn infant, the use of rasburicase and other supportive care measures may still be inadequate, warranting further study.
Criminogenic need and women offenders: A critique of the literature
Authors: Hollin Clive R. , Palmer Emma J.
Published: July 2006

Purpose. This paper considers the criminogenic needs of women offenders, raising the question of whether there may be women‐specific criminogenic needs.

Arguments. The risk‐needs model of offending has become increasingly influential in both research and practice. Simply, the risk–needs model holds that some aspects of an individual's functioning are risk factors for offending. The distinction can be drawn between static and dynamic risk factors: the former are historical, the latter reflect current functioning and are amenable to change. These dynamic attributes linked to offending – such as financial status, emotional problems, and substance use – are referred to as criminogenic needs. Needs assessment instruments, such as the Level of Service Inventory‐Revised (LSI‐R; Andrews & Bonta, 1995) have been developed to assess criminogenic need and predict risk of offending. Much of the research informing the risk–needs model has been carried out with male offenders, leading to questions about the criminogenic needs of women offenders and whether there may be women‐specific criminogenic needs.

Conclusion. An overview of typical criminogenic needs, as assessed by the LSI‐R, suggests that there are probably common needs for male and female offenders. A common need does not imply that aetiology or level of importance of that need is the same for men and women, while some events, such as physical and sexual abuse, are arguably criminogenic needs for women. The implications for practice and research of understanding more about women‐specific criminogenic needs are considered.
The relative validity of psychopathy versus risk/needs‐based assessments in the prediction of adolescent offending behaviour
Authors: Marshall John , Egan Vincent , English Marie , Jones Robin M.
Published: July 2006

Purpose. The predictive validity of the psychopathy checklist‐youth version (PCL:YV) and Youth Level of Service/Case Management Inventory (YLS/CMI) for juvenile offenders were compared to examine whether a broad needs–risk tool predicted violence better than a focused individual assessment of psychopathy.

Methods. 94 adolescents from residential and secure units were interviewed and assessed using the PCL:YV and YLS/CMI. Total scores were retrospectively applied to staff‐recorded incidents of violence, total number of charges and convictions and formally recorded assaults. The predictive accuracy of each tool was assessed using correlational and receiver operator characteristic analyses.

Results. The PCL:YV was a better predictor of staff‐recorded violence than the YLS/CMI; both instruments were similar in their ability to predict total number of charges and convictions and assaults. When subdivided by gender, the correlations for predicting staff recorded violence in male participants were significantly higher than for female participants for both test instruments. Both instruments were broadly equivalent in their association with assaults and charges and convictions by gender.

Conclusion. The PCL:YV is a better predictor of recorded violence than the YLS/CMI, but for charges and convictions and assaults, the YLS/CMI and PCL:YV were comparable for UK adolescent offenders. When recalculated to exclude the likelihood of predictor–criterion overlap, the results were the same. These findings are discussed in relation to the value of using risk–needs assessment instruments as compared with scales with a more psychopathological and personality focus.
When stereotypes backfire: Trying to suppress stereotypes produces false recollections of a crime
Authors: Peters Maarten J. V. , Jelicic Marko , Merckelbach Harald
Published: July 2006

Purpose. This study examined whether participants' memories of a racially neutral crime story are influenced by stereotypes and the instruction to suppress stereotypes while reading the crime story. We expected that participants who saw a photograph of a foreign group (negative stereotype prime) and were given the instruction to suppress stereotypes before reading a crime story would make significantly more stereotype‐consistent errors on a recognition test than participants who received a neutral prime and a suppression instruction.

Methods. Participants were 88 undergraduate students (59 women) who were randomly allocated to the cells of a 2 (negative stereotype versus neutral prime)×2 (thought suppression versus control) between‐subjects design. The dependent variables were recognition of accurate items, stereotype‐consistent items and confabulation items.

Results. The critical stereotype × suppression interaction was statistically significant for false recognition of non‐presented stereotype‐consistent items. Simple effect analyses of the suppression condition showed that participants who were primed with a negative stereotype made more stereotype‐consistent recognition errors than those who had been exposed to a neutral prime.

Conclusions. Stereotypes not only make cognitive processing easier, but might also contribute to recognition errors when people do what they often are told to do in the legal arena: suppress stereotypical thinking.
The measurement of concern about victims: Empathy, victim advocacy and the Victim Concern Scale (VCS)
Authors: Clements Carl B. , Brannen Dia N. , Kirkley Shalene M. , Gordon Trina M. , Church Wesley T.
Published: July 2006

Purpose. In a series of studies, the authors developed the Victim Concern Scale (VCS) to assess levels of concern for diverse types of crime victims. The goal was to derive a psychometrically sound instrument and to assess victim concern in relation to other crime‐related attitudes and victim advocacy endorsements.

Methods. Through several scale iterations, participant responses to the VCS were examined. Participants also completed measures of empathy and provided judgments about specific victim/crime scenarios. In addition, in two large samples (college [N = 276] and community [N = 478]), victim concern was compared with other attitudes, attributions and participant demographics.

Results. Participants readily distinguished among different victims. Four factors emerged from the VCS. Raters endorsed the highest levels of concern for victims of violent crimes and the lowest level for ‘culpable’ victims. Women and older respondents showed higher levels of concern across all categories of victims. Both victim concern and emotional empathy influenced advocacy responses to victimization. Victim concern was unrelated to such traits and attitudes as authoritarianism, political ideology or punishment goals; moreover, a high level of concern for victims did not preclude endorsement of rehabilitative goals for offenders.

Conclusions. The VCS appears to be a valid instrument for assessing levels of concern for victims. It differs meaningfully from measures of general empathy. The VCS could be used to assess differential attitudes across demographic groups or as a measure of change following exposure to educational or other persuasive intervention.
A fundamental attribution error? Rethinking cognitive distortions†
Authors: Maruna Shadd , Mann Ruth E.
Published: July 2006

The notion of ‘cognitive distortion’ has become enshrined in the offender treatment literature over the last 20 years, yet the concept still suffers from a lack of definitional clarity. In particular, the umbrella term is often used to refer to offence‐supportive attitudes, cognitive processing during an offence sequence, as well as post‐hoc neutralisations or excuses for offending. Of these very different processes, the last one might be the most popular and problematic. Treatment programmes for offenders often aim to eliminate excuse‐making as a primary aim, and decision‐makers place great weight on the degree to which an offender “takes responsibility” for his or her offending. Yet, the relationship between these after‐the‐fact explanations and future crime is not at all clear. Indeed, the designation of post hoc excuses as criminogenic may itself be an example of fallacious thinking. After all, outside of the criminal context, post hoc excuse‐making is widely viewed as normal, healthy, and socially rewarded behaviour. We argue that the open exploration of contextual risk factors leading to offending can help in the identification of criminogenic factors as well as strengthen the therapeutic experience. Rather than insist that offenders take “responsibility” for the past, we suggest that efforts should focus on helping them take responsibility for the future, shifting the therapeutic focus from post hoc excuses to offence‐supportive attitudes and underlying cognitive schemas that are empirically linked to re‐offending.
Three-Point Bending of Rat Femur in the Mediolateral Direction: Introduction and Validation of a Novel Biomechanical Testing Protocol
Authors: Leppänen Olli , Sievänen Harri , Jokihaara Jarkko , Pajamäki Ilari , Järvinen Teppo LN
Published: July 2006

Mediolateral three-point bending of the rat midfemur was developed to enable the assessment of the mechanical competence of the elliptic bone cross-section in terms of its widest diameter, the apparent primary direction of bone adaptation to loading.

Introduction: Today, the most commonly used method to characterize the biomechanical properties of appendicular long bones is the three-point bending testing of the midfemur in the anteroposterior (AP) direction. However, as the diameter of the elliptic cross-section of femoral diaphysis is widest in the orthogonal mediolateral (ML) direction, the femoral diaphysis should also show the highest resistance to bending along this direction. The objective of this study was thus to introduce and validate a mechanical testing protocol for femoral midshaft along the ML direction.

Materials and Methods: To determine the repeatability of the novel testing protocol, 38 pairs of rat femora underwent a comprehensive structural analysis by pQCT followed by ML three-point bending. For comparison of the repeatability, corresponding tests were performed on the femoral neck. To validate the novel testing direction, the left hindlimb of 24 rats was neurectomized for 6 months, whereas the right limb served as an intact control. After excision, one half of these pairs of femora were randomly subjected to three-point bending test in the conventional AP direction and the remaining in the orthogonal ML direction.

Results: The precision (CVrms) of breaking load, stiffness, and energy absorption of the femoral midshaft in the ML direction was 3.8%, 6.6%, and 14.5%, respectively. The corresponding values for femoral neck compression test were 7.6%, 17.9%, and 18.7%, respectively. The loading-induced effect on the femoral midshaft (difference between the neurectomized [nonloaded] and contralateral intact [loaded] femur) was +2.2%, +1.9%, and +2.1% in the AP direction and −18.9%, −17.6%, and −20.3% in the ML direction (p < 0.01 for all comparisons), respectively.

Conclusions: Our results show that testing of rat femoral midshaft in the ML direction is a precise and biologically valid method to determine the structural strength of this widely used skeletal site in experimental bone research.
Differentiation-Inducing Factor-1 Alters Canonical Wnt Signaling and Suppresses Alkaline Phosphatase Expression in Osteoblast-Like Cell Lines
Authors: Matsuzaki Etsuko , Takahashi-Yanaga Fumi , Miwa Yoshikazu , Hirata Masato , Watanabe Yutaka , Sato Noriharu , Morimoto Sachio , Hirofuji Takao , Maeda Katsumasa , Sasaguri Toshiyuki
Published: July 2006

Because DIF-1 has been shown to affect Wnt/β-catenin signaling pathway, the effects of DIF-1 on osteoblast-like cell lines, SaOS-2 and MC3T3-E1, were examined. We found that DIF-1 inhibited this pathway, resulting in the suppression of ALP promoter activity through the TCF/LEF binding site.

Introduction: Differentiation-inducing factor-1 (DIF-1), a morphogen of Dictyostelium, inhibits cell proliferation and induces cell differentiation in several mammalian cells. Previous studies showed that DIF-1 activated glycogen synthase kinase-3β, suggesting that this chemical could affect the Wnt/β-catenin signaling pathway. This pathway has been shown to be involved in bone biology.

Materials and Methods: We studied the effects of DIF-1 on SaOS-2 and MC3T3-E1, osteosarcoma cell lines widely used as a model system for ostoblastic cells and murine osteoblast-like cell line, respectively. Reporter gene assays were also carried out to examine the effect of DIF-1 on the Wnt/β-catenin signaling pathway.

Results: DIF-1 inhibited SaOS-2 proliferation and reduced alkaline phosphatase (ALP) activity in a concentration- and a time-dependent manner. The expression of ALP was markedly suppressed by DIF-1-treatment in protein and mRNA levels. DIF-1 also suppressed the expression of other osteoblast differentiation markers, including core binding factor α1, type I collagen, and osteocalcin, in protein and mRNA levels and inhibited osteoblast-mediated mineralization. Subsequently, we examined the effect of DIF-1 on the Wnt/β-catenin signaling pathway. We found that DIF-1 suppressed the expression of β-catenin protein and the activity of the reporter gene containing T-cell factor/lymphoid enhancer-binding factor (TCF/LEF) consensus binding sites. We examined the effect of DIF-1 on a reporter gene driven by the human ALP promoter and found that DIF-1 significantly reduced the ALP reporter gene activity through the TCF/LEF binding site (−1023/−1017 bp). Furthermore, the effect of DIF-1 on MC3T3-E1, a murine osteoblast-like cell line, was examined, and it was found that DIF-1 suppressed ALP mRNA expression by the reduction of the ALP reporter gene activity through the TCF/LEF binding site.

Conclusions: Our data suggest that DIF-1 inhibits Wnt/β-catenin signaling, resulting in the suppression of ALP promoter activity. To our knowledge, this is the first report to analyze the role of the TCF/LEF binding site (−1023/−1017 bp) of the ALP gene promoter in osteoblast-like cell lines.