bluuebunny/crossref_metadata_2025 huggingface dataset:
Generation and Characterization of 1,3-Di-t-butyl- and 1,3-Di-t-butyl-4,6-dimethylthieno[3,4-c]thiophenes
Authors: Ishii Akihiko , Ida Yutaka , Nakayama Juzo , Hoshino Masamatsu
Published: July 2006

1,3-Di-t-butyl- and 1,3-di-t-butyl-4,6-dimethylthieno[3,4-c]thiophenes (1g and 1h) are generated by Pummerer dehydration of the corresponding sulfoxides (4 and 5, respectively) in boiling acetic anhydride and can be trapped with N-phenylmaleimide (NPM). Both endo- and exo-adducts are formed from 1g and NPM, while only exo-adduct is formed from 1h and NPM. Reduction and isomerization of the starting materials occur in the reactions of 4 and 5 with trifluoroacetic anhydride. The reaction of 5 with trifluoroacetic anhydride in the presence of 2,6-lutidine also gives 4,6-di-t-butyl-1-(trifluoroacetylmethylene)-3-methyl-1H,3H-thieno[3,4-c]thiophene.
Reactions of 1,2-Propadienyl Sulfides with Aldehydes and Acetals Catalyzed by BF3·OEt2
Authors: Narasaka Koichi , Shibata Takanori , Hayashi Yujiro
Published: July 2006

Ene reaction proceeds between 1-alkyl-1,2-propadienyl sulfides and aldehydes in the presence of BF3·OEt2 to afford 1,3-dienes possessing an alkylthio group. On the other hand, the reactions of 1-silyl-1,2-propadienyl sulfides with aldehydes or their dimethylacetals give aldol-type addition products, α-methylene acylsilanes.
Refinement of the Crystal Structure of Pentaerythritol Tetracetate
Authors: Uechi Tetsuo , Fuchita Yoshio
Published: July 2006

The crystal structure of the title compound has been refined to a final R value of 0.041 (weighted R = 0.032), with 380 reflection data measured on a four-circle X-ray diffractometer. The overall structural features show no significant differences from those in the original determimation, while the structural parameters have been improved in precision.
Partial Reduction of Dithioacetals with Phosphorus Reagents
Authors: Saimoto Hiroyuki , Kanzaki Atsuhiro , Miyazaki Kazumi , Sashiwa Hitoshi , Shigemasa Yoshihiro
Published: July 2006

Acyclic dithioacetals 1 derived from di- and monoaryl ketones were monodesulfurized with diphosphorus tetraiodide or dimethyl phosphonate. A side product 5 from the reaction of 9,9-bis(ethylthio)-9H-fluorene with phosphorus triiodide suggested the intermediacy of an anionic species.
A Convenient Preparation of 2,4,6-Trisubstituted 1,3,5-Triselenanes by Treating Aldehydes or Their Acetals with 2,2,4,4,6,6-Hexamethyl-1,3,5-triselena-2,4,6-tristannacyclohexane in the Presence of BF3·OEt2 and AlCl3
Authors: Shimada Kazuaki , Okuse Satoshi , Takikawa Yuji
Published: July 2006

A convenient preparation of 2,4,6-trisubstituted 1,3,5-triselenanes was achieved by the treatment of aldehydes or their acetals with 2,2,4,4,6,6-hexamethyl-1,3,5-triselena-2,4,6-tristannacyclohexane, (Me2SnSe)3, in the presence of BF3·OEt2 and AlCl3.
Studies on Aromatic Sesquiterpenes. XIII. Synthesis of Lacinilene A and Its Structural Isomer
Authors: Tanaka Juichi , Miyake Takashi , Iwasaki Noboru , Adachi Kazuo
Published: July 2006

Lacinilene A (6-norcadalen-7-ol) was synthesized from anisole through 6-norcalamenen-7-ol. 6-Nordaucalen-7-ol also synthesized.
Tetrakis(pyridine)silver(II) Peroxodisulfate, [Ag(py)4]S2O8, a Reagent for the Oxidative Transformations
Authors: Firouzabadi Habib , Salehi Peyman , Mohammadpour-Baltork Iraj
Published: July 2006

Tetrakis(pyridine)silver(II) peroxodisulfate oxidizes aromatic aldehydes to carboxylic acids, benzylic alcohols to carbonyl compounds, aromatic thiols, and allylaryl thioethers to arylsulfonic acids and benzylic carbon–hydrogen bonds to carbonyl groups. α-Hydroxycarboxylic acids and phenylacetic acids are decarboxylated to produce carbonyl compounds. Dibenzyl ether and its sulfur analogue are converted to their corresponding ester and the thioester, respectively.
2,3-Dichloro-6-(3-carboxy-2-hydroxy-1-naphthylazo)quinoxaline as an Analytical Reagent for the Spectrophotometric Determination of Microamount of Gold(III)
Authors: Amin Alaa S , Shakra S , Abdalla A A
Published: July 2006

The synthesis, spectral characteristics, and analytical application of 2,3-Dichloro-6-(3-carboxy-2-hydroxy-1-naphthylazo)quinoxaline (DCHNAQ) are described. A simple, rapid, selective, and sensitive spectrophotometric method for the determination of microgram amounts of gold, alone, or in the presence of associated metals, is developed, based on the color reaction between the metal ion and the reagent. The yellowish brown complex (λmax = 575 nm) has stoichiometric ratio (1 : 1) [metal : ligand] over the pH range 3.4 to 7.0. Beer’s law is obeyed over the concentration range 0.1—6.9 μg cm−3 of gold. The molar absorptivity and Sandell’s sensitivity of the method are 1.52 × 104 dm3 mol−1 cm−1 and 0.016 μg Au cm−1 respectively. The relative standard deviation for six replicate determination of 2.95 μg cm−3 of gold(III) is 1.37%. The interference of various ions has been studied and conditions were developed for the determination of gold in alloys and some synthetic samples without the need for extraction or heating.
Kinetics and Diffusing Species of the High-Temperature Selenidization of Molybdenum
Authors: Wakatsuki Noboru , Sasaki Yoshinori
Published: July 2006

A molybdenum sheet was selenidized at a selenium vapor pressure of 0.40—13.3 kPa at 773—973 K by means of a sealed-tube method. X-Ray diffraction patterns and an electron probe microanalysis of the product films showed that a single layer comprising MoSe2 was formed under all of the selenidization conditions employed. All of the selenidizations obeyed a parabolic rate law and, therefore, the rate-determining step was apparently a diffusion process. The parabolic rate constant (Kp) was expressed as a function of the absolute temperature, and the selenium vapor-pressure dependence of Kp could be clearly recognized. A marker experiment indicated that selenium was the component which diffused.
Solution Equilibria of Binary and Ternary Zinc(II) Halogeno Complexes in N,N-Dimethylacetamide
Authors: Suzuki Honoh , Koide Makoto , Ishiguro Shin-ichi
Published: July 2006

Solution equilibria between zinc(II) and halide ions have been studied in N,N-dimethylacetamide (DMA) by calorimetry at 298 K. Formation constants, enthalpies, and entropies of mononuclear binary complexes, [ZnIICln](2−n)+ (n = 1—4), [ZnIIBrn](2−n)+ (n = 1—3), and [ZnIIIn](2−n)+ (n = 1,2), have been determined. In addition, mixed-ligand complexes have been detected in ternary Zn–Cl–Br and Zn–Br–I systems: [ZnClBr], [ZnCl2Br]−, [ZnClBr2]−, and [ZnBrI]. Complexation is more favorable and more exothermic in the order Cl > Br > I. Formation of the monohalogeno complexes is particularly endothermic and entropy-productive, suggesting that geometric transition from octahedral to tetrahedral is complete at this step, i.e., all the halogeno complexes are tetrahedral. Thus, the transition occurs earlier in DMA than in N,N-dimethylformamide (DMF). Compared with DMF, complexation in DMA is more favorable and more exothermic exclusively at the first and second steps, and little difference is found for the later steps. This is attributed to the steric hindrance of DMA molecules, which is crucial in octahedral coordination structures but not important in tetrahedral geometry. Among the first-row bivalent transition metal ions, ZnII is exceptional in its ΔHβ4° and ΔSβ4° values of overall formation of the tetrachloro complex, consistent with the existence of a solvation equilibrium: [Zn(dma)6]2+   [Zn(dma)4]2+ + 2dma.
Phase Separation in Silica Sol–Gel System Containing Poly(ethylene oxide). I. Phase Relation and Gel Morphology
Authors: Nakanishi Kazuki , Komura Hiroshi , Takahashi Ryoji , Soga Naohiro
Published: July 2006

Phase separation and gelation behaviors have been studied for the acid-catalyzed, alkoxide-based silica systems containing poly(ethylene oxide) (PEO) with an average molecular weight of 100000. Gels with micrometer range interconnected porous morphology were obtained similarly to the systems containing other water-soluble polymers, in which the structure development by the spinodal decomposition and the gel forming process take place concurrently. In spite of the morphological similarity, the thermogravimetric analysis revealed that the reacting solution decomposed into phases one rich in PEO and the other rich in solvent. Macropore volume of gels depended mainly on the amount of solvent phase.
Concentration- and Structure-Dependent Effects of Amides on Protease Activity in Organic Solvents
Authors: Yamamoto Yasuhito , Kise Hideo
Published: July 2006

The catalytic activity of α-chymotrypsin (CT) in the transesterification of N-acetyl-l-tyrosine methyl ester to its ethyl ester in aqueous-organic media was markedly enhanced by replacing a part of water with formamide. The activity of CT was strongly dependent on the formamide/water ratio, and excess formamide retarded the activity. Addition of formamide to reaction mixtures at constant water contents exhibited similar activation–deactivation profiles for CT. A kinetic study revealed that the rate acceleration is due to an increase in kcat rather than a change in Km. At a given concentration of amides (0.5 M, M = mol dm−3), propionamide and DMF were much less effective than formamide for activation of CT. The results suggest that formamide interacts with CT in a different way from water.
Studies on Synthesis of Antibacterial Agent (NM441). I. Kinetics and Mechanism of the Reaction of 4-(Bromomethyl)-5-methyl-1,3-dioxol-2-one with 1-Substituted Piperazine (NM394)
Authors: Nishida Hiroshi , Fujii Tatsuya , Abiru Yoshiaki , Yatsuki Katsuya , Yamamoto Masashi , Shimizu Naoki , Kakemi Kazuo , Mikawa Miyako , Kise Masahiro
Published: July 2006

When a tertiary amine (4,NM441) is synthesized from 4-bromomethyl-5-methyl-1,3-dioxol-2-one (DMDO-Br) and a secondary amine (3,NM394) in N,N-dimethylformamide (DMF), the quaternary ammonium salt 5, the ring-opened compound 6, and the 1,2-adduct 7 are formed as by-products. The tertiary amine 4 is formed by nucleophilic attack of 3 on the α-carbon to the bromine atom of DMDO-Br. The ring-opened compound 6 is formed by nucleophilic attack of 3 on carbonyl carbon of DMDO-Br. The quaternary ammonium salt 5 is formed by the reaction of DMDO-Br with 4 (the Menshutkin reaction). Main pathway for the formation of 7 is the Michael addition of 3 to 6. Kinetics of the reactions have been studied and the methods to obtain 4 suppressing the formations of 5, 6, and 7 have been proposed based on the kinetic results.
Second-Harmonic Generation from Single and Mixed Crystals of p-Nitroaniline and Its Derivatives
Authors: Matsushima Ryoka , Hiramatsu Kiyonari , Shimamoto Katsuhisa
Published: July 2006

Noncentrosymmetric and thermostable single crystals (space group of Pna21) of N-(2-butenyl)-p-nitroaniline were obtained by slow crystallization from solution, with SH activities of 150—200 × urea measured by the SHG powder method with a 1064 nm Nd : YAG laser source. Single crystals of N-(3-methyl-2-butenyl)-, N-(2-propenyl)-, or N-butyl-p-nitroaniline showed nil SH activities. On the other hand, mixed crystals of these derivatives with p-nitroaniline showed much higher SH activities (up to 2000), though thermally not stable.
New Synthetic Methods and Reagents for Complex Carbohydrates. IX. Aryl d-Glucopyranosides and 1-Aryl-1-deoxy-d-glucopyranoses from 2,3,4,6-Tetra-O-benzyl-α-d-glucopyranosyl Dimethylphosphinothioate
Authors: Yamanoi Takashi , Fujioka Ayumi , Inazu Toshiyuki
Published: July 2006

The reactions of 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosyl dimethylphosphinothioate and phenolic compounds gave the corresponding aryl α-d-glucopyranosides predominantly in good yields, even when the trimethylsiloxy derivatives of benzene, which are known to afford 1-aryl-1-deoxy-d-glucopyranoses by the conventional methods, were used as acceptors. On the other hands, 1-ary-1-deoxy-β-d-glucopyranose was obtained in good yield when 1,3,5-trimethoxybenzene was used as an acceptor.
Pressure Effect on the Inter- and Intramolecular Vibrations of 1,2,4,5-Tetrachlorobenzene Crystal
Authors: Matsukuma Sinichiro , Kawano Hiroshi , Nibu Yoshinori , Shimada Hiroko , Shimada Ryoichi
Published: July 2006

The effect of pressure on the frequencies and band structures of the Raman active inter- and intramolecular vibrations of the 1,2,4,5-tetrachlorobenzene crystal was studied under hydrostatic pressures upto 4 GPa at 300 K in a gasketed diamond anvil cell. Changes of the Raman frequencies and band structures of the vibrations suggest that the phase transition takes place under about 0.7 GPa. The frequency shift of the intramolecular vibrations induced by pressure was calculated using an intermolecular potential of the atom–atom type based on the two-site molecular exciton theory. The calculation shows that the observed pressure-induced frequency shift is mainly caused by the repulsive force between the chlorine atoms belonging to the adjacent molecules.
Structural Essentials of Ser-1 in Tethered Peptide Ligand of Human Thrombin Receptor for Phosphoinositide Hydrolysis
Authors: Sakaguchi Kazuyasu , Kodama Hiroaki , Ogino Yoshio , Costa Tommaso , Nose Takeru , Shimohigashi Yasuyuki
Published: July 2006

In order to inspect the structural elements of Ser-1 in receptor activation by SFLLRNP (one-letter amino acid code), a ligand peptide tethered to the thrombin receptor, a series of analogs with such replacements as d-Ser, Ala, Thr, and Ac-Ser have been synthesized. These analogs were evaluated for their ability to hydrolyze the phosphoinositide in human neuroblastoma SH-EP cells. It was found that the α-amino group and l-configuration of Ser-1 are very important in the activation of receptors. N-Acetylation or deletion of Ser-1 completely eliminated the activity of SFLLRNP (a half-maximal effective concentration, EC50 = 0.89 μM (1 M = 1 mol dm−3)), and these modifications induced no antagonist activity. Incorporation of d-Ser also drastically diminished the activity, but retained about 50% activity of the maximal response by 100 μM SFLLRNP. The Ser/Ala substitution sustained 30% of the activity of SFLLRNP to elicit a full stimulation. The Ser/Thr substitution, however, enhanced the activity (20%) in spite of its decreased activity (60%) reported for platelet aggregation. These results indicated that the β-hydroxyl group of Ser-1 is important to receptor activation, but not essential. The effect of chemical modifications on the receptor activities of the tethered ligand is discussed with regard to the efficacy between phosphoinositide hydrolysis and biological activities.
Generation of 2-Lithio-2-(trimethylsilyl)silacyclopentane and 2-Lithio-2-(phenylthio)silacyclopentane and Their Use for the Synthesis of 1,4-Butanediols and γ-Hydroxy Ketones
Authors: Matsumoto Kozo , Yokoo Toshiaki , Oshima Koichiro , Utimoto Kiitiro , Rahman Noorsaadah Abd
Published: July 2006

Treatment of 2-(trimethylsilyl)silacyclopentane with t-butyllithium in THF–HMPA gave 2-lithio-2-(trimethylsilyl)silacyclopentane in good yield. An addition of alkyl iodides to the lithium compound provided 2-alkyl-2-(trimethylsilyl)silacyclopentanes which were converted into 1-alkyl-1,4-butanediols upon treatment with H2O2–KF and successively with n-Bu4NF. Reaction of 2-lithio-2-(trimethylsilyl)silacyclopentane with aldehydes gave 2-alkylidenesilacyclopentanes, which were transformed into γ-hydroxy ketones by oxidative cleavage of carbon-silicon bonds. 2-Lithio-2-(phenylthio)silacyclopentane, derived from 2-(phenylthio)silacyclopentane and t-butyllithium, afforded alkenyl sulfides having silylalkyl substituent upon treatment with aldehydes. Oxidative cleavage of carbon–silicon bonds followed by hydrolysis of alkenyl sulfide moiety also provided γ-hydroxy ketones.
Practical Preparation of (Z)-2-(5-Amino-1,2,4-thiadiazol-3-yl)-2-methoxyiminoacetic Acid: A Side-Chain of the Fourth Generation of Cephem Antibiotics
Authors: Tatsuta Kuniaki , Miura Shozo , Gunji Hiroki , Tamai Tetsuro , Yoshida Ryonosuke , Inagaki Takashi , Kurita Yasuyuki
Published: July 2006

A Z-isomer (4) of 2-(5-amino-1,2,4-thiadiazol-3-yl)-2-(methoxyimino)acetic acid, which is the common acyl moiety of clinically useful cephem antibiotics, has been prepared from the aminoisoxazoles through the skeletal rearrangement in several routes. Reaction of 3-amino-5-methoxyisoxazole (7) with alkoxycarbonyl isothiocyanates gave methyl 2-(5-alkoxycarbonylamino-1,2,4-thiadiazol-3-yl)acetates (8), which were converted into the target compound 4 through the reaction of the corresponding keto ester with O-methylhydroxylamime. Compound 4 was prepared similarly from 3-aminoisoxazole (10). Also, O-methylation of 2-hydroxyimino-2-(5-methoxycarbonylamino-1,2,4-thiazol-3-yl)acetate (15) with methyl iodide or dimethyl sulfate in the presence of barium oxide and barium hydroxide octahydrate was found to afford exclusively the desired Z-isomer (14a) of methyl 2-(5-methoxycarbonylamino-1,2,4-thiadiazol-3-yl)-2-(methoxyimino)acetate, which was led to 4.
Diastereo- and Enantioselective Synthesis of syn- and anti-1,2-Diol Units by Asymmetric Aldol Reactions
Authors: Mukaiyama Teruaki , Shiina Isamu , Uchiro Hiromi , Kobayashi Shu
Published: July 2006

syn- and anti-1,2-Diol units were prepared by using asymmetric aldol reactions of the silyl enol ethers derived from α-alkoxythioacetic S-esters with aldehydes. In the presence of tin(II) triflate, a chiral diamine, and dibutyltin diacetate, (Z)-2-benzyloxy-1-ethylthino-1-(trimethylsiloxy)ethene reacted with aldehydes to afford the corresponding anti-aldol adducts in high yields with excellent diastereo- and enantioselectivities, while syn-adducts were obtained from (Z)-2-(t-butyldimethylsiloxy)-1-ethylthio-1-(trimethylsiloxy)ethene and aldehydes under the same reaction conditions. Thus, both diastereomers can be synthesized in excellent enantiomeric excesses by simply choosing the protective groups of the alkoxyl parts of the silyl enol ethers.
Preparation and Magnetic Properties of Dicopper(II) Hydroxide Tris(pyrazolide)s
Authors: Emori Shuji , Sadakata Kazutoshi
Published: July 2006

Dicopper(II) hydroxide tris(pyrazolide)s Cu2(OH)(4-Xpz)3 (pz = pyrazolide ion; X = H, CH3, Cl, Br) and Cu2(OH)(4-Xpz)3(4-XpzH)2 (X = Cl, Br) were prepared and characterized by means of magnetic susceptibility and IR spectroscopy. Their magnetic-moment values increased in the substituent sequence X = CH3 < H < Br ≈ Cl, and were correlated with the basicities and coordinating angles of the pyrazolido ligands.
Photochromism of 1,1-Diaryl-1-alkanols
Authors: Matsui Masaki , Tsuge Michinori , Shibata Katsuyoshi , Muramatsu Hiroshige
Published: July 2006

1,1-Bis[4-(dimethylamino)phenyl]-1-alkanols were found to show photochromism.
Chemoselective Reactions of Tellurium Tetraethoxide towards Thioamides and Amides
Authors: Omote Kazushi , Aso Yoshio , Otsubo Tetsuo , Ogura Fumio
Published: July 2006

Tellurium tetraethoxide reacts with primary thioamides at room temperature, forming nitriles in high yields. On the other hand, the reactions with amides are largely temperature-dependent, giving predominantly esters at 80 °C and nitriles at a higher temperature. Similarly, tellurium tetraethoxide readily induces the C–N bond cleavage of ureas to give carbamates and amines.
Convenient Chemical Actinometer with 2-Hydroxy-4′-methoxychalcone
Authors: Matsushima Ryoka , Mizuno Hirotaka , Kajiura Atsushi
Published: July 2006

The quantum yields for the photochemical conversion of 2-hydroxy-4′-methoxychalcone into the flavylium ion are in the range of 0.25—0.35 in acetic acid and 0.14—0.2 in aqueous ethanol at pH 2, depending on the wavelength of UV light. The quantum yields are essentially constant against any changes in the light intensity, temperature, or substrate concentration, which is a favorable feature regarding use as a convenient chemical actinometer. A one-photon mechanism involving excited-state proton-transferred tautomer is proposed.
Intramolecular Photocycloaddition of the C=C Double Bond to the C≡N Triple Bond Resulting in the Formation of a Novel Cyclic System
Authors: Sakuragi Hirochika , Koyama Toshiya , Sakurazawa Mamoru , Yasui Norimichi , Tokumaru Katsumi , Ueno Katsuhiko
Published: July 2006

Irradiation of a bichromophoric 1-(o-cyanobenzyloxy)-2-(p-methoxyphenyl)-2-butene (1a) in cyclohexane gave an isoquinoline derivative, 8-methoxy-6-methyl-11,13-dihydro[2]benzoxepino[5,4-c]isoquinoline (2a). The structure was determined by X-ray analysis. The formation of 2a can be accounted for by the initial cycloaddition of 1a in the excited singlet state between the C=C double bond and C≡N triple bond, followed by cleavage of the resulting azetine ring and recyclization.
STUDIES ON REACTIONS BETWEEN GAS AND SOLID. III. AZOTATION OF CALCIUM CARBIDE AND THE EFFECT OF PRESSURE OF NITROGEN ON THE REACTION VELOCITY
Authors: Aono Takeo
Published: July 2006

It has been experimentally determined that the velocity of reaction between nitrogen and calcium carbide at high temperatures is not directly proportional to the nitrogen-pressure, but there exists the following relation: (Remark: Graphics omitted.) \oindentwhere P denotes the pressure, K and α certain constants depending upon temperature and other conditions of the reaction.

It has also been found that the higher the temperature the greater is the effect of pressure-increase to the velocity of reaction, though the effect of the pressure-increase becomes smaller at higher pressures. At lower pressures the velocity of the reaction is nearly proportional to the pressure.
SORPTION VELOCITY OF GAS BY POROUS SOLID
Authors: Sameshima Jitsusaburo
Published: July 2006

1. The sorption by porous solid of gas under constant pressure and temperature proceeds, generally, in two stages. The mechanisms of sorption of each stage are described.

2. The velocity of the former stage is expressed by the equation

(Remark: Graphics omitted.)

where x denotes the amount of gas sorbed at time t, and K, s and n are constants. In the simplest case where n=1, this equation is integrated in the following form,

(Remark: Graphics omitted.)

3. The velocity of the latter stage of sorption is expressed by x-a logt=k

where α and k are constants.
ON THE CATALYTIC ACTION OF JAPANESE ACID EARTH. VIII. THE RELATION BETWEEN THE CATALYTIC ACTIVITY AND THE ADSORPTION
Authors: Ishimura Koshiro
Published: July 2006

(1) The catalytic activity of Japanese acid earth on naphthalene has been compared with its adsorptive powers for water, benzene, and naphthalene.

(2) The relations between the adsorptive powers and the surface area of the earth have been discussed.

(3) It has been concluded that the larger the surface area the greater is the catalytic activity and therefore the magnitude of the catalytic activity depends upon the surface area possessing active centres equally distributed but not on the number of the active centres on the equal surface area.

(4) The influence of the chemical composition of the earth on its surface area has been suggested.
The experiences of mentors on a career development and mentoring programme for female mental health nurses in the UK National Health Service
Authors: Woolnough Helen M , Davidson Marilyn J , Fielden Sandra L
Published: July 2006

This paper presents the experiences of executive and non-executive UK National Health Service (NHS) Trust directors and senior managers as mentors in a career development and mentoring programme for a cohort of 27 female mental health nurses from six NHS mental health trusts. Baseline interview data was collated from 27 mentors prior to the programme. Twenty-four mentors participated in semi-structured telephone interviews investigating their experiences of being a mentor at the end of the programme. The interview transcripts were analysed using thematic content analysis. Experience as a mentor impacted on mentors in a variety of ways and the common themes which emerged from the data included: increased understanding of the mentoring role, increased awareness of career barriers for female mental health nurses, improved ground-level insight in relation to nursing staff and the patients they care for, improved professional reputation, increased networks, new insights into organizational issues, personal enjoyment and fulfilment and desire to implement organizational change. All mentors interviewed stated that they would consider becoming a mentor again. The mentoring relationship was an invaluable learning experience for mentors and results from this study suggested that trained mentors have an important role to play as change agents in the NHS.
An illustration of whole systems thinking
Authors: Kalim Kanwal , Carson Ewart , Cramp Derek
Published: July 2006

The complexity of policy-making in the NHS is such that systemic, holistic thinking is needed if the current government's plans are to be realized. This paper describes systems thinking and illustrates its value in understanding the complexity of the diabetes National Service Framework (NSF); its role in identifying problems and barriers previously not predicted; and in reaching conclusions as to how it should be implemented. The approach adopted makes use of soft systems methodology (SSM) devised by Peter Checkland. This analysis reveals issues relating to human communication, information provision and resource allocation needing to be addressed. From this, desirable and feasible changes are explored as means of achieving a more effective NSF, examining possible changes from technical, organizational, economic and cultural perspectives. As well as testing current health policies and plans, SSM can be used to test the feasibility of new health policies. This is achieved by providing a greater understanding and appreciation of what is happening in the real world and how people work. Soft systems thinking is the best approach, given the complexity of health care. It is a flexible, cost-effective solution, which should be a prerequisite before any new health policy is launched.
How to do a telemedical consultation
Authors: Ferguson James
Published: July 2006

In a telemedical consultation, medical information is sought at a distance. Two techniques may be used: asynchronous ('store and forward') and synchronous ('realtime'). Asynchronous consultations have the advantage that the two parties do not have to be available simultaneously; email, for example, has been used successfully for teledermatology. Synchronous consultations depend on communication media such as the telephone, radio or videoconferencing. Successful videoconferencing will involve consideration of four factors: the environment, session initiation, dialogue and session closure. The environment is very important for good-quality consultations and involves planning, equipment and training. Recognizing the advantages and limitations of the available media combined with appropriate planning and training will maximize the utilization of teleconsultations.
Equity in the development of telemedicine sites in an Arkansas high-risk pregnancy programme
Authors: Britt David W , Norton Jonathan D , Lowery Curtis L
Published: July 2006

We investigated where telemedicine sites were placed in a telemedicine network to assist high-risk pregnancies in Arkansas. There were 14 telemedicine sites in 75 counties, excluding the central site in Pulaski county. Logistic regression was used to examine site placement. Five potential predictors of site placement were examined: (1) the logarithm of the number of births in the county (LOGBIRTHS); (2) an indicator of whether a county had an abnormal rate of low birthweight babies (HIGHLBW); (3) the proportion of the county population below the government's poverty level; (4) the ratio of black to white births; (5) an indicator of whether the county bordered the telemedicine hub site county. The results suggested that telemedicine sites were placed where there were more births (LOGBIRTHS, P = 0.001) and more low birthweight babies (HIGHLBW, P = 0.004). After controlling for these variables, the county poverty level did not reduce the likelihood of site placement. Thus telemedicine sites had been established in those areas where the need was great both in terms of immediate risk (rate of low birthweight babies) and in terms of the continuing pressure of large numbers of births. This is significant in view of the concentration of poor minorities in certain areas, which historically have not been matched by past distribution of resources.
Videophone support for an eight-year-old boy undergoing paediatric bone marrow transplantation
Authors: Bensink Mark , Shergold Jill , Lockwood Liane , Little Margaret , Irving Helen , Russell Trevor , Wootton Richard
Published: July 2006

We report the use of an Internet-based videophone to support a child undergoing bone marrow transplantation (BMT). Over the Christmas period, an eight-year-old boy with an underlying diagnosis of attention-deficit/hyperactivity disorder (ADHD) and a history of absconding and aggressive non-compliant behaviour was treated by BMT. We installed an Internet-based videophone in the patient's hospital room two days post-transplant. A second videophone was installed in the patient's home and used the existing home telephone line. In all, 14 videophone calls were made over a nine-day period. The videophone improved interfamily social and emotional support, and appeared to reduce some of the inherent anxiety and distress resulting from paediatric bone marrow transplantation.
Relatives' opinions of IT support, perceptions of irritations and life satisfaction in dementia care
Authors: Engström Maria , Lindqvist Ragny , Ljunggren Birgitta , Carlsson Marianne
Published: July 2006

We studied relatives' opinions of IT support at a residential home for persons with dementia. We also investigated the relatives' perceptions of irritations and life satisfaction before and after increased IT support. This was accomplished using an experimental group ( n = 14) and a control group ( n = 8) of subjects in dementia care. The design was quasi-experimental with baseline assessments and three follow-ups. Data were collected using two questionnaires measuring opinions of the IT support: irritations in care (the Nursing Home Hassles Scale) and life satisfaction (the Life Satisfaction Questionnaire). Results showed that relatives' opinions of IT support were generally positive. In the experimental group, relatives' perceptions of practical/logistical irritations decreased between baseline and 12-month follow-up. In the control group, there was an increase in the total Nursing Home Hassles score between baseline and three-month follow-up. This difference did not persist at seven- and 12-month follow-ups. No significant differences were found for life satisfaction. We conclude that relatives had positive opinions of IT support, and their perceptions of practical/logistical irritations decreased after implementation of the IT support package.
Formulary Forum: Intrathecal Ziconotide for Refractory Chronic Pain
Authors: Lynch Shalini S , Cheng Christine M , Yee Jennie L
Published: July 2006

Objective:

TO describe the pharmacology, efficacy, and safety of ziconotide for treatment of severe chronic pain in patients who are candidates for intrathecal therapy.

Data Sources:

A PubMed/MEDLINE search (1966–June 2006) was conducted using the terms ziconotide, Priait, and SNX-111. Manufacturer-provided data, the Food and Drug Administration medical review of ziconotide, and abstracts presented at American Pain Society meetings (2001–2006) were also reviewed.

Study Selection and Data Extraction:

Human studies evaluating the efficacy and safety of ziconotide for the treatment of chronic pain were considered. Animal data were excluded.

Data Synthesis:

Ziconotide is the first and only neuronal-type (N-type) calcium-channel blocker. Ziconotide must be administered intrathecally via continuous infusion. A programmable implanted variable-rate microinfusion device, or an external microinfusion device and catheter must be utilized. In double-blind, placebo-controlled studies, ziconotide significantly improved patient perception of pain from baseline to the end of the study periods, which ranged from 11 to 21 days. Patients enrolled in clinical trials were intolerant of or refractory to other treatment modalities. There have been no studies that directly compared ziconotide with other intrathecal or systemic analgesics. Key ziconotide-related adverse events are neuropsychiatrie, including depression, cognitive impairment, and hallucinations; depressed levels of consciousness; and elevation of creatine kinase levels. Ziconotide is also associated with a risk of meningitis due to possible contamination of the microinfusion device.

Conclusions:

Ziconotide is a therapeutic option for treatment of severe chronic pain in patients who have exhausted all other agents, including intrathecal morphine, and for whom the potential benefit outweighs the risks of serious neuropsychiatric adverse effects and of having an implanted device. Further studies are needed to determine the comparative efficacy of ziconotide and other pain therapies.
Pegaptanib: A Novel Approach to Ocular Neovascularization
Authors: Chapman Julie A , Beckey Cherylyn
Published: July 2006

Objective:

TO review pegaptanib, a novel aptamer for the treatment of age-related macular degeneration (AMD).

Data Sources:

A literature search using MEDLINE (1980–January 2006) and the Cochrane Database of Systematic Reviews (1978–January 2006) for peer-reviewed, English-language publications was conducted. Abstracts from recent meetings, including the Association for Research in Vision and Ophthalmology and American Society of Retinal Specialists, were reviewed for relevant abstracts and poster presentations.

Study Selection and Data Extraction:

Pharmacokinetic and pharmacology data were extracted from animal and human studies, and double-blind, randomized, controlled trials were included to describe the efficacy and adverse effects of pegaptanib.

Data Synthesis:

The efficacy of pegaptanib has been evaluated in 2 concurrent, prospective, randomized, double-blind trials. Patients with AMD were randomly assigned to receive placebo or pegaptanib intravitreous injection into 1 eye every 6 weeks for 48 weeks. The effectiveness of pegaptanib was realized as early as week 6 and continued through week 54. At week 54, 38% of patients receiving pegaptanib 0.3 mg were classified as legally blind versus 56% of those receiving the sham injection.

Conclusions:

Pegaptanib, a new inhibitor of ocular neovascularization, provides patients with an alternative to photodynamic therapy with verteporfin and offers a novel approach to future drug developments for AMD. Pegaptanib offers the advantage of not requiring photodynamic therapy in conjunction with drug delivery and may be a viable option for institutions where this service is not easily accessible. Results of clinical trials have shown that pegaptanib is effective in delaying progression of AMD.
Long QTc Interval and Torsade de Pointes Caused by Fluconazole
Authors: Pham C Phu , de Feiter Peter W , van der Kuy P Hugo M , van Mook Walther NKA
Published: July 2006

Objective:

To describe a patient who developed torsade de pointes while being treated with fluconazole.

Case Summary:

A 33-year-old woman with a 5 year history of systemic lupus erythematosus was admitted to the intensive care unit because of respiratory insufficiency due to Candida albicans pneumonia. Therapy with intravenous fluconazole 200 mg/day, with dose later adjusted according to her renal function, was started. Prolongation of the QTc interval and torsade de pointes occurred. Initially, domperidone, which had been initiated the day before fluconazole, was suspected as the possible cause and was discontinued; ultimately, both drugs were discontinued. However, torsade de pointes recurred several weeks later when the patient was treated with fluconazole for a second time and disappeared again on withdrawal of the drug. According to the Naranjo probability scale, this adverse reaction was highly probable.

Discussion:

The risk of torsade de pointes does not correlate in a linear fashion with prolongation of the QTc interval, but an interval beyond 500 msec is considered a significant risk factor. Given that both fluconazole and domperidone are metabolized by the cytochrome P450 system, they may intensify each other's proarrhythmic effects, particularly in patients with concurrent renal dysfunction. These risks are of particular concern in patients whose baseline QTc interval is prolonged for any reason.

Conclusions:

From the case history, as well as use of the Naranjo scale, we concluded that fluconazole was the highly probable cause of the development of torsade de pointes in our patient.
Adverse Drug Event Reporting in Intensive Care Units: A Survey of Current Practices
Authors: Kane-Gill Sandra L , Devlin John W
Published: July 2006

Background:

With the incidence of adverse drug events (ADEs) and adverse drug reactions (ADRs) higher in the intensive care unit (ICU) than other areas of the hospital, it is suspected that ADE/ADR surveillance systems differ between ICU and non-ICU areas. However, there is a lack of information about ADE/ADR identification, reporting, and evaluation strategies in the ICU. Understanding the frequency with which institutions incorporate standardized operational ADE/ADR definitions, triggers, and evaluation tools in this population will facilitate benchmarking between hospitals.

Objective:

To determine whether ADE/ADR identification, reporting, and evaluation strategies differ between ICU and non-ICU populations and to characterize ADE/ADR reporting strategies in the ICU.

Methods:

A validated survey was mailed to pharmacy directors at 590 randomly selected hospitals in the US having at least one ICU. A reminder was sent one week after the surveys were mailed. Five weeks later, a second survey was mailed to hospitals that did not respond.

Results:

The response rate was 22% (132/590); institutions were predominantly community (68.2%), with 199 or fewer (54.5%) operational beds and 19 or fewer (60.6%) ICU beds. ICU types included mixed medical/surgical (62.1%), medical (48.5%), surgical (31.8%), coronary (29.5%), neonatal (22.7%), and cardiothoracic (15.2%). Operational definitions for ADEs and ADRs varied little between ICU and non-ICU areas, as 92.4% of institutions used the same term for both settings. Triggers were used to identify ADE/ADRs hospital-wide (75%) and were usually the same between ICU and non-ICU areas (88.6%). ADE reporting was nearly always voluntary (94.7%), using paper reports (88.6%), phone calls (22.7%), e-mail (12.1%), Intranet (12.1%), Web-based/Internet (10.6%), or PDA (1.5%). Only 22% of hospitals tracked ICU-specific data.

Conclusions:

ADE identification, reporting, and evaluation strategies are similar between ICU and non-ICU areas. Few institutions currently track ICU-specific ADE/ADR data. The institution of ICU-specific ADE detection and prevention strategies may improve the safety of critically ill patients.
Dopamine D1/D5Receptors Gate the Acquisition of Novel Information through Hippocampal Long-Term Potentiation and Long-Term Depression
Authors: Lemon Neal , Manahan-Vaughan Denise
Published: July 2006

Hebbian learning models require that neurons are able to both strengthen and weaken their synaptic connections. Hippocampal synaptic plasticity, in the form of long-term potentiation (LTP) and long-term depression (LTD), has been implicated in both spatial memory formation as well as novelty acquisition. In addition, the ventral tegmental area–hippocampal loop has been proposed to control the entry of information into long-term memory, whereas the dopaminergic system is believed to play an important role in information acquisition and synaptic plasticity. D1/D5dopamine receptors are positively coupled to adenylyl cyclase and have been to modulate certain forms of synaptic plasticity, particularlyin vitro. We investigated how D1/D5dopamine receptors modify long-lasting synaptic plasticity at CA1 synapses of adult freely moving rats and found that receptor activation lowered the threshold for the induction of both LTP and LTD. Specific types of learning are associated with specific types of hippocampal synaptic plasticity. We found that object-configuration learning, facilitation of late-phase LTD by object exploration, and late-phase LTP by exploration of empty space were all prevented by D1/D5receptor antagonism. Furthermore, receptor antagonism prevented electrically induced late-LTP, whereas receptor activation facilitated induction of both LTP and LTD by patterned electrical stimulation. These findings suggest that the dopaminergic system, acting via D1/D5receptors, gates long-term changes in synaptic strength and that these changes are a critical factor in the acquisition of novel information.
Signaling from Blood Vessels to CNS Axons through Nitric Oxide
Authors: Garthwaite Giti , Bartus Katalin , Malcolm Denise , Goodwin David , Kollb-Sielecka Martha , Dooldeniya Chaminda , Garthwaite John
Published: July 2006

Brain function is usually perceived as being performed by neurons with the support of glial cells, the network of blood vessels situated nearby serving simply to provide nutrient and to dispose of metabolic waste. Revising this view, we find from experiments on a rodent central white matter tract (the optic nerve)in vitrothat microvascular endothelial cells signal persistently to axons using nitric oxide (NO) derived from the endothelial NO synthase (eNOS). The endogenous NO acts to stimulate guanylyl cyclase-coupled NO receptors in the axons, leading to a raised cGMP level which then causes membrane depolarization, apparently by directly engaging hyperpolarization-activated cyclic nucleotide-gated ion channels. The tonic depolarization and associated endogenous NO-dependent cGMP generation was absent in optic nerves from mice lacking eNOS, although such nerves responded to exogenous NO, with raised cGMP generation in the axons and associated depolarization. In addition to the tonic activity, exposure of optic nerves to bradykinin, a classical stimulator of eNOS in endothelial cells, elicited reversible NO- and cGMP-dependent depolarization through activation of bradykinin B2receptors, to which eNOS is physically complexed. No contribution of other NO synthase isoforms to either the action of bradykinin or the continuous ambient NO level could be detected. The results suggest that microvascular endothelial cells participate in signal processing in the brain and can do so by generating both tonic and phasic NO signals.
Complex Spike Activity of Purkinje Cells in the Oculomotor Vermis during Behavioral Adaptation of Monkey Saccades
Authors: Soetedjo Robijanto , Fuchs Albert F.
Published: July 2006

Throughout life, the oculomotor system can correct itself when saccadic eye movements become inaccurate. This adaptation mechanism can be engaged in the laboratory by displacing the target when the saccade toward it is in flight. Forward and backward target displacements cause gradual increases and decreases in saccade amplitude, respectively. Equipped with this paradigm, we asked whether Purkinje cells (P-cells) in the vermis of the oculomotor cerebellum, lobules VIc and VII, changed their complex spike (CS) discharge during the behavioral adaptation of horizontal saccades. We tested the hypothesis that CS activity would change only when a targeting saccade caused an error in eye position relative to the target, i.e., during the error interval between the primary and corrective saccades. We examined only those P-cells whose simple spike activity exhibited either a burst or pause with saccades in several directions. Approximately 80% of such P-cells exhibited an increase in CS activity during the error interval when the adaptation paradigm imposed horizontal eye-position errors in one direction and a decrease in activity for errors in the other. As adaptation progressed and errors were reduced, there was no consistent change in the CS activity. These data suggest that the CS activity of P-cells in the oculomotor vermis signals the direction but not the magnitude of eye-position error during saccade adaptation. Our results are consistent with cerebellar learning models that have been proposed to explain adaptation of the vestibulo-ocular reflex so similar mechanisms may also underlie plasticity of this precision voluntary oculomotor behavior.
Why Molecular Chaperones Buffer Mutational Damage: A Case Study With a Yeast Hsp40/70 System
Authors: Bobula Joanna , Tomala Katarzyna , Jez Elzbieta , Wloch Dominika M , Borts Rhona H , Korona Ryszard
Published: July 2006

The malfunctioning of molecular chaperones may result in uncovering genetic variation. The molecular basis of this phenomenon remains largely unknown. Chaperones rescue proteins unfolded by environmental stresses and therefore they might also help to stabilize mutated proteins and thus mask damages. To test this hypothesis, we carried out a genomewide mutagenesis followed by a screen for mutations that were synthetically harmful when the RAC–Ssb1/2 cytosolic chaperones were inactive. Mutants with such a phenotype were found and mapped to single nucleotide substitutions. However, neither the genes identified nor the nature of genetic lesions implied that folding of the mutated proteins was being supported by the chaperones. In a second screen, we identified temperature-sensitive (ts) mutants, a phenotype indicative of structural instability of proteins. We tested these for an association with sensitivity to loss of chaperone activity but found no such correlation as might have been expected if the chaperones assisted the folding of mutant proteins. Thus, molecular chaperones can mask the negative effects of mutations but the mechanism of such buffering need not be direct. A plausible role of chaperones is to stabilize genetic networks, thus making them more tolerant to malfunctioning of their constituents.
Site-Specific Amino Acid Frequency, Fitness and the Mutational Landscape Model of Adaptation in Human Immunodeficiency Virus Type 1
Authors: da Silva Jack
Published: July 2006

Analysis of the intensely studied HIV-1 gp120 V3 protein region reveals that the among-population mean site-specific frequency of an amino acid is a measure of its relative marginal fitness. This surprising result may arise if populations are displaced from mutation–selection equilibrium by fluctuating selection and if the probability of fixation of a beneficial amino acid is proportional to its selection coefficient.
Poly(4‐vinylpyridine) and Quadrapure TU as Selective Poisons for Soluble Catalytic Species in Palladium‐Catalyzed Coupling Reactions – Application to Leaching from Polymer‐Entrapped Palladium
Authors: Richardson John M. , Jones Christopher W.
Published: July 2006

Poly(4‐vinylpyridine) and Quadrapure TU were successfully used as poisons for palladium‐catalyzed Heck couplings of iodoarenes and n‐butyl acrylate using a poly(urea) entrapped palladium precatalyst, Pd‐EnCat 40, in a variety of reaction solvents and conditions. These results suggest that all of the Heck coupling takes place outside the poly(urea) matrix via a soluble palladium species leached from the solid. This observation is consistent with previous conclusions that leached species are also solely active when using other supported catalysts such as Pd/C or with supported palladacycles. Control experiments including poisoning by Hg(0), hot filtration, 3‐phase tests, and monitoring of reaction kinetics after recycle support this conclusion. The quantity of PVPy or Quadrapure TU needed for quenching depends on the amount of palladium that is leached and thus applying these poisons to other palladium catalysts in which the amount of soluble palladium is unknown requires an initial trial and error approach.
Asymmetric Hydrogenation of β‐Keto Esters Using Chiral Diphosphonites
Authors: Reetz Manfred T. , Li Xiaoguang
Published: July 2006

The BINOL‐derived diphosphonite having an achiral backbone based on diphenyl ether is a readily accessible and cheap ligand for the enantioselective Ru‐catalyzed hydrogenation of β‐keto esters (ee=95–99 %).