bluuebunny/crossref_metadata_2025 huggingface dataset:
From the Editor's desk
Authors: Tyrer Peter
Published: May 2004

There is a nice mix of international and local messages in this month's Journal. Nine contributions refer to the causes, features and treatment of depression, ranging from George Szmukler's (pp. 457–460) reminder of the importance of Brown and Harris' work on life events in depression, through studies showing that both prematurity and child sexual abuse may precipitate depression (Patton et al, pp. 446–447 and Spataro et al, pp. 416–421) and that alcohol use may lead to suicidal behaviour (McCloud et al, pp. 439–445), somatization as a depressive symptom (Okulate et al, pp. 422–427), and accounts of variation in depression and its associated burden both in the European Union and across the world (Marušiä, pp. 450–451; Crawford, pp. 379–380; üstün et al, pp. 386–392; and Chisholm et al, pp. 393–403). It is pleasing to report that none of these articles is weighed down by the undoubted burden of this highly prevalent condition; but although we now have clear ways of preventing and treating it, it is a matter of some concern that, hydra-like, it returns time and again in so many different forms. But although common factors are invariably present, local differences can tell us much, and Peet's (pp. 404–408) challenging thesis on diet as a cause of this variation in both depression and schizophrenia is bound to stimulate further enquiry, as indeed will the bothering evidence from Tolmac & Hodes (pp. 428–431) that adolescent psychotic disorder is more common in people from Black ethnic groups. The attraction of biological psychiatry is that local variation should not occur, and if Jensen et al (pp. 409–415) are correct that glycerophosphocholine levels are increased in the anterior cingulate gyrus in first-episode schizophrenia, this should be similar across the world. Or perhaps there might be variation, and that's when we go back to Peet's hypothesis.
Clinical Guidelines in Mental Health I: the National Collaborating Centre for Mental Health
Authors: Kendall Tim , Pilling Steve , Pettinari Catherine , Whittington Craig
Published: May 2004

The first national clinical guideline for the National Health Service (NHS) was produced by the National Collaborating Centre for Mental Health (NCCMH) for the National Institute for Clinical Excellence (NICE) and launched in December 2002. That the first guideline to emerge was a guideline in mental health was important. Furthermore, that the guideline was about the treatment of the most severe form of mental illness, schizophrenia, has drawn a great deal of attention to the plight of people with mental health problems, both within NICE, its Citizens Council and Partners Council, and in the medical press (Battacharya & Gough, 2002; Mayor, 2002; Hargreaves, 2003).
A national survey of psychiatric day hospitals
Authors: Briscoe Jane , McCabe Rosemarie , Priebe Stefan , Kallert Thomas
Published: May 2004

Aims and Method

We conducted a postal questionnaire survey of all psychiatric day hospitals in England to identify the range of aims, organisational structure and content of service provision.

Results

Of 102 identified day hospitals, 77% responded to the questionnaire. The findings confirmed that there is great heterogeneity in English day hospital service provision. The function or aim with the highest mean rating was ‘providing an alternative to in-patient care’, with 66% of day hospitals giving this a rating of great or greatest importance. However, the majority of respondents prioritised multiple roles, with many day hospitals aiming to provide acute and chronic care concurrently.

Clinical Implications

The label ‘day hospital’ covers a considerable range of community psychiatric services. The heterogeneity of service provision in existing day hospitals could lead to difficulties in generalising research findings on day hospital efficacy.
A dedicated nurse-led service for antipsychotic-induced weight gain
Authors: Ohlsen Ruth I. , Treasure Janet , Pilowsky Lyn S.
Published: May 2004

Aims and Method

To evaluate a psychosocial intervention for patients treated with antipsychotics with body mass index (BMI) > 25. A total of 44 patients (mean age (s.e.) 37.6 (1.2); 28 female, 16 male) received dietary and exercise advice with motivational interviewing. Weight and BMI were measured at baseline and monthly thereafter. Patients were offered weight monitoring for 1 year.

Results

Overall mean weight loss was 3.1 kg (mean 3.22%). Modal (range) weight change was 74.2 (719.2 kg to +8.7 kg).

Clinical Implications

Overall weight loss was not significant after 355.7 (32.5) (mean, s.e.) days. Determinants of response remain unclear. Avoiding weight gain in the first instance is critical. Further research will explore determinants of antipsychotic-induced weight gain and prevention strategies.
Providing a primary care service for psychiatric in-patients
Authors: Welthagen Enone , Talbot Sarah , Harrison Oliver , Phelan Michael
Published: May 2004

Aims and Method

A prospective descriptive study was set up to evaluate the feasibility, acceptability and activity of an innovative weekly primary care service for patients admitted for acute psychiatric care.

Results

During 10 months, 36 clinics were held and 123 appointments were attended. Presenting complaints included a wide range of acute and chronic conditions, affecting all body systems. As well as treating specific complaints, the doctor providing this service undertook considerable health promotion work and gave advice about patient management to junior psychiatrists.

Clinical Implications

It appears that there is considerable need for primary care expertise within an acute psychiatric unit, and that a weekly clinic is a feasible model of care.
Service innovations
Authors: Slowik Michael , Willson Susie Wynne , Loh Ezra Chun-Chong , Noronha Sandra
Published: May 2004

It is a stressful experience for parents and/or carers when their child is admitted to an in-patient unit because of severe mental illness.
Research activity of specialist registrars
Authors: Petrie Rachel , Anderson Kay , Hare Elizabeth , Mayfield Neil , Tipper Rebecca
Published: May 2004

Aims and Method

There has been much discussion about the productivity and training value of protected research sessions at specialist registrar (SpR) level. We used questionnaire survey to investigate the research experience of senior psychiatric SpRs and first-year psychiatric consultants in Scotland.

Results

The survey had an 80% response rate. Two-thirds of respondents were able to take protected research sessions, and a similar proportion had published research work during their higher training. Specific difficulties in conducting research are identified and discussed.

Clinical Implications

Scottish SpRs in psychiatry are usually able to protect research sessions, but experience difficulties with lack of experience, resources and supervision. Almost a third of those near the end of their training have published nothing. It is important to explore options other than research projects to gain relevant research experience.
A Seismic Retrofit Design Methodology for R/C Bridge Columns Using Fiber Composites
Authors: Tian Ying , Chaturvedi Shive K.
Published: May 2004

Fiber-reinforced polymers (FRP) are attractive materials for seismic upgrading. This paper proposes a design approach for retrofitting reinforced concrete bridge piers with fiber composites in which the nonlinear behavior of the retrofitted column is taken into account. The flexural and shear capacities are investigated and some intuitive conclusions are advanced and utilized in design at the component level. In a multiperformance-based design approach, the capacity spectrum method is utilized to identify the feasibility of using FRP as a retrofit scheme by solving a nonlinear programming problem and then determining the seismic demand. A design example is provided to illustrate the proposed retrofit design procedures.
Electronic Spectra of the Electrogenerated 1,4-Benzoquinone π-Dianion and the Strongly Hydrogen-Bonded Charge-Transfer Complex with Methanol
Authors: Okumura Noriko , Uno Bunji
Published: May 2004

Electronic spectra of the active π-electronic dianion of 1,4-benzoquinone and its hydrogen-bonded complex with CH3OH, generated at sequential electroreduction steps, have been discussed from the points of view of the observation techniques and n–σ charge-transfer interaction of the dianion with a weak hydrogen donor. An improved method involving rapid circulation of the electrolyzed solution via a photodiode array detector to avoid comproportionation and side reactions was used for successful measurements of the clear spectra resulting from the dianion generation. CNDO/S-CI calculations well reproduced the longest-wavelength band observed for the dianion, assigning to the benzenoid 1B3u←1Ag band under D2h symmetry. The hydrogen-bonding interaction of the 1,4-benzoquinone dianion with CH3OH allows the 1B3u←1Ag band to be blue-shifted. This behavior has been well explained in terms of the strong n–σ type charge-transfer interaction of the dianion with CH3OH. These results have been extensively discussed with regard to coupled electron and proton transfer reactions in the quinone–hydroquinone redox system.
Unusual Isotope Effects of Molybdenum in Chemical Exchange Reaction Using Dicyclohexano-18-Crown-6
Authors: Fujii Toshiyuki , Inagawa Jun , Nishizawa Kazushige
Published: May 2004

Molybdenum isotopes were fractionated in a liquid–liquid extraction system using dicyclohexano-18-crown-6 (DC18C6). The enrichment factors showed a breakdown of the conventional mass-dependent rule. Some unusual and larger isotope effects were observed in the even atomic mass isotopes, 92Mo and 94Mo. The unusual features in the present study were not responsible for the field shift effect, which was regarded as a primary factor of the anomalous isotope effect in the recent theory, but were due to an anomaly on the vibrational levels. The largest isotope effect was observed in the isotope pair of 94Mo–96Mo, it was ε96,94 = 0.0086 ± 0.0007, its initial aqueous phase was 0.91 M molybdenum chloride, and its organic phase was 0.2 M DC18C6 in chloroform: this was 0.0043 ± 0.0004 in terms of the enrichment factor for unit mass difference.
X-Ray Absorption Fine Structure (XAFS) Studies on Cobalt(II) Bromo Complexes in Acetic Acid Solutions
Authors: Akai Toshio , Okuda Masami , Nomura Masaharu
Published: May 2004

X-Ray absorption fine structure (XAFS) studies were performed for cobalt(II) bromo complexes prepared for the ratio Br/Co from 0.0 to 4.0 and for their oxidized complexes with ozone in acetic acid solvent. The multivariate curve resolution method indicates the existence of two kinds of chemical species both before and after the oxidation. Before oxidation, the two species are cobalt(II) acetate and tetrahedral cobalt(II) complex coordinated by Br. The oxidized sample with ozone consists of cobalt(II) acetate and trinuclear cobalt(III) complex; however, cobalt(III) complexes including Br are not detected. The rate of the change from the cobalt(II) complex coordinated by Br to the trinuclear cobalt(III) complex is lower than that from cobalt(II) acetate complex. This indicates that the tetrahedral cobalt(II) complex coordinated by Br is more difficult to be oxidized than the octahedral cobalt(II) acetate complex.
Mechanism and Simulation of Electrochemical Current Oscillations Observed in the H2O2-Reduction Reaction on Platinum Electrodes in Acidic Solutions
Authors: Mukouyama Yoshiharu , Hommura Hayato , Nakanishi Shuji , Nishimura Takashi , Konishi Hidemitsu , Nakato Yoshihiro
Published: May 2004

Mechanisms of electrochemical current oscillations of two types, named oscillation A and B, both observed for the H2O2-reduction reaction on Pt electrodes in acidic solutions, have been studied experimentally and by mathematical simulation. Oscillation A appears in a potential region just before hydrogen evolution, while oscillation B appears in a region of hydrogen evolution. A phase diagram we obtained has shown that oscillations A and B appear in limited ranges of the H+ and H2O2 concentrations and their ratio. The oscillation period for oscillation A increases with decreasing H2O2 concentration and negative shift of the electrode potential, mainly determined by the current density in the low-current state. Mathematical simulation by taking account of all plausible interfacial reactions (H2O2 reduction, hydrogen adsorption, and hydrogen evolution) reproduces the essential features of oscillation A, but does not reproduce oscillation B. It is shown that a positive feedback mechanism works in sudden transitions between the high- and low-current states for oscillation A.
Kinetic Study of Ligand Exchange Reactions of Bis(1,5-cyclooctadiene)nickel(0) with 2,2′-Bipyridine, 4,4′-Dimethyl-2,2′-bipyridine, and 4,4′,5,5′-Tetramethyl-2,2′-bipyridine
Authors: Abla Mahmut , Yamamoto Takakazu
Published: May 2004

Ligand exchange reactions of bis(1,5-cyclooctadiene)nickel(0), Ni(cod)2, with bpy, DMbpy, and TMbpy (bpy = 2,2′-bipyridine, DMbpy = 4,4′-dimethyl-2,2′-bipyridine, TMbpy = 4,4′,5,5′-tetramethyl-2,2′-bipyridine) in THF and DMF have been investigated kinetically. The reaction obeys the pseudo first-order kinetics, R = −d[Ni(cod)2]/dt = kobs[Ni(cod)2], with respect to the concentration of Ni(cod)2 in both the solutions. In THF, the kobs value linearly increases with [L] at a low concentration region of the exchanging ligand L; but it levels off at high concentrations of L and approaches a limiting value (e.g., about 1.0 × 10−4 s−1 at 25 °C). Addition of cod to the THF solution accelerates the exchange reaction. On the other hand, in DMF, the rate of the reaction (R) obeys the second-order rate law, R = k[Ni(cod)2][L], over a wide range of [L]. In DMF, the k value is independent of the concentration of cod added. Based on the kinetic results and NMR analysis, a reaction mechanism involving coordination of bpy, cod, or DMF to Ni(cod)2 to form a 20 e intermediate complex is proposed. DMbpy and TMbpy have a reactivity comparable to that of bpy in THF. In DMF, their reactivity increases in the order of bpy < DMbpy < TMbpy at 25 °C.
Aggregation, Complexation with Guest Molecules, and Mesomorphism of Amphiphilic Phthalocyanines Having Four- or Eight Tri(ethylene oxide) Chains
Authors: Kobayashi Nagao , Higashi Ryuji , Ishii Kazuyuki , Hatsusaka Kazuaki , Ohta Kazuchika
Published: May 2004

Zinc and metal-free amphiphilic phthalocyanines (pcs) substituted by four or eight tri(ethylene oxide) chains (3,6,9-trioxadecyloxy groups) {(H2(4EGpc), [Zn(4EGpc)], H2(8EGpc), and [Zn(8EGpc)] in Fig. 1)} have been prepared in order to study their aggregation in water, dioxane, and dioxane/water mixtures, their complexation phenomena with guest molecules in benzene, and mesomorphism in the neat state. In particular, tetra-substituted pcs have C4h symmetry and do not contain other positional isomers. [Zn(8EGpc)] forms aggregates in water and water–organic solvent mixtures; the extent of this was examined by electronic absorption and fluorescence spectroscopy. 1H NMR and fluorescence spectroscopy indicated that H2- and [Zn(8EGpc)] form inclusion complexes with quinones in benzene via hydrogen bonding. Benzoquinones with more hydroxy groups form complexes more effectively, plausibly laterally outside of the pc plane. From the higher field shift of the 1H singals of 2,2′-dihydroxy-1,1′-binaphthyl (BINAP) in the presence of [Zn(8EGpc)], BINAP molecules were suggested to lie above or below the pc plane. The mesomorphism of H2(8EGpc), [Zn(4EGpc)], and H2(4EGpc) was studied. In the case of H2(8EGpc), the discotic hexagonal ordered columnar (Dho) phase was seen in the range of from room temperature to 265 °C. However, liquid-crystalline phases were not observed for H2(4EGpc) and [Zn(4EGpc)].
Reductions of {RuNO}6-Type Nitrosyls. Characteristics of the Two-Electron Reduction Species Isolated as a Complex Having a Formally Negatively Charged μ-Nitrosyl ({RuNO}8–{RuNO}8) and the One-Electron Reduction Species Generated Electrochemically ({RuNO}7)
Authors: Nagao Hirotaka , Nagao Noriharu , Yukawa Yasuhiko , Ooyama Dai , Sato Yoshinobu , Oosawa Tohru , Kuroda Hiroshi , Howell Frank Scott , Mukaida Masao
Published: May 2004

The reaction between cis-[Ru(NO)(H2O)(bpy)2]3+ ({RuNO}6) and formic acid gives [{Ru(μ-NO)}2(bpy)4]2+ (2) ({RuNO}8–{RuNO}8), along with some other products species: cis-[Ru(NO)(OCHO)(bpy)2]2+ (1)({RuNO}6), and cis-[Ru(OCHO)(H2O)(bpy)2]+. The μ-nitrosyl complex (2) consists of two cis-Ru(bpy)2fragments connected by two formally negatively charged bridging nitrosyl ligands. Electrochemical study of the complex shows that two successive one-electron oxidation waves to give [{Ru(μ-NO)}2(bpy)4]4+({RuNO}7–{RuNO}7) are found. The generated two-electron oxidation species is disintegrated to afford a one-electron reduction species, cis-[Ru(NO·)(CH3CN)(bpy)2]2+ ({RuNO}7), along with a small amount of an unexpected nitro species, cis-[Ru(NO2)(CH3CN)(bpy)2]+. The characteristics of electrochemically generated one-electron reduction species cis-[Ru(NO·)X(bpy)2](n−1)+ ({RuNO}7) (X = H2O, OCHO) are investigated in the connection. During the degradation process of the one-electron reduction species, a nitrosyl-to-nitro conversion was found to proceed in cis-[Ru(NO·)(H2O)(bpy)2]2+, via the formation of cis-[Ru(NO·) (CH3CN)(bpy)2]2+ mentioned above; this is the first observation which explains the electrochemically-induced nitrosyl-to-nitro conversion observed in the reduction process of {RuNO}6-type complexes.
Substituent Effects on Fluorescent Properties of Imidazo[1,2-a]pyridine-Based Compounds
Authors: Tomoda Haruhiko , Hirano Takafumi , Saito Shojiro , Mutai Toshiki , Araki Koji
Published: May 2004

In order to search for novel fluorescent organic compounds, 20 derivatives of imidazo[1,2-a]pyridine (1) were synthesized, and their fluorescent properties were studied. Though the parent compound 1 (λfl = 370.5 nm, Φ = 0.57 in ethanol) was in the liquid state at ambient temperature, 2-phenylimidazo[1,2-a]pyridine (5), 2-(2-naphthyl)imidazo[1,2-a]pyridine (16), 7-methylimidazo[1,2-a]pyridine (3), 7-methyl-2-phenylimidazo[1,2-a]pyridine (12), and 7-methyl-2-(2-naphthyl)imidazo[1,2-a]pyridine (17) were found to give thermally stable solid compounds (mp 55—190 °C) without much affecting the fluorescent properties of the parent compound (λfl = 374—381 nm, Φ = 0.50—0.78 in ethanol). Among the 4′-substituted 2-phenyl derivatives, it was found that the introduction of the strong electron-donating amino and dimethylamino groups (2-(4-aminophenyl)imidazo[1,2-a]pyridine (7) and 2-[4-(dimethylamino)phenyl]imidazo[1,2-a]pyridine (8), respectively) caused marked red shift of their fluorescence (λfl = 445 and 446 nm, respectively, in ethanol), thus providing the way for tuning the fluorescence color of the IP derivatives. The observed red shift of the fluorescence of 7 and 8 was ascribed to the contribution of the excited intramolecular charge transfer state.
A 12-Porphyrin System: Syntheses of Peptide Porphyrins with Multiple Histidines and the Aggregation Behavior in the Presence of Hemin
Authors: Ushiyama Masato , Yoshino Atsushi , Yamamura Takeshi , Shida Yasuo , Arisaka Fumio
Published: May 2004

We succeeded in combining multiple-histidine peptides with porphyrins; that is to say, we synthesized three peptide porphyrins consisting of α4-meso-tetrakis(o-aminophenyl)porphyrin, α4-H2TAPP, and amphiphilic peptide, α4-(PepA18)n(AG)4−n-H2TAPP (n = 1, 3, and 4; PepA18 = EEALEKHEKALEKHEKAG), in the liquid phase. These compounds were designed to construct multiple porphyrin systems; in other words, each peptide attached on the H2TAPP was designed to contain two histidines. The stability of the porphyrins, (AG)4-H2TAPP and (AG)1(Boc-AG)3-H2TAPP, as well as the coupling conditions between the porphyrin fragments and the 16-residue peptide, EEALEKHEKALEKHEK, to give α4-(PepA18)n(AG)4−n-H2TAPP (n = 1, 3, and 4) were studied in detail with respect to the temperature, solvents, coupling reagents, additives, and amines. This search revealed that the combination of DMF/benzotriazol-1-yl-oxy-tris(pyrrolidino)phosphonium hexafluorophosphate (PyBOP)/N,N-diisopropylethylamine is suitable for the purpose. The search also clarified that it is possible to synthesize α4-(PepA18)4-H2TAPP and α4-(PepA18)3(AG)1-H2TAPP selectively by choosing the coupling additives 1-hydroxy-7-azabenzotriazole (HOAt) and 1-hydroxybenzotriazole (HOBt), respectively.

All of the compounds showed 40% helicity in a solution (phospate buffer, pH = 7.0) containing 2,2,2-trifluoroethanol (TFE). The UV-vis and circular-dichroism spectrophotometric titrations of Fe(III) protoporphyrin IX chloride, B, with α4-(PepA18)4-ZnTAPP, A, indicated that up to three equivalents of B were incorporated into A in a buffer solution containing 15% TFE. Sedimentation-equilibrium ultracentrifugation experiments showed that A is a dimer in the solution, and that this dimer is transformed to a trimer when B is incorporated into A. These results suggest that A achieves a 12-porphyrin system consisting of different kinds of metalloporphyrin.
Crystal Structures of Unsolvated Lithiosilanes with Si–Si Bonds
Authors: Nanjo Masato , Sekiguchi Akira , Sakurai Hideki
Published: May 2004

The molecular structures of lithiopentamethyldisilane ([LiSiMe2SiMe3]4, 1a), 2-lithio-1,1,2,3,3-pentamethyl-1,3-diphenyltrisilane ([LiSi(SiMe2Ph)2Me]2, 1b), and 2-lithio-1,1,1,3,3,3-hexamethyl-2-phenyltrisilane ([LiSi(SiMe3)2Ph]2, 1c) have been determined by X-ray diffraction. The silyllithium 1a is a tetramer in the solid state with intramolecular Li···CH3 agostic interactions. The silyllithiums 1b and 1c are dimers with intramolecular lithium-phenyl interactions. The latter adopts a molecular structure with not only an intramolecular Li–Ph interaction, but also an intermolecular Li···CH3 agostic interaction. The structures of these organometallic derivatives show novel features not observed in solvent-coordinated lithiosilanes. These features provide valuable insights into structures that differ markedly from those of lithiosilanes containing coordinated donor solvent molecules.
Guest-Exchange and Guest-Release via Gas–Solid Contact in Clathrate Crystals Based on 2,5-Bis(9-hydroxyfluoren-9-yl)thieno[3,2-b]thiophene as a Host Compound
Authors: Kuruma Koji , Nakagawa Hiro-o , Imakubo Tatsuro , Kobayashi Keiji
Published: May 2004

The host compound 2,5-bis(9-hydroxyfluoren-9-yl)thieno[3,2-b]thiophene (1) afforded clathrate crystals represented by the formula (1)(guest)2 for the guests EtOH, n-PrOH, and i-PrOH. Their X-ray crystal analyses revealed that the host frameworks are isostructural. The guest molecules, which are embedded in a channel-type of host void, were exchanged with other guest species by vapor contact. Upon exposure of these crystals to methanol vapor, guest elimination was induced to give the guest-free host 1 crystal [β-form, P1-, a = 13.111(4), b = 13.724(3), c = 9.766(3) Å, α = 97.11(2), β = 98.64(3), γ = 64.56(2)°, V = 1565.3(8) Å3]. The crystal thus obtained is a polymorphic form of the guest-free 1 crystal which is obtained by recrystallization from dichloromethane [α-form, P21/n, a = 17.403(3), b = 20.654(4), c = 8.695(1) Å, β = 99.73(1)°, V = 3080.4(9) Å3]. Once the guest molecules have been lost, gas-sorptive enclathration was not accomplished for either of these polymorphic host crystals; host 1 does not act as an apohost.
Catalytic Performance of Tantalum–η2-Alkyne Complexes [TaCl3(R1C≡CR2)L2] for Alkyne Cyclotrimerization
Authors: Oshiki Toshiyuki , Nomoto Hiroshi , Tanaka Kouji , Takai Kazuhiko
Published: May 2004

Structurally characterized tantalum–η2-alkyne complexes [TaCl3(η2-EtC≡CEt)L2] (1, L2 = 1,2-dimethoxyethane (DME); 2, L = py) acted as catalysts for the cyclotrimerization of terminal alkynes. The catalytic reaction proceeded at 25 °C within few hours and the trisubstituted benzenes were obtained without the formation of linear oligomers. A new tantalum complex having a terminal alkyne ligand, [TaCl3(η2-Me3SiC≡CH)(dme)] (3), was prepared, and its catalytic performance was also investigated.
Both Enantiomers of N-Boc-indoline-2-carboxylic Esters
Authors: Kurokawa Masayuki , Sugai Takeshi
Published: May 2004

An immobilized form of Candida antarctica lipase (Chirazyme L-2) catalyzed enantioselective hydrolysis (E > 1000) of N-Boc-indoline-2-carboxylic acid methyl ester. The reaction proceeded efficiently at 60 °C, a temperature over the melting point of substrate, in the conversion of 49.9% to provide the hydrolyzed product, (S)-carboxylic acid with >99.9% ee and the unreacted (R)-ester with 99.6% ee. A newly developed expeditious route to the racemic substrate (a total of six steps, 60% yield), starting from aniline and ethyl α-methylacetoacetate, established the scalable chemo-enzymatic synthesis of the desired compounds in both enantiomerically pure forms.
Ethyl Acetate as a Pro-Reducing Agent in an One-Pot Reductive Deamination of Nitroanilines
Authors: Bacherikov Valeriy A , Wang May-Jane , Cheng Shu-Yun , Chen Ching-Huang , Chen Kuo-Tung , Su Tsann-Long
Published: May 2004

The one-pot reductive deamination of mono or dinitro substituted anilines to the corresponding nitrobenzenes by using ethyl acetate or ethanol was compared. It revealed that ethyl acetate is more suitable for the reductive deamination of mononitroanilines, while ethanol is more appropriate for dinitroanilines.
Evidence of the Hypsithermal Verified Using the Racemization Rate Constant of Amino Acids: An Estimation of Paleo-Ground Temperatures
Authors: Takano Yoshinori , Kudo Junya , Kaneko Takeo , Kobayashi Kensei , Ishikawa Yoji , Marumo Katsumi
Published: May 2004

The kinetics of a racemization reaction for aspartic acid in boreal terrestrial sediment core samples was investigated in detail to determine the rate constant (kASP) and the difference of the paleo-ground temperatures. The Arrhenius plot between the rate constant (kASP) and the literature data of corresponding temperatures is defined as

Log kASP = 16.1 − 5820/T

where T is the absolute temperature (K). From the beginning of the Holocene, estimated annual ground temperatures increased to reach the warmest period, after which a slight decrease was observed. The present findings are geologically consistent with the global transgression period called “the Hypsithermal”.
The Synthesis of (±)-Monomorine I Starting with the Palladium-Catalyzed Carbonylative 1,4-Acylation of an Organozinc Chloride
Authors: Yuguchi Motoki , Tokuda Masao , Orito Kazuhiko
Published: May 2004

The synthesis of the indolizidine alkaloid (±)-monomorine I has successfully been achieved by a new route starting with a one-pot four-component connecting reaction based on a palladium-catalyzed carbonylative 1,4-addition of an organozinc halide to a α,β-enone in an atmosphere of carbon monoxide.
Reduction of Light-Decomposition and Enhancement of Photocatalysis of Photocatalyst by Au-Coat
Authors: Nemoto Yoshihiro , Hirai Takayuki
Published: May 2004

A photocatalyst can be used for various applications. Such materials are semiconductors which are stable to photoirradiation, for example, TiO2. Most of these materials require UV light. There are many kinds of semiconductors which are unstable to photoirradiation, but which have a visible light response. In this study, it is shown that a thin Au film or Au nano particles on the surface of the photocatalyst reduced the photodecomposition of the photocatalyst. Although the surfaces of the samples were completely covered by Au, photocatalytic activity was observed in all the Au-coated samples. The Au-coating on the surface enhances the photocatalysis of a coated photocatalyst.
The Radiation-Induced Coloration of Amorphous Photochromic Dithienylethene Films
Authors: Irie Setsuko , Kim Myeong-Suk , Kawai Tsuyoshi , Irie Masahiro
Published: May 2004

The radiation-induced coloration of bulk amorphous films of five photochromic diarylethenes was studied with the aim of developing reusable, sensitive color dosimeters. The films contain an extremely high concentration of diarylethenes. The most intense coloration was observed for the film containing 1,2-bis(2,4-dimethyl-3-thienyl)perfluorocyclopentene having 3-phenyl-4-diphenylyl substituents. The color disappeared upon irradiation with visible light. The coloration increased linearly with an increase in the absorbed dose up to 3000 Gy. The relative sensitivity of radiation-induced coloration among the five derivatives qualitatively agreed with the sensitivity of photo-induced coloration from UV light (254 nm) irradiation.
Evolution of Synthetic Strategies for Highly Functionalized Natural Products: A Successful Route to Bryostatin 3
Authors: Ohmori Ken
Published: May 2004

A convergent asymmetric synthesis of the antineoplastic marine macrolide, bryostatin 3 (1), has been achieved. This synthesis relied upon stereo-controlled construction of two major fragments, the top-half fragment 2 and the bottom half fragment 3, and their coupling by the Julia–Lythgoe olefination and Yamaguchi macrolactonization. The top-half fragment 2 could successfully be synthesized by tandem connection of the three key fragments. The bottom-half fragment 3 was prepared by the union of vinyl iodide 39 and α-alkoxy aldehyde 30.
Cause for Unusually Large Thermal Hysteresis of Spin Crossover in [Fe(2-pic)3]Cl2·H2O
Authors: Nakamoto Tadahiro , Bhattacharjee Ashis , Sorai Michio
Published: May 2004

Thermodynamic properties of an iron(II) spin crossover complex [Fe(2-pic)3]Cl2·H2O (2-pic: 2-picolylamine or 2-aminomethylpyridine), for which an unusually large thermal hysteresis with a width of [Tc(↑) − Tc(↓) = 91 K] in its spin-state transition has been observed by 57Fe Mössbauer spectroscopy, were investigated by adiabatic heat capacity calorimetry. Contrary to the previous observation, the preliminary DTA result showed much smaller thermal hysteresis around 200 K, with a width of [Tc(↑) − Tc(↓) = 12 K]. The present heat capacity measurement by adiabatic calorimetry revealed that there exists a metastable low-spin low-temperature phase, besides the stable low-spin low-temperature phase and that this complex undergoes stabilization from the metastable low-spin phase to the stable low-spin phase accompanied by a large heat evolution when the sample is annealed around 200 K. The stable low-spin phase exhibited a phase transition to the high-spin high-temperature phase around 280 K upon heating. The high-spin state was found to be always undercooled down to ∼200 K. The large thermal hysteresis earlier reported for the title complex turns out to be apparent and is caused by the existence of the metastable low-spin phase. Moreover, another intermediate metastable (low-spin?) phase was found when the sample in the metastable low-spin phase was heated from 150 K at a heating rate of ∼5 K h−1. This metastable phase exhibited a phase transition to the undercooled high-spin phase at ∼265 K.
Single-Crystalline Photochromism of a Diarylethene Dimer
Authors: Kobatake Seiya , Kuma Shunpei , Irie Masahiro
Published: May 2004

A fluorene derivative having two diarylethene units at the 9,9′-positions was synthesized, and the photochromic behavior was examined in a single-crystalline phase as well as in solution. Upon irradiation with ultraviolet light (λ = 313 nm), a hexane solution of the diarylethene dimer (1a) turned blue. The blue solution was found to contain the one closed-ring form dimer (1b) and the two closed-ring form dimer (1c). Both 1b and 1c returned to 1a upon irradiation with visible light (λ > 500 nm). The photocyclization quantum yields of 1a to 1b and 1b to 1c were determined to be 0.46 and 0.29, respectively. The photocycloreversion quantum yields of 1c to 1b and 1b to 1a were 5.8 × 10−3. The single crystal of the dimer exhibited photochromism. The diarylethene chromophores were aligned almost perpendicular to each other in the crystal, and one of the units in the dimer could be selectively isomerized by irradiation with linearly polarized light.
Spectroscopic Observation of the Dimerization Reactions of the 9-Phenylcarbazole Cation Radical in Acetonitrile
Authors: Oyama Munetaka , Matsui Jun
Published: May 2004

The dimerization reaction processes of the 9-phenylcarbazole cation radical (PCZ•+) in acetonitrile (AN) were observed using an electron-transfer stopped-flow method. Although the lifetime of PCZ•+ in AN is less than a few hundred milliseconds, the dynamic transformation of the absorption spectra of PCZ•+ was successfully observed in AN for the first time with the proposed method. By observing the changes in the absorption spectra in the visible region, the decrease in PCZ•+ and the concurrent increase in the dimer cation radical were observed with isosbestic points. In addition, in the presence of neutral PCZ, the acceleration of the dimerization of PCZ•+ was clearly confirmed. Consequently, in the presence of PCZ, the rate law was determined to be −d[PCZ•+]/dt = 3Kk′[PCZ•+]2[PCZ], where 3Kk′ is 1.4 × 109 M−2 s−1. This means that the reaction mechanism involves a two-step interaction with the catalytic effect of neutral PCZ. Although the difference in the reactivity had already been known between PCZ•+ and the triphenylamine cation radical, the reaction mechanism has been clarified to be different in both cases.
A Reaction Network for Triglycine Synthesis under Hydrothermal Conditions
Authors: Mitsuzawa Shigenobu , Yukawa Tetsuyuki
Published: May 2004

It has been hypothesized that chemical evolution leading to the origin of life might have occurred in hydrothermal environments on primitive Earth. To examine this hypothesis, we investigated how the polymerization of amino acids proceeds under high-temperature and high-pressure conditions. We investigated a reaction network consisting of glycine and oligoglycines up to trimer, and the condensation/hydrolysis reactions among these molecules. We determined the rate constants of these reactions in experiments employing a flow reactor at 200 °C and 25 MPa. We found that two condensation reactions of glycine, which yield diglycine and diketopiperazine as products, have larger equilibrium constants under these conditions than at 25 °C. This result supports the hypothesis that hydrothermal conditions are thermodynamically favorable for chemical evolution. We also found that triglycine formation is mediated by diketopiperazine at 200 °C and 25 MPa. This implies that diketopiperazine acts as an important intermediate in the polymerization process of amino acids, which might have occurred in hydrothermal environments on primitive Earth.
Crystal Structure and Ionic Conduction Mechanism of AgHgSX (X = Br, I)
Authors: Moro’oka Masakazu , Ohki Hiroshi , Yamada Koji , Okuda Tsutomu
Published: May 2004

New Ag+ ionic conductors AgHgSX (X = Br, I) were synthesized by solid-state reactions of AgX (X = Br, I) and HgS. AgHgSI shows a phase transition at 578 K. The crystal structure of the high temperature phase has been determined to be P212121 (No. 19) by the Rietveld refinement using the powder X-ray diffraction pattern. The electric conductivity at 500 K measured by the AC impedance method was 2.6 × 10−4 S cm−1 for the high temperature phase of AgHgSI, 1.2 × 10−4 S cm−1 for the low temperature phase of AgHgSI, and 1.1 × 10−4 S cm−1 for AgHgSBr. The charge density analysis of the AgHgSX (X = Br, I) clearly showed the Ag+ ionic conduction path when analyzed by the Maximum Entropy Method (MEM) combined with Rietveld analysis.
Preparations of Low-Spin Tetra Cyano Iron Complexes of N-Benzyl-1,2-ethanediamine and Its Oxidative Dehydrogenation: Isolation of the Intermediate with Monoimine Ligand
Authors: Goto Masafumi , Ohse Yasuhiko , Koga Sayuri , Kudo Yuka , Kukihara Rinko , Kurosaki Hiromasa
Published: May 2004

The oxidation of tetracyano(N-benzyl-1,2-ethanediamine) with one equivalent oxidant, hydrogen peroxide or peroxodisulfate, under neutral or basic conditions yielded tetracyano(2-benzylimino-ethylamine)ferrate(II), owing to an acceleration of disproportionation by the presence of N-benzyl substituents. Further oxidation yielded the corresponding conjugated 1,2-diimineferrate(II) complex.
Synthesis and Properties of New, Spatially Relaxed Dendrons Containing Internal Carboxyl Groups
Authors: Kikuzawa Yoshihiro , Nagata Toshi
Published: May 2004

We synthesized a series of new dendrons with up to fourteen internal carboxyl groups. These dendrons are made from a branching unit and a spacer unit with a carboxyl group. The growth reactions (formation of the benzylic ether bonds) are completed within a few hours, which suggests high reactivity at the “focal” point of the dendritic framework. The final deprotection of the internal ester groups also proceeded smoothly. These high reactivities were attributed to the presence of spacer units, which caused spatially relaxed conformations of these molecules. The carboxylate salt form of the dendron produced both normal and reverse micelles in a THF/water mixed solvent according to the fraction.
O-Glycosidation of Telluroglycoside by Electrochemical Oxidation
Authors: Yamago Shigeru , Kokubo Koji , Yoshida Jun-ichi
Published: May 2004

The electrochemical oxidation of telluroglycosides in the presence of primary or secondary alcohols results the O-glycosidation with high efficiency. Difference of the oxidation potential is nicely accounted for that of the reactivity of armed- and disarmed-telluroglycosides.
Detection of Potential Molecular Recognition Ability in Linear Poly(methyl acylate)
Authors: Ihara Hirotaka , Tanaka Hideaki , Shibata Masaaki , Sakaki Shigeyoshi , Hirayama Chuichi
Published: May 2004

Linear poly(methyl acrylate) was immobilized onto silica gels at the one side of the terminal group. The silica-supported polymer showed good selective retention for polycyclic compounds and seems to recognize the π-electron and molecular shape. Comparison with long-chain alkyl acylate polymer is also described.
Preferential Association of 7-Azaindole Dimer in Acetonitrile Studied by Mass Spectrometry
Authors: Arai Tatsuo , Koyama Tetsuo , Wakisaka Akihiro
Published: May 2004

The preferential association of 7-azaindole (Az) dimer was observed by the mass spectrometric analysis of clusters isolated from liquid droplets containing Az and acetonitrile. In the mass spectrum, the peaks corresponding to the even-numbered Az clusters, (Az)2,4,6,8···, were observed much more prominently than those neighboring odd-numbered Az clusters, (Az)3,5,7,9···.
Alternately Assembled Ultrathin Film of Silica Nanoparticles and Linear Polycations
Authors: Ariga Katsuhiko , Lvov Yuri , Onda Mitsuhiko , Ichinose Izumi , Kunitake Toyoki
Published: May 2004

Anionic silica nanoparticles were assembled with linear polycation by alternate adsorption technique. Regular growth and surface smoothness of the films were confirmed by QCM and SEM, respectively.
Synthesis and Characterization of Porphyrin-Dimanganese Composite Molecules
Authors: Nagata Toshi
Published: May 2004

The first porphyrin-dimanganese composite molecules were synthesized. Fluorescense of the porphyrin moiety was effectively quenched by the dimanganese moiety. The oxidation potentials of porphyrins showed no significant change, whereas the oxidation potentials of dimanganese moiety showed about +0.1 V shift from the porphyrin-free reference compound.
Enantioselective Allylation of Aldehydes Using Tartrate Ester Modified Allylsilanes
Authors: Zhang Luo Cheng , Sakurai Hideki , Kira Mitsuo
Published: May 2004

Tartrate-ester modified allylsilanes, 2-allyl-1,3,2-dioxasilolane-4,5-dicarboxylic esters, (1), were found to serve as useful reagents for regiospecific and stereoselecive allylation of aldehydes. Reactions of 1 with achiral aldehydes without any catalyst gave the corresponding homoallyl alcohols in good yields (70-90%) with the ee values up to 80%.
Reductive Electrochemical Decomposition of Chloroform on Metal Electrodes
Authors: Sonoyama Noriyuki , Hara Kohjiro , Sakata Tadayoshi
Published: May 2004

The electrochemical reductive decomposition of chloroform was carried out using 15 kinds of metal electrodes. The efficiency of the decomposition and the main product of reaction largely depended on the metal electrodes. The hydrogenation of chloroform by Ag, Zn, Pd and Cu electrodes proceeded in about 100% efficiency. These electrodes produced methane mainly. Pb electrode produced dichloromethane selectively.
Modification on Ni-P Amorphous Catalyst with SiO2 and Pd
Authors: Li Hexing , Dai Weilin , Shen Chun , Zhou Shiyao , Deng Jingfa
Published: May 2004

Ni-P amorphous alloy is prepared by chemical reduction with hypophosphite and modified by introducing trace Pd to the alloy and depositing it on SiO2, which results in the great improvement on both the thermal stability and hydrogenation activity. The stabilizing effect of SiO2 and activating effect of Pd have been observed and discussed.
Liquid Crystalline Oligosilanes with Alkoxybiphenyl Groups
Authors: Yatabe Tetsuo , Sasanuma Yuji , Kaito Akira , Tanabe Yoshikazu
Published: May 2004

Oligosilane derivatives, ROC12H8(SiMe2)nC12H8OR, were synthesized by treatment of α,ω-dichloropermethyloligosilanes with Grignard reagents derived from 4-alkoxy-4′-bromobiphenyls. Oligosilanes with n = 6; R = C8H17 and n = 6; R = C10H21 showed smectic B and E phases, respectively.
Intermolecular π-π Interaction of Poly(4,4′-dialkyl-2,2′-bithiazole-5,5′-diyl)s and Photoluminescence of the Polymers
Authors: Yamamoto Takakazu , Maruyama Tsukasa , Suganuma Hajime , Arai Minoru , Komarudin Dharma , Sasaki Shintaro
Published: May 2004

UV-vis. adsorption spectra of films of regioregular poly(4,4′-dialkyl-2,2′-bithiazole-5,5′-diyl)s PRBTz’s show bathochromic shifts from those of PRBTz’s in solutions and their corresponding regio-irregular polymers. This bathchromic shift is considered to originate from stacking of the polymer, and powder X-ray diffraction and photoluminescence data support this view.
Electric Field-Induced Surface Morphology in a Copolymer of Vinylidene Cyanide and Vinyl Acetate
Authors: Seto Takatoshi , Nozoye Hisakazu
Published: May 2004

We investigated the surface morphology of the film of a copolymer of vinylidene cyanide and vinyl acetate, using atomic force microscopy. It was found that when a high electric field is imposed to the film near its glass transition temperature, a thin fiber–like assembly about 10 nm thick appears on the surface. The surface structure was discussed relating to the relatively high piezoelectricity in this amorphous–type polymer.
Recoverable Chiral Sulfoxide: Asymmetric Diels–Alder Reaction Using Optically Active 1-(2-p-Tolylsulfinyl)pyrrolyl α,β-Unsaturated Ketones as a Dienophile
Authors: Arai Yoshitsugu , Masuda Tsutomu , Masaki Yukio
Published: May 2004

The Diels–Alder reaction of chiral cinnamoyl- and crotonyl(2-p-tolylsulfinyl)pyrrole with cyclopentadiene in the presence of AlCl3 or Yb(OTf)3 proceeded smoothly to give the corresponding endo adducts in excellent yield with high diastereoselectivity, ranging from 92 to 99% d.e. The chiral auxiliary, 2-pyrrolesulfoxide was efficiently recovered after alcoholysis of the adduct without loss of optical purity.
Synthesis and Reactivity of S-Sulfiliminothiazynes
Authors: Ohkubo Masanori , Fujii Takayoshi , Ono Shin , Morita Hiroyuki , Yoshimura Toshiaki , Horn Ernst , Sato Soichi
Published: May 2004

Reaction of S,S-diphenyl-S-fluorothiazyne with N-unsubstituted S,S-diphenylsulfilimine afforded the corresponding S-sulfiliminothiazyne. Measurement of the pKa value of S-sulfiliminothiazyne and its reactivity were examined. The molecular structure of the sulfonediiminosulfonium salt was determined by the X-ray crystallographic analysis.
Photocatalyzed Degradation of Metal-EDTA Complexes in TiO2 Aqueous Suspensions and Simultaneous Metal Removal
Authors: Kagaya Shigehiro , Bitoh Yoshiro , Hasegawa Kiyoshi
Published: May 2004

Cu(II)-, Fe(III)-, and Zn(II)-EDTA complexes are degraded rapidly in aerated aqueous suspensions of TiO2 with a high-pressure mercury lamp (irradiation wavelength > ca.290 nm), accompanying a full removal of the metals. Total organic carbons (TOCs) in their solutions decrease with the irradiation time, however, TOCs remained after 5 h irradiation. Although Co(II)- and Ni(II)-EDTA complexes are degraded, the removal of their metals is slow. Mn(II)-EDTA complex is degraded incompletely even after 5 h irradiation.
Two Distinct Solvated Structures of p-Nitroaniline in Acetonitrile
Authors: Mohanalingam Kathaperumal , Hamaguchi Hiro-o
Published: May 2004

The presence of two distinct forms of p-nitroaniline (pNA) associated with solvent acetonitrile (AN) molecules is shown by using an SVD (Singular Value Decomposition) analysis of the UV-VIS spectra of pNA in AN/CCl4 mixed solvents. All the three species (including the unassociated form in pure CCl4) observed have varying degrees of intramolecular charge transfer due to the association.
Alcoholysis of Benzotrichloride Studied by Liquid Beam - Multiphoton Ionization Technique
Authors: Horimoto Noriko , Mafuné Fumitaka , Kondow Tamotsu
Published: May 2004

Chemical reactions of benzotrichloride in an alcohol solution initiated by multiphoton ionization were observed by irradiation of a tightly focused laser beam at wavelength of 274 nm. The product ions ejected from the liquid surface were analyzed by a time-of-flight mass spectrometer. The mass spectra of the ions indicate that alcoholysis occurs between PhCCl2+ produced by multiphoton ionization and alcohol molecules, ROH, giving PhCCl(OR)+ and PhC(OR)2+.
Specific Adsorption of Metal Complexes of Tetraphenylporphyrin at Dodecane-Water Interface
Authors: Nagatani Hirohisa , Watarai Hitoshi
Published: May 2004

Interfacial adsorption of the metal complexes of tetraphenylporphyrin (TTP) was found out in the dodecane-water system by a high-speed stirring method. Among metalloporphyrins of five metals examined, ZnTPP and VOTPP showed appreciable adsorptivity at dodecane-water interface and adsorption constants were determined by applying Langmuir isotherm. The interfacial adsorptivity of complexes decreased in the order, ZnTPP > VOTPP > CoTPP, NiTPP, CuTPP.
Generation of α-Alkylthio Radicals by Photoinduced One-Electron Oxidation of α-Stannyl Sulfides and Their Use for Carbon-Carbon Bond Formation
Authors: Ikeno Taketo , Harada Manabu , Arai Noriyoshi , Narasaka Koichi
Published: May 2004

Cation radicals, generated from α-stannyl sulfides by the photoinduced single electron transfer, cleave into α-alkylthio radical intermediates with the elimination of the stannyl group. The α-alkylthio radicals thus formed are utilized for carbon-carbon bond forming reactions.
High Conversion Efficiency Photovoltaic Cell Enhanced by Lanthanide Complex Phosphor Film Coating
Authors: Jin Tetsuro , Inoue Satoshi , Tsutsumi Shuji , Machida Ken-ichi , Adachi Gin-ya
Published: May 2004

Maximal outputs of amorphous silicon (a-Si) photovoltaic cells (PVC) coated by the organically modified silicate (ORMOSIL) composite film containing a terbium bipyridine complex were increased to be 8 % higher than those of the uncoated a-Si PVC, owing to the effective optical modulation from UV to visible light by the lanthanide complex incorporated into the ORMOSIL matrix.
Solvent Effect and Molecular Orbital Study on the Specific Rotation of a Methacrylamide Having l-Leucine Structure in the Side Chain
Authors: Sanda Fumio , Nakamura Masafumi , Endo Takeshi
Published: May 2004

Solvent effect and molecular orbital studies on the specific rotation of a methacrylamide (MA-(L)-L-M) having l-leucine structure in the side chain were carried out. The larger the relative dielectric constant of the solvent, the more stable the conformation of MA-(L)-L-M showing larger polarity was. This conformation change depending on the solvent might be the reason for the solvent effect on the specific rotation of MA-(L)-L-M.
Formation of Conjugated Double Bonds in Poly(vinyl alcohol) Film under Irradiation with γ-Rays at Elevated Temperature
Authors: Zhao Wenwei , Yamamoto Yukio , Seki Shu , Tagawa Seiichi
Published: May 2004

Irradiation with γ-rays promotes the formation of conjugated double bonds in a poly(vinyl alcohol) film at an elevated temperature. The unsaturation structures resulted by γ-irradiation were assigned to be mainly polyenones -(CH=CH)n-CO-, whereas thermal activation produces mainly polyenes, -(CH=CH)n-.