bluuebunny/crossref_metadata_2025 huggingface dataset:
Attitudes and emotions of trainees in learning disability psychiatry
Authors: Graham Simon , Herbert Rosemary , Price Sarah , Williams Shan
Published: July 2004

Aims and Method

We aimed to formally examine the attitudes and emotions engendered in a group of senior house officers (SHOs) working in learning disability, by means of focus groups held both during and immediately after placement. Three hour-long focus group sessions, facilitated by a consultant psychotherapist, were recorded on audio- and video-tape. Transcripts of the audiotapes were examined in order to identify themes and categorise them in terms of attitudes, behaviours and emotions.

Results

Many of the thoughts, feelings and behaviours identified showed negative themes originating from the trainees, particularly towards themselves and patients. The trainees only twice perceived themselves to be the recipients of any positive themes.

Clinical Implications

Addressing these negative experiences as a potential problem might enrich and enhance trainees' experiences of their learning disability placements. A Balint group could be a starting point for this. If the problem were addressed, recruitment to and retention within the specialty might improve.
A Prospective, Double‐blind, Randomized Trial of Midazolam versus Haloperidol versus Lorazepam in the Chemical Restraint of Violent and Severely Agitated Patients
Authors: Nobay Flavia , Simon Barry C. , Levitt M. Andrew , Dresden Graham M.
Published: July 2004

Objectives: To determine if midazolam is superior to lorazepam or haloperidol in the management of violent and severely agitated patients in the emergency department. Superiority would be determined if midazolam resulted in a significantly shorter time to sedation and shorter time to arousal. Methods: This was a randomized, prospective, double‐blind study of a convenience sample of patients from an urban, county teaching emergency department. Participants included 111 violent and severely agitated patients. Patients were randomized to receive intramuscular midazolam (5 mg), lorazepam (2 mg), or haloperidol (5 mg). Results: The mean (±SD) age was 40.7 (±13) years. The mean (±SD) time to sedation was 18.3 (±14) minutes for patients receiving midazolam, 28.3 (±25) minutes for haloperidol, and 32.2 (±20) minutes for lorazepam. Midazolam had a significantly shorter time to sedation than lorazepam and haloperidol (p < 0.05). The mean difference between midazolam and lorazepam was 13.0 minutes (95% confidence interval [95% CI] = 5.1 to 22.8 minutes) and that between midazolam and haloperidol was 9.9 minutes (95% CI = 0.5 to 19.3 minutes). Time to arousal was 81.9 minutes for patients receiving midazolam, 126.5 minutes for haloperidol, and 217.2 minutes for lorazepam. Time to arousal for midazolam was significantly shorter than for both haloperidol and lorazepam (p < 0.05). The mean difference in time to awakening between midazolam and lorazepam was 135.3 minutes (95% CI = 89 to 182 minutes) and that between midazolam and haloperidol was 44.6 minutes (95% CI = 9 to 80 minutes). There was no significant difference over time by repeated‐measures analysis of variance between groups in regard to changes in systolic and diastolic blood pressure (p = 0.8965, p = 0.9581), heart rate (p = 0.5517), respiratory rate (p = 0.8191), and oxygen saturation (p = 0.8991). Conclusions: Midazolam has a significantly shorter time to onset of sedation and a more rapid time to arousal than lorazepam or haloperidol. The efficacies of all three drugs appear to be similar.
Emergency Department Visits for Home Medical Device Failure during the 2003 North America Blackout
Authors: Greenwald Peter W. , Rutherford Anne F. , Green Robert A. , Giglio James
Published: July 2004

Objectives: During a widespread North American blackout in August 2003, the authors identified a cluster of patients presenting to their northern Manhattan emergency department (ED) with complaints related to medical device failure. The characteristics of this group with respect to presenting complaint, type of device failure, time spent in the ED, and disposition are described in an effort to better understand the resource needs of this population. Methods:This was a retrospective chart review for all patients evaluated in an urban teaching ED during a 24‐hour period spanning the duration of regional power failure. Charts for patients presenting with medical device failure as part of their triage complaint were abstracted. Results: Twenty‐three of 255 patients coming to the ED during the 24‐hour period presented with medical device failure. Nineteen of the device failures were due to nonfunctioning oxygen conservers, three to ventilator failure, and two to airway suction device failure (one patient had two devices fail). Thirteen of these patients were admitted to the hospital and accounted for 22% of all admissions during the study interval. Discharged patients spent a mean of 15.1 hours (range: 3.8–24.4 hours) in the ED. Conclusions: Patients using electrical medical devices seek care in the ED when power failure occurs, and they require significant ED and hospital resources. Effective disaster planning should anticipate the needs of this population.
Derivation of Clinical Prediction Rules to Identify Children with Fractures after Twisting Injuries of the Ankle
Authors: Dayan Peter S. , Vitale Michael , Langsam Daniel J. , Ruzal‐Shapiro Carrie , Novick Michael K. , Kuppermann Nathan , Miller Steven Z.
Published: July 2004

Objective: The authors sought to derive maximally sensitive prediction rules for identifying children with significant fractures after acute twisting injuries to the ankle. Methods: The authors prospectively enrolled a convenience sample of patients younger than 18 years of age who presented to the pediatric emergency department of an urban, tertiary care center after sustaining acute twisting injuries of the ankle. The ankle was defined in two regions: the malleolar zone and the midfoot zone. Clinical findings were documented on standardized data collection sheets by faculty physicians before completion of ankle and/or foot radiograph series. Significant fracture was defined a priori as any fracture other than an avulsion ≤3 mm. The authors conducted binary recursive partitioning with cross‐validation to develop models to predict fracture. Results: Data from 717 enrolled patients with a median age of 12.9 years were analyzed. Significant malleolar zone and midfoot zone fractures were diagnosed in 81 of 682 (11.9%) and 10 of 173 (5.8%) patients for whom ankle and foot radiographs were obtained. Recursive partitioning identified patients at low risk for malleolar zone fracture if 1) they had no bone tenderness at either malleolus or the region just proximal to the fibula malleolus or 2) they had bone tenderness at either malleolus but were able to walk four steps in the emergency department and had no swelling at either malleolus. The two‐part malleolar zone rule had a sensitivity of 100% and specificity of 19.1% on the learning data and 95.1% (95% confidence interval [95% CI] = 87.8% to 98.6%) and 20.0% (95% CI = 16.8% to 23.4%) on the test data. Tenderness either at the proximal fifth metatarsal or cuboid identified midfoot zone fractures with a sensitivity of 100% and specificity of 31.9% on the learning data and 90.0% (95% CI = 55.4% to 99.7%) and 35.0% (95% CI = 27.7% to 42.8%) on the test sample. Conclusions: A set of sensitive prediction rules was developed to identify children with significant fractures after twisting injuries to the ankle. External validation and refinement of the rules will be needed before recommendation of widespread use.
Financing of Emergency Medicine Graduate Medical Education Programs in an Era of Declining Medicare Reimbursement and Support
Authors: Baumann Michael R. , Vadeboncoeur Tyler F. , Schafermeyer Robert W. ,   on behalf of the Society for Academic Emergency Medicine National Affairs Committee
Published: July 2004

In May 2004, the Society for Academic Emergency Medicine (SAEM) National Affairs Committee was tasked with evaluation of graduate medical education (GME) funding in the face of declining Medicare reimbursement and support, and its implications for emergency medicine. This article was developed to educate the SAEM membership on the current status and climate of funding for GME and to serve as the basis of a position statement from SAEM on this topic. The paper presents the history and background on GME financing followed by currently known changes from the recently signed Medicare Act of 2003.
Fgf3 signaling from the ventral diencephalon is required for early specification and subsequent survival of the zebrafish adenohypophysis
Authors: Herzog Wiebke , Sonntag Carmen , von der Hardt Sophia , Roehl Henry H. , Varga Zoltan M. , Hammerschmidt Matthias
Published: July 2004

The pituitary gland consists of two major parts: the neurohypophysis, which is of neural origin; and the adenohypophysis, which is of non-neural ectodermal origin. Development of the adenohypophysis is governed by signaling proteins from the infundibulum, a ventral structure of the diencephalon that gives rise to the neurohypophysis. In mouse, the fibroblast growth factors Fgf8, Fgf10 and Fgf18 are thought to affect multiple processes of pituitary development: morphogenesis and patterning of the adenohypophyseal anlage; and survival, proliferation and differential specification of adenohypophyseal progenitor cells. Here, we investigate the role of Fgf3 during pituitary development in the zebrafish, analyzing lia/fgf3 null mutants. We show that Fgf3 signaling from the ventral diencephalon is required in a non-cell autonomous fashion to induce the expression of lim3,pit1 and other pituitary-specific genes in the underlying adenohypophyseal progenitor cells. Despite the absence of such early specification steps, fgf3 mutants continue to form a distinct pituitary anlage of normal size and shape, until adenohypophyseal cells die by apoptosis. We further show that Sonic Hedgehog (Shh) cannot rescue pituitary development, although it is able to induce adenohypophyseal cells in ectopic placodal regions of fgf3 mutants, indicating that Fgf3 does not act via Shh, and that Shh can act independently of Fgf3. In sum, our data suggest that Fgf3 signaling primarily promotes the transcriptional activation of genes regulating early specification steps of adenohypophyseal progenitor cells. This early specification seems to be essential for the subsequent survival of pituitary cells, but not for pituitary morphogenesis or pituitary cell proliferation.
Microvilli appear to represent the first step in actin bundle formation inDrosophilabristles
Authors: Tilney Lewis G. , Connelly Patricia S. , Guild Gregory M.
Published: June 2004

During bristle development the emerging bristle shaft, socket cell, and the apical surface of thoracic epithelial cells form tiny protuberances or pimples that contain electron-dense material located on the cytoplasmic surface of the pimple tip. In a few cases short actin filaments extend from this material into the cortical cytoplasm. When cultured in the presence of jasplakinolide, an agent that prevents filament disassembly, pimples elongate to form microvilli containing a core of crosslinked filaments. Emerging-bristle mutants delay cortical bundle formation and are aggregated by forked protein crossbridges. Using these mutants and enhancing core bundle formation with jasplakinolide we found that microvillar formation represents the first stage in the morphogenesis of much larger actin bundles in Drosophila bristle shaft cells. Evidence is presented showing that socket cells do not contain forked protein crossbridges, a fact that may explain why cortical bundles only appear in bristle shaft cells. Furthermore, as pimples and microvilli form in the absence of both forked and fascin crossbridges, we also conclude that neither of these crossbridges account for core bundle formation in microvilli, but there must exist a third, as yet unidentified crossbridge in this system. Immunocytochemisty suggested that this new crossbridge is not Drosophila villin. Finally, ultrastructural comparisons suggest that microspikes and microvilli form very differently.
Photoswitching of a Vectorial Electron Transfer Reaction at a Diarylethene Modified Electrode
Authors: Nakashima Naotoshi , Nakanishi Takashi , Nakatani Akihiro , Deguchi Yonekazu , Murakami Hiroto , Sagara Takamasa , Irie Masahiro
Published: July 2004

We describe here the construction of a diarylethene modified electrode system in which the photoswitchable vectorial electron-transfer from the electroactive diarylethene on the electrode to hexacyanoferrate(III) in solution is possible.
Rearrangements of Tricyclo[5.3.1.0]undecatrienyl Anion; Chemical Evidence Supporting Cyclopropane Ring Circumambulation of Anionic Species
Authors: Oda Mitsunori , Masaki Yoshimi , Okazaki Yoshimi , Kajioka Takanori , Izawa Mayumi , Miyatake Ryuta , Kuroda Shigeyasu , Scott Lawrence T
Published: July 2004

The tricyclic anion 5, generated from the corresponding hydrocarbon 3 with n-BuLi, undergoes the circumambulatory rearrangement at −78 °C to afford the anion 6, which stereoselectively reacts with deuterium oxide at low temperature and undergoes further rearrangements to the stable cyclopentadienyl anion derivative 9 at elevated temperature.
Synthesis, Structural Characterization, and Biological Activity of Two Different Nickel(II) Complexes Derived from N′-[1-(2-pyridyl)ethylidene]morpholine-4-carbothiohydrazide
Authors: Kasuga Noriko Chikaraishi , Ohashi Atsushi , Koumo Chisa , Uesugi Jun , Oda Munehiro , Nomiya Kenji
Published: July 2004

The reaction of Ni(OAc)2 with N′-[1-(2-pyridyl)ethylidene]morpholine-4-carbothiohydrazide (HL) afforded two nickel(II) complexes, [Ni(L)2] (1) and [Ni(L)(OAc)] (2), depending on reaction temperature and starting molar ratio; the former was a 6-coordinate, paramagnetic complex and the latter a 4-coordinate, diamagnetic complex. X-ray analysis of the complex 2 revealed that the ligands, L and OAc, were coordinated to the central metal ion to form a square-planar geometry. The complex 2 showed enhanced antimicrobial activities against selected Gram-positive bacteria, compared with those of the ligand alone, whereas the other complex 1 showed no activity.
Reduction of Aryl Mesylates Catalyzed by Nickel Complexes
Authors: Sasaki Ken , Kubo Tatsuya , Sakai Mutsuji , Kuroda Yasuhisa
Published: July 2004

Aryl mesylates were found to be deoxygenatively reduced into the corresponding aromatic hydrocarbons by using nickel(0)-dppb/PPh3 catalyst with zinc powder and an alcohol as a hydrogen donor.
Anisotropy of Electrical Polarizability of a DNA Fragment
Authors: Washizu Hitoshi , Kikuchi Kazuo
Published: July 2004

Metropolis Monte Carlo Brownian dynamics simulations are performed on model DNA solutions. It is shown that the induced dipole moment responsible for the orientation of a DNA fragment in an applied electric field may have its origin in the displacement of Manning’s condensed counterions along DNA rod axis.
Electrochromic Polymer Derived from Oxidized Tetrakis(2-hydroxyphenoxy)Phthalocyaninatocobalt(II) Complex
Authors: Kimura Mutsumi , Horai Takashi , Hanabusa Kenji , Shirai Hirofusa
Published: July 2004

Tetrakis(2-hydroxyphenoxy)phthalocyaninatocobalt(II) complex 3 is synthesized and electrochemically polymerized to give polyphenyleneoxide films containing Co(II) phthalocyanine which exhibit an electrochromic behavior.
A Novel Reverse Micellar System Composed of Bis(octylethylenediamine)zinc(II) Chloride in Aqueous Benzene and Chloroform Solutions
Authors: Iida Masayasu , Yonezawa Akira , Tanaka Junko
Published: July 2004

We prepared Zn(octylethylenediamine(= oct-en))2Cl2 and found that its solubilities to benzene and chloroform are appreciably enhanced with an addition of water. This solubilizaiton can be attributed to the formation of reverse micelles. Vapor pressure osmometry(VPO) showed appreciable aggregations in benzene solutions, and 13C and 2H NMR relaxations for the zinc complex and water molecules, respectively, suggest their extensive motional restrictions in benzene and chloroform solutions by the aggregations.
New BETS Salt with Iodomercurate Anion: (BETS)4Hg3I8
Authors: Bogdanova O A , Gritsenko V V , Dyachenko O A , Zhilyaeva E I , Kobayashi Akiko , Kobayashi Hayao , Lyubovskaya R N , Lyubovskii R B , Shilov G V
Published: July 2004

Two phases of new BETS salt of (BETS)4Hg3I8 are synthesized. X-ray analysis of θ-phase revealed a strong interstack interaction in organic layers and the occurrence of infinite chains of iodomercurate anions.
Synthesis of Ti-beta Zeolite with High Oxidation Activity by a Dry-gel Conversion Technique
Authors: Tatsumi Takashi , Xia Qinghua , Jappar Nizamidin
Published: July 2004

A new method of synthesizing zeolite Ti-beta has been developed based on a dry-gel conversion technique. The obtained Ti-beta samples exhibited high activity for oxidation of cyclohexene with H2O2, irrespective of the presence of sodium.
Coprecipitation of Trace Metal Ions with Scandium Hydroxide for Graphite Furnace Atomic Absorption Spectrometry
Authors: Ueda Joichi , Minami Tomoharu
Published: July 2004

Scandium hydroxide is a useful coprecipitant for the preconcentration of copper, tin(IV), lead, antimony(III), bismuth(III), cadmium, chromium(III), cobalt, and nickel on the graphite furnace atomic absorption spectrometry. The determination of trace amount of copper in water was demonstrated.
Infrared Spectra of Water Isotopes(H2O, HDO, and D2O Molecules) in Hydrophobic Poly(vinylidene fluoride)
Authors: Kusanagi Hiroshi
Published: July 2004

FTIR spectra of water isotopes H2O, HDO, and D2O in hydrophobic polymer solid have been first observed on poly(vinylidene fluoride) (PVDF), although the similar spectra had been measured in solid nitrogen and other inactive-gas solids by the matrix-isolation method. The spectra of H2O and D2O reveal that water molecules exist as a monomeric species in PVDF and does not take dimer or cluster structures. This restricted isolated water state in PVDF originates from the rather strong intermolecular interaction between the water molecules and the hydrophobic polymer.
Preparation of Tetraphenylazulenequinodimethanes from the Reactions of Azulenequinones with Diphenylketene and the 1H NMR and UV-vis Spectral Studies in Acidic Media
Authors: Mori Akira , Yan Yong Zhe , Takeshita Hitoshi , Nozoe the late Tetsuo
Published: July 2004

3-Bromo-1,5-azulenequinone and 3-bromo-1,7-azulenequinone reacted with diphenylketene to give the corresponding tetraphenylazulenequinodimethane, which has both diphenylfulvene and diphenylheptafulvene structures. The protonation occurred at the diphenylmethylene group on the seven-membered ring to form a cycloheptatrienylium ion.
Sonochemical, Aerobic Conversion of Alkyl Halides into Alcohols Promoted by Trialkyltin Halide/NaBH3CN Catalytic System
Authors: Sawamura Masaya , Kawaguchi Yasuhide , Sato Kenichi , Nakamura Eiichi
Published: July 2004

Under sonochemical conditions, various alkyl halides were converted into the corresponding alcohols in high yields through an aerobic radical reaction promoted by trialkyltin halide/NaBH3CN catalytic system.
DNA Binding and Cleaving Activity of Antitumor Metal Complex: Sodium trans-dinitrobis(2,4-pentanedionato)cobalt(III)
Authors: Tamura Hiroshi , Fujita Hiroyuki
Published: July 2004

The antitumor metal complex, sodium trans-dinitrobis(2,4-pentanedionato)cobalt(III) bound to adenine rich regions of DNA helix and caused single strand scission under the irradiation of light.
Detection of Morphine in ppb Range by Using SPR (Surface- Plasmon-Resonance) Immunosensor
Authors: Miura Norio , Ogata Kyoko , Sakai Go , Uda Taizo , Yamazoe Noboru
Published: July 2004

Highly sensitive detection of morphine (MO) in ppb range was realized by using an immunosensor based on surface-plasmon-resonance (SPR) phenomena. The addition of MO into the antibody solution was found to reduce the incident angle shift of the SPR sensor system sharply because of the inhibition effect of MO. Based on this inhibiting principle, the present sensor could detect MO very sensitively in the concentration range of 0.1 - 10 ng/cm3 (ppb).
The Role of α-Chymotrypsin Active Site in the Proton Dissociation of Aromatic Sulfonium-Salt Pendants Attached to the Methionine-192 Residue
Authors: Sakurai Tadamitsu , Fujita Kiyoshi , Takahashi Naoki , Kubo Kanji , Inoue Hiroyasu
Published: July 2004

Hammett and 13C NMR analyses of proton-dissociation processes for sulfonium-salt pendants on α-chymotrypsin which had been modified by 2-bromoacetophenone and its derivatives (as well as for their corresponding model sulfonium salts) show that a hydrophobic environment around the pendants destabilizes the sulfonium-salt form so as to substantially promote its proton-dissociation reaction. This produces a sulfonium ylide with a keto structure.
Effect of Hydrogen Bonding on the Stability of Thiol Self-Assembled Monolayers (SAMs) on Gold
Authors: Zhang Haoli , Xia He , Li Hulin , Liu Zhongfan
Published: July 2004

The electrochemical stability of SAMs prepared from dodecanethiol (1), (N-2′-mercaptoethyl)-amino)octaneamide (2) and ((N-(2′-mercaptoethyl)-amino)carbonyl)azobenzene (3) in ethanol was studied. The results reveal that introducing hydrogen bonds into SAMs could effectively increase their stability in electrical environment. The presence of large rigid aromatic group in the film may, however, cause a decrease of stability.
Novel Microstructures of Self-Assembled Microcrystallites of (NH4)3PW12O40 and Cs3PW12O40
Authors: Ito Takeru , Song In-Kyu , Inumaru Kei , Misono Makoto
Published: July 2004

Three different microstructures of self-assembled microcrystallites (or of aggregates) of heteropoly compounds, (NH4)3PW12O40 and Cs3PW12O40, have been found: (1) microcrystallites that self-assembled with unidirectional orientation and were epitaxially connected with each other to form dodecahedra, (2) microcrystallites that self-assembled with unidirectional orientation, but were little connected epitaxially each other to form round aggregates, and (3) dispersed fine particles. This variation of the microstructure was consistently explained by the change in the solubility of the compounds, that is, the precipitation temperature and the kind of cation.
Femtosecond Diffuse Reflectance Spectroscopy on Some Standard TiO2 Powder Calalysts
Authors: Furube Akihiro , Asahi Tsuyoshi , Masuhara Hiroshi , Yamashita Hiromi , Anpo Masakazu
Published: July 2004

Transient diffuse reflectance spectroscopic analysis using a femtosecond white-light continuum as a probe pulse was applied to commercially available catalysts of TiO2 powder; ”standard TiO2 catalysts” (JRC-TIO-2 and -4) supplied by the Catalysis Society of Japan. The ultrafast dynamics of photogenerated charge carriers under vacuum and air conditions was compared and discussed.
An Efficient and General Entry to (Z)-α-Fluoro-β-substituted Acrylaldehydes Based on the Coupling Reaction of α-Fluoro-β-amino Acrylaldehydes with Organolithium Reagents
Authors: Funabiki Kazumasa , Kurita Takao , Matsui Masaki , Shibata Katsuyoshi
Published: July 2004

α-Fluoro-β-amino acrylaldehydes (2), readily available from the reaction of polyfluoroalkenyl tosylates (1) with dialkylamines in the presence of triethylamine and a catalytic amount (10 mol%) of tetrabutylammonium fluoride (TBAF), reacted smoothly with various organolithium reagents at −78 °C for 0.5 h, followed by hydrolysis with 10% hydrochloric acid at room temperature for 1 h to afford the corresponding (Z)-α-fluoro-β-substituted acrylaldehydes (3) via allylic rearrangement in good to excellent yields.
Ferromagnetic Dimer of π-Conjugated Organic Free Radicals 9,9-Bis(p-tolyl)-9,10-dihydroacridin-10-yloxyl
Authors: Imachi Ron , Ishida Takayuki , Suzuki Motohiro , Yasui Masanori , Iwasaki Fujiko , Nogami Takashi
Published: July 2004

The magnetic property of the title radical crystals was analyzed by the Bleaney-Bowers equation with J/kB = +8.85 K, which is consistent with the dimetic molecular arrangement with “pseudo-ortho” stacking determined by crystallographic analysis. The inter-dimer interaction was antiferromagnetic.
The Effect of Packing Density on the Electron-Transfer Kinetics of an Azobenzenethiol Monolayer on Gold
Authors: Shao Hui-Bo , Yu Hua-Zhong , Zhao Jian-Wei , Zhang Hao-Li , Liu Zhong-Fan
Published: July 2004

The effect of molecular packing density on the electron transfer kinetics in an azobenzene self-assembled monolayer on gold was investigated for the first time by controlling the assembling time. The apparent electron transfer rate constant (kS) showed a gradual decrease with increasing the molecular packing density, which can be well understood in terms of a structural inhibition occurred in the closely packed monolayer on the reduction/oxidation of azobenzene.
Enhancement of Photocatalytic Oxidation Activity by Surface-Modified CdS Nanoparticles of High Photostability
Authors: Han M Y , Gan L M , Huang W , Chew C H , Zou B S
Published: July 2004

High photostable CdS nanoparticles modified with alkyl group were prepared by an improved microemulsion technique using hexanethiol (RSH) as co-surfactant. The surface-modified CdS nanoparticles (R-CdS) catalyzed the photooxidation of 4-chlorophenol via continuous bubbling oxygen under UV light. The photocatalytic oxidation activity of R-CdS nanoparticles was enhanced due to the high photostability generated by heat-treatment.
Continuous Spectroscopic and Redox Tuning of Dinuclear Compounds: Chlorotetrakis(μ-N,N′-diarylformamidinato)diruthenium(II,III)
Authors: Lin Chun , Ren Tong , Valente Edward J , Zubkowski Jeffrey D , Smith Eugene T
Published: July 2004

The color of the Ru2(μ-N,N′-diarylformamidinato)4Cl series displays a dramatic red-shift as the electron-withdrawing power of aryl-substituent is increased.
Observation of Three Bands in Fluorescence Spectra of Asymmetric Diamines Having Primary and Tertiary Amino Groups
Authors: Yamamoto Shunzo , Habara Hidemasa
Published: July 2004

Broad and asymmetric emission spectra were observed with some saturated diamines which have a primary and a tertiary amino group in cyclohexane. These spectra were resolved into three component bands. The shortest and longest wavelength bands were assigned to an excited tertiary amino group moiety and an exciplex formed between the excited tertiary and the ground-state primary amino groups. The middle band was observed for the first time, and its assignment has been discussed.
Nitric Oxide Synthesis Capabilities of Cytochrome P450 1A2 and NADPH-Cytochrome P450 Reductase from N
G-Hydroxy-l-Arginine
Authors: Sano Hiroaki , Sato Hideaki , Sagami Ikuko , Shimizu Toru
Published: July 2004

NO was formed from NG-hydroxy-l-arginine by cytochrome P450 1A2 (P450 1A2) with turnover numbers of 0.6 - 1.2 nmol/nmolP450/min and 62 pmol/nmolP450/min in peroxide-supported shunt and reconstituted systems, respectively. A Glu318Ala mutation of P450 1A2 enhanced the shunt-reaction activity up to 7.3-fold, whereas the mutation abolished the activity with the reconstituted system. Involvement of H2O2 or superoxide anion in the NO synthesis is also suggested.
1,2-Bis(dimethylphenylsilyl)tetrafluoroethane. Application to the Trifluorovinylation and Tetrafluoroethylenation of Carbonyl Compounds
Authors: Hagiwara Toshiki , Fuchikami Takamasa
Published: July 2004

The reaction of 1,2-bis(dimethylphenylsilyl)tetrafluoroethane with a small excess of benzaldehyde in the presence of the promoter gave the trifluorovinylated product, 1,1,2-trifluoro-3-phenylpropen-3-ol, selectively. The tetrafluoroethylenated product, 2,2,3,3-tetrafluoro-1,4-diphenylbutane-1,4-diol, was also obtained in benzaldehyde solvent or at low temperatures.
Coadsorption of Cationic Dyes with Surfactants on Colloidal TiO2 Particles to Achieve Photosensitization in Highly Acidic Media
Authors: Zang Ling , Qu Ping , Zhao Jincai , Shen Tao , Hidaka Hisao
Published: July 2004

Absorption and emission characteristics of rhodamine B (RB) were investigated in aqueous solutions of sodium dodecylbenzenesulfonate (DBS) at pH 0.9 in the absence and presence of colloidal TiO2. From the spectral changes one can obtain detailed information about the interaction between RB, DBS and TiO2. No adsorption of RB onto the surface of TiO2 occurred at the quite low pH due to the strong electrostatic repulsion between RB molecules and the positively charged TiO2 particles. Addition of DBS was found to be capable of improving the coadsorption of RB onto the surface of TiO2 particles, and thus realizing and efficient charge injection from the excited state of RB into the conduction band of TiO2.
Oxidative Reaction of 1,5-Dithioniabicyclo[3.3.0]octane Bis(trifluoromethanesulfonate) with Diene Complexes of Zirconium and Tantalum: Synthesis of Cp2Zr(OTf)2(thf) and Cp(η4-1,3-butadiene)Ta(OTf)2
Authors: Mashima Kazushi , Oshiki Toshiyuki , Matsuo Yutaka , Tani Kazuhide
Published: July 2004

Oxidative addition of a hypervalent organosulfur compound, 1,5-dithioniabicyclo[3.3.0]octane bis(trifluoromethanesulfonate) (1), to diene complexes of zirconium and tantalum, Cp2Zr(η4-1,3-butadiene) and CpTa(η4-1,3-butadiene)2, in THF resulted in the almost quantitative formation of bis(triflate) complexes of zirconium, Cp2Zr(OTf)2(thf) (3), and tantalum, CpTa(η4-1,3-butadiene)(OTf)2 (5), respectively.
Lanthanoid Complexes of Azobenzene and Benzo[c]cinnoline Derived from Metallic Lanthanoids: Crystal Structures of Binuclear [SmI(thf)3(μ-η2:η2-trans-PhNNPh)SmI(thf)3] and Mononuclear [Yb(benzo[c]cinnoline)3(thf)2]
Authors: Nakayama Yuushou , Nakamura Akira , Mashima Kazushi
Published: July 2004

A binuclear samarium complex of azobenzene, [SmI(thf)3(μ-η2:η2-trans-PhNNPh)2SmI(thf)3], prepared by treating metallic samarium with azobenzene in the presence of iodine was characterized crystallographically. Reaction of metallic ytterbium with benzo[c]cinnoline, a cis-azo compound, gave Yb(bc)3(thf)2 (bc = benzo[c]cinnoline) that is monomeric and adopts distorted dodecahedral geometry, determined by X-ray analysis.
Reaction of Silyl(carbonyl)iron Complexes with LiAlH4 Giving Methylsilanes: Reduction of a Carbonyl Ligand and Coupling with a Silyl Group
Authors: Tobita Hiromi , Shiozawa Rie , Ogino Hiroshi
Published: July 2004

Treatment of CpFe(CO)2SiR3 (R3 = (pTol)2H, (pTol)2Me, MePh(1-Nap); 1-Nap = 1-naphthyl) with LiAlH4 in ether or THF at room temperature gave CH3SiR3 as a major product in moderate to high yield. The labeling experiments using LiAlD4 and CpFe(13CO)2SiR(pTol)2 (R = H, Me) proved unambiguously that the carbonyl ligand is reduced with LiAlH4 and coupled with the silyl group to give the methylsilane.
Accumulation of Cationic-polymer Grafted Poly(styrene) Nanospheres onto an Anionic-polymer Surface
Authors: Serizawa Takeshi , Akashi Mitsuru
Published: July 2004

Styrene nanospheres bearing cationic-polymers such as poly(vinylamine) on their surfaces were accumulated on an anionic-polymer surface by both electrostatic and hydrophobic interactions. Quantitative analyses of the adsorption amount by a quartz crystal microbalance (QCM) revealed that the adsorption behavior of the nanospheres was strongly influenced by the ionic strength in aqueous solution of the nanosphere.
4,5-Diiodo-4′,5′-ethylenedioxytetrathiafulvalene and Its Metallic Radical Salts
Authors: Kuwatani Yoshiyuki , Ogura Eiji , Nishikawa Hiroyuki , Ikemoto Isao , Iyoda Masahiko
Published: July 2004

4,5-Diiodo-4′,5′-ethylenedioxy-TTF (EDO-TTFI2) was synthesized in moderate yield by the reaction of EDO-TTF with LDA, followed by quenching with CF3(CF2)5I. Although EDO-TTF contains electron-withdrawing iodine as the substituent, this compound has a similar donor ability to BEDT-TTF. The radical-cation salt (EDO-TTFI2)2·ClO4 shows a metallic conductivity down to 50 K, reflecting the strong I···O interaction.
Synthesis and Crystal Structure of the Tetranuclear Copper(I) Complex [Cu4I4(MPTQ)2] with a N,S,N′-Tridentate Ligand(MPTQ = 8-((2-Pyridylmethyl)thio)quinoline)
Authors: Su Cheng-Yong , Kang Bei-Sheng , Sun Jie
Published: July 2004

Copper(I) iodide reacts with 8-((2-pyridylmethyl)thio)quinoline (MPTQ) to give the tetranuclear cluster complex [Cu4I4(MPTQ)2] which has been structurally characterized, showing that the Cu4I4 core exists in a distorted chair-like structure with four copper atoms forming parallelogram which is bridged by iodine atoms on each short sides, by S, N-MPTQ on each long sides and with two additional iodine atoms face-bridging sets of three copper atoms on opposite sides of the parallelogram.
Palladium-Catalyzed Reaction of Aryl Bromides with Dialkylacetylenes to Produce Allenic Compounds
Authors: Pivsa-Art Sommai , Satoh Tetsuya , Miura Masahiro , Nomura Masakatsu
Published: July 2004

It has been found that aryl bromides, especially ortho-substituted ones, effectively react with dialkylacetylenes in the presence of a palladium catalyst and an appropriate base to give the corresponding aryl-substituted allenes as the predominant products.
Use of an Organometallic Reagent in Water: Sc(OTf)3-Catalyzed Allylation Reactions of Aldehydes in Micellar Systems
Authors: Kobayashi Shu , Wakabayashi Takeshi , Oyamada Hidekazu
Published: July 2004

The Sc(OTf)3-catalyzed allylation reactions of aldehydes with tetraallyltin proceeded smoothly in micellar systems to afford the corresponding homoallylic alcohols in high yields. The reactions were successfully carried out in the presence of a small amount of a surfactant in water without using any organic solvents.
Reaction Dynamics of Ba + CH3Br/HBr → BaBr + CH3/H
Authors: Wu Victor Wei-Keh , Han Ke-Li , He Guo-Zhong
Published: July 2004

QCT calculations for reactions Ba + CH3Br and Ba + HBr on LEPS surfaces within 0.01 ≤ Erel ≤ 3.0 eV by comparison with available experimental data within 0.075 ≤ Erel ≤ 2.31 eV have been done. The reaction dynamics of both chemical reactions have been obtained and their mechanisms have been deduced. The difference of the reaction dynamics via stripping and migration have been graphically described. The H atom of HBr shows enormous contribution of migration in the reaction of Ba+HBr, though the volume of H is comparably much smaller.
Hydrogen Abstraction From Unactivated Hydrocarbons Using a Photochemically Excited Isoindoline Nitroxide
Authors: Bottle Steven E , Chand Ugesh , Micallef Aaron S
Published: July 2004

The photochemically excited nitroxide, 1,1,3,3-tetramethylisoindolin-2-yloxyl (1*), abstracts primary, secondary or tertiary hydrogens from unactivated hydrocarbons including cyclohexane, isobutane and n-butane. The resultant carbon-centred radicals are rapidly and efficiently trapped by ground state nitroxide. Hydrogen abstraction from methane may also occur, but is masked by secondary photochemical reactions.
Photocatalytic Decomposition of Water into H2 and O2 over Novel Photocatalyst K3Ta3Si2O13 with Pillared Structure Consisting of Three TaO6 Chains
Authors: Kudo Akihiko , Kato Hideki
Published: July 2004

The novel catalysts of native and NiO-loaded K3Ta3Si2O13 with pillared structure consisting of three linear TaO6 chains showed luminescence and high photocatalytic activities for the decomposition of distilled water into H2 and O2 in stoichiometric amounts under UV irradiation.
Synthesis of Benzene from Methane and Carbon Monoxide over Silica-Supported Rh, Ru and Pd Catalysts
Authors: Naito Shuichi , Karaki Tadahiko , Iritani Toshiaki
Published: July 2004

Benzene was formed selectively among hydrocarbons produced in CH4-CO reaction over silica supported Rh, Ru and Pd catalysts at 573-723 K under atmospheric pressures, although CO2 was the main product, which was formed by the disproportionation of CO. Addition of H2 to CH4-CO reaction accelerated the rate of benzene formation several times, and the selectivity increased considerably.
A Catenated Cyclic Octamine: A Noncovalently Bonded Molecular System without Attractive Interaction between the Two Units
Authors: Takata Toshikazu , Shoji Junko , Furusho Yoshio
Published: July 2004

A novel [2]catenane consisted of two cyclic tetramine units (6) was prepared and characterized in terms of mobility of the units. The preparation of 6 was performed by reduction of the corresponding cyclic octamide-type [2]catenane (3) with borane. Varying temperature NMR study indicated that the units of 6 actually move or rotate quite freely unlike those of 3, evidently suggesting a noncovalently bonded molecule without attractive interaction1 between the two units.
The Formation of Monomethyl Carbonato-bridged Dinuclear Nickel(II) Complexes by an Efficient CO2 Uptake in Methanol Containing Urea Derivatives
Authors: Hosokawa Yoko , Yamane Heitaro , Nakao Yasuo , Matsumoto Keiji , Takamizawa Satoshi , Mori Wasuke , Suzuki Shinnichiro
Published: July 2004

Monomethyl carbonato-bridged dinuclear nickel(II) complexes [Ni2(L)(OOC-O-CH3)(CH3OH)2](ClO4)2·H2O·CH3OH, 1 and [Ni2(L)(OOC-O-CH3)(H2O)2](ClO4)2·H2O, 2 were obtained in the presence of [Ni2(L)(OH)(H2O)2](ClO4)2 and N-methylurea at room temperature in air, where HL is N,N,N′,N′-tetrakis[(1-ethyl-2-benzimidazolyl)methyl]- 2-hydroxy-1,3-diaminopropane. The crystal structure of 1 was determined by X-ray crystallography and 2 was characterized by the magnetic susceptibility and visible absorption spectrum.
Efficient and General Synthesis of Novel β-Polyfluoroalkoxy Vinamidinium Salts
Authors: Kase Koichiro , Katayama Mitsuyoshi , Ishihara Takashi , Yamanaka Hiroki , Gupton John T
Published: July 2004

Novel β-polyfluoroalkoxy vinamidinium salts 3 and/or 4 were synthesized in good yields by the reaction of N-(2-polyfluoroalkoxy-3,3-difluoro-1-propenyl)trimethylammonium iodides (2), prepared from N-(2,3,3-trifluoro-1-propenyl)trimethylammonium iodide (1), with secondary amines in MeCN at 70 °C for 1 h. The salts were also obtainable in comparable yields by the one-pot reaction of 1 with sodium polyfluoroalkoxide followed by treatment with amines.
Cyclic Oligo(thio-2,5-thienylenes) (Sulfur-bridged Calixarenes)
Authors: Nakayama Juzo , Katano Naoki , Sugihara Yoshiaki , Ishii Akihiko
Published: July 2004

Thiacalix[4]-, thiacalix[5]-, and thiacalix[6]arenes were synthesized by condensation of dibromo derivatives of the corresponding linear oligomers with Na2S. An X-ray diffraction analysis was performed on the last compound.
Construction of C60 Monolayer on the Water Surface
Authors: Yanagida Masami , Kuri Taishi , Kajiyama Tisato
Published: July 2004

A C60 monolayer was constructed on the water surface by the multi-step creep method for the first time. The surface morphology of the C60 monolayer was homogeneous and the C60 molecules in the monolayer were closely and regularly packed in hexagonal array.
Coupling of Oscillation with Transport Mediated by Polyoxyethylene p-Nonylphenyl Ether in Liquid Membrane System
Authors: Igawa Manabu , Otani Kazuyoshi , Horiguchi Shinpei , Okochi Hiroshi
Published: July 2004

Oscillation coupled with transport phenomena occurred in a liquid membrane system containing polyoxyethylene p-nonylphenyl ether under the concentration gradient of ethyl alcohol. The solutes of ethyl alcohol and some alkaline metal salts were transported without oscillation but their transport rates were enhanced by the periodical convection synchronous with the oscillation in this system.
Porphyrin Architectures Constructed by CH···π Interactions: Synthesis and Crystal Structures of 5,10,15,20-Tetrakis(4-methylchalcogenophenyl)-21H,23H-porphyrins
Authors: Sugiura Ken-ichi , Ushiroda Kantaro , Tanaka Takanori , Sawada Masami , Sakata Yoshiteru
Published: July 2004

Tetraphenylporphyrins substituted with methylchalcogeno groups (XMe: X = Te, Se, S, and O) were prepared. Crystal structure analysis revealed that a novel type of molecular alignments was achieved by intermolecular CH···π interactions between XCH3 and porphyrin π-systems.
New Analogs of the Pyripyropene Family of ACAT Inhibitors via α-Pyrone Fragmentation and γ-Acylation/Cyclization
Authors: Obata Rika , Sunazuka Toshiaki , Tian Zhiming , Tomoda Hiroshi , Harigaya Yoshihiro , Omura Satoshi , Smith Amos B
Published: July 2004

The pyridine moiety of pyripyropene A was replaced with other aromatic and heteroaromatic substituents via α-pyrone degradation followed by dienolate γ-acylation and in situ cyclization.
Synthesis and Characterization of Calcium Endohedral Fullerenes
Authors: Baopeng Cao , Zujin Shi , Xihuang Zhou , Zhennan Gu , Hongzhan Xiao , Jingzun Wang
Published: July 2004

The calcium endohedral fullerenes were synthesized by vaporizing the graphite anode filled with CaC2 grains with DC arc, extracted by CS2, and characterized by field desorption mass spectra. It is found that in the extract most fullerenes between C58 and C100 encapsulated one calcium atom and some trapped two calcium atoms inside. The results show that filling the graphite anode with CaC2 grains is more favorable to the formation of calcium endohedral fullerenes than filling with other materials.
Sandwiching Interaction of Peptides with a Porphyrin
Authors: Sugimoto Naoki , Nakano Shu-ichi
Published: July 2004

Designed oligopeptides were able to bind a porphyrin, 5,10,15,20-tetrakis (N-methylpyridinium-4-yl)-21H,23H-porphine; H2TMpyP with sandwiching interaction, and in this binding a position of aromatic residues and secondary structures of the peptides played an important role. The importance of the sandwiching interaction of the peptides was also indicated in the selection (combinatorial chemistry) of peptides binding H2TMpyP from a large number of peptide sequences.
Chiral Recognition in Disproportionation of Monoradical Cation of Optically Active Bisviologen in an Aqueous Solution
Authors: Tsukahara Keiichi , Abe Kaya , Matsuoka Maki
Published: July 2004

Optically active bisviologens, containing 1-(1-naphthyl)-, 1-phenyl-, and 1-cyclohexylethylamine, were synthesized. Disproportionation of monoradical trications produced by one-electron reduction occurred more easily in the (S,R)-isomers than in the (S,S)- and (R,R)-ones. The disproportionation is controlled by steric bulk of the chiral substituents in intramolecular association between two viologen radical units of diradical dications.
Tentative Structure of Molybdenum Oxycarbide
Authors: Oyama S T , Delporte P , Pham-Huu C , Ledoux M J
Published: July 2004

Scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), and selected area electron diffraction (SAED) are employed to deduce the atomic arrangement of defect molybdenum oxycarbide. The structure is built up of fcc cells of lattice constant 0.41 nm, with semi-ordered metal vacancies giving rise to a larger, 3-fold periodicity of 1.23 nm.
Synthesis and Ion Channel Formation of Novel Cyclic Peptides Containing a Non-natural Amino Acid
Authors: Ishida Hitoshi , Donowaki Kiyoshi , Inoue Yoshihisa , Qi Zhi , Sokabe Masahiro
Published: July 2004

A series of novel cyclic peptides possessing an alternate natural / non-natural amino acid sequence were prepared from l-alanine and 5-(N-acylamino)-3-aminobenzoic acid with a long acyl chain. Upon examination by the voltage clamp method, membranes composed of the synthetic cyclic peptides with varying ring sizes and side-chain lengths were found to form cation selective channels with a conductance of ca. 9 pS in aqueous KCl (500 mM).
Ligand Coupling Mechanism of Nucleophilic Vinylic Substitution of Iodonium Salts with Hypervalent 10-I-3 and 12-I-4 Intermediates
Authors: Okuyama Tadashi , Takino Tomoki , Sato Koichi , Ochiai Masahito
Published: July 2004

Reaction of 2-bromo-1-decenyl iodonium salt with bromide ion in acetonitrile results in nucleophilic substituion with complete retention. Observed rate constants show unexpected dependence on the bromide concentration, conforming with a mechanism involving ligand coupling within a bromoiodane 10-I-3 intermediate.
Lewis Acid Catalysis in Aqueous Media: Copper(II)-Catalyzed Aldol and Allylation Reactions in a Water-Ethanol-Toluene Solution
Authors: Kobayashi Shu , Nagayama Satoshi , Busujima Tsuyoshi
Published: July 2004

Cu(OTf)2 was found to be a stable Lewis acid in aqueous media and to activate carbonyl compounds effectively. Aldol reactions of silyl enol ethers with aldehydes and allylation reactions of tetraallyltin with carbonyl compounds proceeded smoothly in aqueous media, to afford the corresponding adducts in high yields. In addition, the catalyst could be easily recovered quantitatively after the reaction was completed and could be reused.
Extra-articular subtalar arthrodesis
Authors: Bourelle S. , Cottalorda J. , Gautheron V. , Chavrier Y.
Published: July 2004

Of 23 children (35 feet) with cerebral palsy who had undergone a Grice extra-articular subtalar arthrodesis for a valgus hindfoot between 1976 and 1981, we reviewed 17 (26 feet), at a mean of 20 years (17 years 3 months to 22 years 4 months) after operation. Seven were quadriplegic, eight spastic diplegic, and two hemiplegic. They were all able to walk at the time of operation.

Thirteen patients (20 feet) were pleased with the Grice procedure, 13 had no pain and 15 (23 feet) were still able to walk. The clinical results were satisfactory for most feet. Radiography showed that the results had been maintained over time but 14 feet developed a mean ankle valgus of 11° (6 to 18) with a compensatory hindfoot varus in 12 feet. No deformity of the talus or arthritis of adjacent joints was noted.

The Grice procedure gives good long-term results in children with cerebral palsy.
Immobilisation after radiofrequency-induced shrinkage of tendon
Authors: Pötzl W. , Kümpers P. , Szuwart T. , Götze G. , Marquardt B. , Steinbeck J.
Published: July 2004

Despite widespread use of radiofrequency (RF) shrinkage, there have been no animal studies on the effects of post-operative immobilisation on the histological properties of the shrunken tissue. We have therefore examined the role of post-operative immobilisation after RF shrinkage with special emphasis on the histological properties of collagenous tissue.

One patellar tendon of 66 New Zealand White rabbits was shrunk. Six rabbits were killed immediately after the operation. Twenty rabbits were not immobilised, 20 were immobilised for three weeks and 20 for six weeks. Fibroblasts, collagen and vascular quality and density were evaluated on sections, stained by haematoxylin and eosin.

Nine weeks after operation the histological properties were inferior to those of the contralateral control tendons. Shrunk tendons did not return to normal at any time after operation irrespective of whether the animals had been immobilised or not. All the parameters improved significantly between zero and three weeks after operation. Immobilised tendons tended to have a better and faster recovery.

Careful rehabilitation is imperative after RF shrinkage. Immobilisation aids recovery of the histological properties. Our findings in this animal model support a period of immobilisation of more than three weeks.
Footballer’s hip
Authors: Saw T. , Villar R.
Published: July 2004

We have reviewed a consecutive series of six professional footballers who presented with intractable hip pain which was attributed at arthroscopy, to an anterior acetabular labral tear with adjacent chondral damage. The location and type of labral tear were identical for each patient. There was no evidence of acetabular dysplasia. A variable area of chondral damage was associated with the labral tear.

All unstable tissue was resected. Five returned to professional football at the highest level. Acetabular labral pathology should be included in the differential diagnosis of footballers with hip or groin pain. Arthroscopy of the hip is an appropriate method of diagnosis and treatment and minimises the length of rehabilitation required.