bluuebunny/crossref_metadata_2025 huggingface dataset:
Perceptions of Informed Consent in the Care of Elderly People in Five European Countries
Authors: Schopp Anja , Välimäki Maritta , Leino-Kilpi Helena , Dassen Theo , Gasull Maria , Lemonidou Chryssoula , Scott P Anne , Arndt Marianne , Kaljonen Anne
Published: January 2003

The focus of this article is on elderly patients’ and nursing staff perceptions of informed consent in the care of elderly patients/residents in five European countries. The results suggest that patients and nurses differ in their views on how informed consent is implemented. Among elderly patients the highest frequency for securing informed consent was reported in Finland; the lowest was in Germany. In contrast, among nurses, the highest frequency was reported in the UK (Scotland) and the lowest in Finland. In a comparison of patients’ and nurses’ perceptions, nurses had more positive views than patients in all countries except Finland. Patients with less need for nursing interventions in Greece and Spain gave their consent less often. The German and Greek patients were older, and the results also point to an association between this and their lower frequency of giving consent. In Spain, patients who were married or who had a family member or friend to look after their personal affairs were more likely to be included in the group whose consent was sought less often.

This is the fourth of a set of five articles published together in this issue of Nursing Ethics in which the results of this comparative research project are presented.
Perceptions of Autonomy, Privacy and Informed Consent in the Care of Elderly People in Five European Countries: comparison and implications for the future
Authors: Leino-Kilpi Helena , Välimäki Maritta , Dassen Theo , Gasull Maria , Lemonidou Chryssoula , Scott P Anne , Schopp Anja , Arndt Marianne , Kaljonen Anne
Published: January 2003

This article discusses nurses’ and elderly patients’ perceptions of the realization of autonomy, privacy and informed consent in five European countries. Comparisons between the concepts and the countries indicated that both nurses and patients gave the highest ratings to privacy and the lowest to informed consent. There were differences between countries. According to the patient data, autonomy is best realized in Spain, privacy in the UK (Scotland), and informed consent in Finland. For the staff data, the best results tended to concentrate in the UK. The conceptual and methodological limitations of the study are identified and discussed. Implications of the results are divided into three areas: nursing practice, education and research. In practice, the analysis of patients’ values and the ethical sensitivity of nurses are important as part of ethically good care. In nurse education, students should learn to recognize ethical problems, generally and particularly, among vulnerable groups of patients. Multicultural international research is needed in this area.

This is the last of a set of five articles published together in this issue of Nursing Ethics in which the results of this comparative research project are presented.
Nursing Ethics, Caring and Culture
Authors: Cortis Joseph D , Kendrick Kevin
Published: January 2003

Recent years have witnessed the publication of numerous articles that draw a critical alignment between ethics and caring. In essence, this theme suggests that caring is a moral pursuit centred on the beneficent attention of one person shown to another. Yet, if such language is to have real poignancy, it must be geared towards an inclusive agenda that meets the needs of all within the community. Research evidence suggests that this is not always the case, especially in terms of the care offered to members of minority ethnic groups.

This article will focus on the findings of a qualitative research study that explored the expectations and perceived experiences of nursing care among members of the Pakistani community in Bradford, West Yorkshire, UK. The findings suggest that nurses should develop a more informed narrative that readily reflects the needs of the Pakistani community.
Dilemmas of development and the environment in a globalizing world: theory, policy and praxis
Authors: Simon David
Published: January 2003

Many key dilemmas in contemporary development studies centre on disjunctures between theoretical innovation, formal policy and practice. Even the very meaning of ‘development’ and its implications are today hotly contested. Questions of scale, sustainability and identity lie at the heart of debates over the supposedly homogenizing effects of pervasive globalization. Many prevailing conventional wisdoms are inadequate, and we need more nuanced and contextual approaches in addressing poverty, disempowerment, environmental degradation and other mantras of ‘development’. Particular dilemmas addressed include the translation of theoretical advances into practice; difficulties of ‘mainstreaming’ radical alternatives; the dialectics of spatial scale; environmental, economic and socio-cultural trade-offs and costs associated with change; and the developmental implications of technological innovations, particularly information and computer technologies.
Flooding, vulnerability and coping strategies: local responses to a global threat
Authors: Few Roger
Published: January 2003

Recent scientific outputs suggest that climate change is likely to cause shifts in the global pattern and intensity of flood events, in some regions increasing the exposure of populations to severe flooding. Potential future risks underline the importance of research and intervention work aimed at strengthening local capacity to cope with flooding, especially for the poor in developing countries. This paper reviews recent theoretical and applied research on vulnerability and adaptive capacity of households and communities in flood-prone areas. It traces the growing tendency for interventions to prioritize action at the local scale and suggests directions for further research to deepen understanding of actual and potential coping strategies.
An empirical study of gas penetration in full-shot gas-assisted injection moulded parts
Authors: Liu S-J , Chang K-H
Published: January 2003

Full-shot gas-assisted injection moulding has increasingly become one of the most important methods used to produce plastic components. It has the advantage of eliminating the switchover mark, which usually occurs on the surface of short-shot gas-assisted injection moulded parts. This paper is devoted to an investigation of the effects of different processing parameters on the length of gas penetration in full-shot gas-assisted injection moulded parts. The first part of this report shows how the gas penetration of moulded parts is optimized. An L'18 experimental matrix design based on the Taguchi method was conducted to investigate the processing factors that affect the length of gas penetration in full-shot moulded parts. The second part of this paper identifies the relative significance of each processing parameter on the gas penetration of moulded products. The materials used were general-purpose polystyrene and polypropylene. Experiments were carried out on an 80 ton injection-moulding machine equipped with a high-pressure nitrogen gas injection unit. For the factors selected in the main experiments, melt temperature, gas injection delay time and gas hold time were found to be the key processing parameters affecting the length of gas penetration in full-shot gas-assisted injection moulded parts. In addition, the sink mark of full-shot moulded parts decreases with the length of gas penetration. Bending strength of full-shot gas-assisted injection moulded parts is higher than that of short-shot moulded parts.
The application of U-shape milled grooves for cooling of injection moulds
Authors: Sun Y F , Lee K S , Nee A Y C
Published: January 2003

In the injection moulding process, productivity and part quality depend largely on the cooling system of the injection mould. Several cooling methods are being adopted by the mould industry, with the straight-drilled cooling channels method being the most popular. Many reported research activities have been based on this method, but the method has several limitations that prevent it from achieving efficient and uniform cooling. In the present work, a U-shape milled groove method was proposed for large and complicated parts, especially for parts with large free-formed surfaces. Simulations were made to compare the cooling effect of U-shape milled grooves with that of straight cooling channels using COSMOS/DESIGNSTAR, an analysis software based on the finite element method (FEM). The heat flux was calculated on a cycle-averaged basis and the natural convection between ambient air and the exterior mould surface was ignored. A mouse cover was used as a case study. The U-shape milled grooves were found to have better temperature control than straight cooling channels. The temperature distributions of the core and cavity with U-shape milled grooves were more uniform than with straight cooling channels. Moreover, the U-shape milled grooves removed the heat efficiently; the mould temperature was lower than that with straight cooling channels. The U-shape milled grooves method has demonstrated its advantages in mould cooling. Although U-shape milled grooves need to be machined using computer numerical control (CNC) machines and more machining time is required, making them more expensive than straight cooling channels, their potential benefits will be explored for practical applications.
An integrated approach to the high-speed machining of moulds and dies involving both a knowledge-based system and a chatter detection and control system
Authors: Sim W M , Dewes R C , Aspinwall D K
Published: January 2003

Over the past decade, high-speed machining (HSM) has provided a step change in productivity for the manufacture of moulds and dies, particularly those made from tool steels in the fully hardened state. Advantages include reduced machining times and costs and favourable workpiece surface integrity. The knowledge and expertise that have been generated in academia and industry are widespread and important for the efficient utilization of HSM. Following a survey of relevant publications, the present paper details the development of an integrated system for the HSM of moulds and dies. This included the design and implementation of a knowledge-based system (KBS) and a chatter detection and control system. The main modules of the KBS related to machine tools, cutting tools and machinability data, toolholders, cutter path strategies and troubleshooting, together with a database management centre. Ranking techniques were employed with combined weighing factors, together with tool rationalization and reduction strategies, fuzzy logic and machinability data optimization. The chatter detection and control system utilized a microphone to detect chatter and employed online spindle speed and feed rate modification strategies for its suppression. The system was capable of being interfaced with the KBS in order to transfer and store local knowledge unique to a particular toolmaker's operations.
Green Process in Glycotechnology
Authors: Shoda Shin-ichiro , Izumi Ryukou , Fujita Masaya
Published: January 2003

Oligo- and poly-saccharides are important macromolecules in living systems. They show their multifunctional characteristics in the construction of cell walls, energy storage, and various biological phenomena like cell recognition. The development of a new glycosylation reaction is demanded in order to supply a sufficient amount of oligo- and poly-saccharides for basic research. Enzymes have several remarkable catalytic properties compared with other types of catalyst in terms of their selectivity, high catalytic activity, lack of undesirable side-reactions, and ability to operate under mild conditions. This account presents an overview of recent advances in the glycosylation reactions for synthesis of oligo- and poly-saccharides catalyzed by glycosyl hydrolases. A new carbon cyclic system of “Glyco-Chemistry Cycles” has been proposed based on the renewable polysaccharide biomass.
Spherical Aromaticity in Fullerenes and the Nucleus-Independent Chemical Shifts at the Cage Centers
Authors: Aihara Jun-ichi
Published: January 2003

Nucleus-independent chemical shifts (NICSs) at the cage centers for closed-shell isolated-pentagon isomers of C82 fullerene lie in the wide range from −11 to +48 although all of the isomers are sufficiently aromatic. This decisively shows that NICS cannot be used as an indicator of spherical aromaticity for fullerenes. NICS is nothing other than the measure of local magnetotropicity. Diatropicity is compatible with aromaticity only for monocyclic π-systems.
Subtle Ligand/Media Effects. Modulation of cis/trans Isomerism in Hydrogen Peroxide Oxidation of Pt(II) to Pt(IV) Complexes
Authors: Lee Young-A , Yoo Kyung Ho , Jung Ok-Sang
Published: January 2003

The modulation of cis/trans isomerism on the oxidation of PtII to PtIV via subtle ligand/media effects has been established. The reaction of [PtII(O-O)(dpda)] (O-O = 1,1-cyclobutanedicarboxylate (cbdc), dibenzylmalonate (dbm); dpda = 2,2-dimethyl-1,3-propanediamine) with hydrogen peroxide in acetic acid produces cis-[PtIV(O2CCH3)2(O-O)(dpda)], while the reaction in acetic anhydride gives trans-[PtIV(O2CCH3)2(O-O)(dpda)]. The crystal structures of cis-[PtIV(O2CCH3)2(cbdc)(dpda)] (orthorhombic Pbca, a = 11.148(2) Å, b = 14.188(5) Å, c = 23.425(3) Å, V = 3705(2) Å3, Z = 8, R = 0.0525) and trans-[PtIV(O2CCH3)2(cbdc)(dpda)]·3H2O (monoclinic P21/c, a = 11.479(2) Å, b = 13.426(3) Å, c = 14.640(5) Å, β = 108.73(2)°, V = 2136.8(9) Å3, Z = 4, R = 0.0251) have been solved and refined. The AcO–Pt–AcO angle (87.4(5)°) of the cis isomer presents a striking contrast to that (172.5(1)°) of the trans isomer. The trans isomer is retained in aqueous solution, but the cis isomer is very slowly converted to the trans isomer in both water and acetic acid.
Use of 6-Mercapto Purinylazo Resin in Chromium Speciation
Authors: Mondal Bhim Chandra , Das Arabinda K
Published: January 2003

The present work describes a procedure of preconcentration, separation and determination of the two forms of chromium, viz. Cr(III) and Cr(VI), in waste water by using 6-mercaptopurine anchored by azo function to a polymeric styrene divinylbenzene (8%) matrix as solid phase extractor. The maximum exchange capacity for Cr(III) at pH 6.5 is 0.44 mmol g−1 and that for Cr(VI) at pH 1.0 is 1.06 mmol g−1. In the column operation, the recoveries of both Cr(III) and Cr(VI) in the presence of various foreign ions which are generally present in waste water were examined; it was observed that no such interferences occur in the sorption step. Flow rate optimization studies show that the column is efficient for the separation of both forms of chromium at a flow rate of 1.2 mL min−1. The metal ion concentration was measured by flame atomic absorption spectrometry. The method has been applied for the separation and speciation of chromium in waste water samples.
Determination of Minor and Trace Elements in Biogenic Carbonate Minerals of Coccolithophores by High-Resolution Inductively Coupled Plasma Mass Spectrometry
Authors: Hasegawa Hiroshi , Mito Saeko , Norisuye Kazuhiro , Matsui Masakazu , Maki Teruya , Ueda Kazumasa
Published: January 2003

The sample preparation and analytical methodology are described for determining minor and trace elements (Al, As, Ba, Cd, Co, Cr, Fe, Mg, Mn, Mo, Ni, Sb, Sr, U, V, W, Y and Zn) in biogenic carbonate minerals of coccolithophores. Coccolith particles isolated from cultivated coccolithophores were purified by centrifugation and resuspension with 0.5 mM sodium hydrogencarbonate solutions (1 M = 1 mol L−1). The concentrations of the elements in the final solutions were determined by high-resolution inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry. The analytical results of coccolith particles suggest that the molar ratios of the minor and trace elements in coccoliths vary with the compositions of the medium in which the coccolithophores are grown.
Synthesis of Cationic Diazacrown Ethers and Their Successful Application as Selectivity Modifiers in the Capillary Electrophoresis Separation of Aromatic Anions Involving Positional Isomers
Authors: Mori Masanobu , Tsue Hirohito , Tanaka Kazuhiko , Tanaka Shunitz
Published: January 2003

Two types of positively charged diazacrown ether derivatives with different ring sizes were investigated concerning their ability as selectivity modifiers in capillary electrophoresis. The addition of the cationic diazacrowns to a migrating solution led to the successful separation of the positional isomers of naphthalenedisulfonate, naphthalenedicarboxylate, and phthalate, such that a total of eight aromatic anions were completely resolved in less than 5 minutes. The separation mechanism was studied by examining the effects of the ionic strength and the pH of the running buffer, by determining the ion-association constants between the analytes and the additives, and by elucidating their molecular structures. As a result, a combination of ion-exchange, hydrophobic interaction, and molecular geometry was found to play an important role in the observed separation behavior.
Synthesis and Characterization of Nickel(II) Schiff Base Complexes with Methoxy or Methyl Groups at 2,6-Positions of the Pendant Phenyl Ring: the Control of cis and trans Geometries
Authors: Kawamoto Tatsuya , Konno Takumi
Published: January 2003

Two nickel(II) complexes with N,S chelates were prepared by the reaction of nickel(II) acetate tetrahydrate with 2-substituted benzothiazolines. Bis[2-(2,6-dimethoxyphenylmethyleneamino)benzenethiolato]nickel(II) 1, in which the 2,6-positions of the pendant phenyl ring are occupied by methoxy groups, has an approximately square-planar geometry around a nickel atom with a cis-N2S2 donor atom arrangement. X-ray and variable-temperature 1H NMR studies indicated the existence of an apical Ni···OMe interaction in 1. On the other hand, bis[2-(mesitmethyleneamino)benzenethiolato]nickel(II) 2 with methyl groups at the 2,4,6-positions of the pendant phenyl ring exhibits a perfect planar trans-N2S2 coordination around the nickel atom. An X-ray study revealed the existence of an intraligand CH/π interaction in 2. A difference in the geometry around –CH=N– (E and Z) was also observed between 1 and 2 (Z for 1 and E for 2).
Chelating Adsorbent for Heavy Metal Ions Prepared by Loading Anion-Exchange Resin with Thiacalix[4]arenetetrasulfonate
Authors: Matsumiya Hiroaki , Masai Hideharu , Terazono Yukiko , Iki Nobuhiko , Miyano Sotaro
Published: January 2003

A chelating adsorbent for heavy metal ions has been prepared by loading an anion-exchange resin with thiacalix[4]arenetetrasulfonate (TCAS). Batchwise extraction studies have revealed a high adsorption ability of the TCAS-loaded resin toward heavy metal ions with high selectivity. The present resin strongly retained the heavy metal ions tested here [Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II)] in a slightly acidic to neutral pH region, while no adsorption was observed for alkaline earth metal ions, Mg(II) and Ca(II), in this pH region. These adsorption characteristics of the present resin should be ascribed to the contribution of the bridging sulfur of the loaded TCAS to selectively coordinate to metal ions categorized to be soft to intermediate Lewis acids by the Hard and Soft Acids and Bases (HSAB) rule. A continuous column adsorption system with the present resin allowed the selective and almost quantitative (more than 99.98%) removal of heavy metal ions.
Schiff-Base Metal(II) Complexes as New Catalysts in the Efficient, Mild and Regioselective Conversion of 1,2-Epoxyethanes to 2-Hydroxyethyl Thiocyanates with Ammonium Thiocyanate
Authors: Sharghi Hashem , Nasseri Mohammad Ali
Published: January 2003

A convenient and efficient procedure for the ring-opening of 1,2- epoxyethanes with ammonium thiocyanate in the presence of some Schiff-base complexes of metal(II) is described. The cleavage of the oxirane ring is found to proceed regioselectively under mild reaction conditions. Thus, several 2-hydroxyethyl thiocyanates, useful intermediates toward biological-active molecules, are easily obtained in very good yields.
Dichlorobis(1,4-diazabicyclo[2.2.2]octane)(tetrahydroborato)zirconium(IV), [Zr(BH4)2Cl2(dabco)2](ZrBDC), as a New, Stable, and Versatile Bench Top Reducing Agent: Reduction of Imines and Enamines, Reductive Amination of Aldehydes and Ketones and Reductive Methylation of Amines
Authors: Firouzabadi Habib , Iranpoor Nasser , Alinezhad Heshmatollah
Published: January 2003

The reducing agent is easily prepared in an almost quantitative yield from commercially available starting materials. This compound is stable under mild aqueous acidic conditions (pH 4–6) and survives in H2O for several days without losing its reducing abilities. ZrBDC has been successfully used for the reduction of imines and enamines, reductive amination of aldehydes and ketones, and reductive methylation of amines.
Alkylsulfonioarylene and Thioarylene Polymers Derived from Sulfonium Electrophiles
Authors: Tsuchida Eishun , Oyaizu Kenichi
Published: January 2003

Superacidification of sulfoxides and sulfinates effects the electrophilic substitution reaction of the resulting hydroxysulfonium ions onto aromatic rings with the elimination of H2O at room temperature. The present account emphasizes the utility of the reaction for use as an elementary step in organic synthesis. The product, the alkyldiarylsulfonium ion, often quantitatively obtained, allows the synthesis of alkylsulfonio-bridged (λ4-alkylsulfanyliumdiyl) aromatic polymers. High molecular-weight poly(alkylsulfonioarylene) salts with a wide range of structural dimensionalities from linear to network architectures have been made accessible by the regioselective condensation of aryl sulfoxides. The polymers possess interesting properties such as good solubility in polar organic solvents and sometimes even in H2O, susceptibility to nucleophiles to provide thioarylene derivatives, photo-degradability, and electric semiconductivity, according to the dimensionality of the molecule. The synthetic chemistry of the alkylsulfonioarylene polymers as well as their possible applications in high molecular-weight poly(thioarylene) synthesis, photochemical recycling processes of an engineering plastic poly(thio-1,4-phenylene), and photo-resist technologies, are reviewed.
Kinetic Analysis of the Cleavage of the Ribose Phosphodiester Bond within Guanine and Cytosine-Rich Oligonucleotides and Dinucleotides at 65–200 °C and Its Implications Concerning the Chemical Evolution of RNA
Authors: Kawamura Kunio
Published: January 2003

A monitoring method of rapid hydrothermal reactions was successfully applied to a kinetic analysis of the cleavage of a ribose phosphodiester bond within oligonucleotides and dinucleotides at 150–200 °C. The apparent rate constants (kapp) of degradation of the ribose 3′,5′-cytidylylguanosine sequence (-C3′pGd-) within oligonucleotides and dinucleotides were determined, where the -C3′pGd- sequence in oligonucleotides is less stable than 2′,5′-cytidylylguanosine (C2′pG) and 3′,5′-cytidylylguanosine (C3′pG). It was unexpected that the stability of the target sequence would be dependent on the surrounding sequences of the oligonucleotides, although the temperatures used in the study were extremely higher than the melting points. The stability of a phosphodiester bond of 2′-deoxycytidylyl-2′-deoxyguanosine (CdpGd) is much higher than that of a ribose phosphodiester bond at low temperatures, but becomes comparable at 200 °C. During the degradation of C2′pG or C3′pG, interconversion between C2′pG and C3′pG was observed along with cleavage of the phosphodiester bond. Based on an analysis of the extent of interconversion, the apparent rate constants of the disappearance of C2′pG and C3′pG were dissected into the rate constants of hydrolysis (khy) and interconversion (kint), where the values of khy were greater than those of kint. The apparent activation energy of the degradation of the target sequence was 100–109 kJ mol−1 for oligonucleotides, 90 kJ mol−1 for C3′pG, and 87 kJ mol−1 for C2′pG, and 139 kJ mol−1 for CdpGd. The apparent activation enthalpy and entropy changes of the degradation of the target sequence were also determined; the values of the activation parameter were ΔH≠app = 94–105 kJ mol−1 and ΔS≠app = −(36–59) J mol−1 T−1 for five oligonucleotides, ΔH≠app = 86 kJ mol−1 and ΔS≠app = −97 J mol−1 T−1 for C3′pG, ΔH≠app = 84 kJ mol−1, ΔS≠app = −105 J mol−1 T−1 for C2′pG, and ΔH≠app = 135 kJ mol−1, ΔS≠app = +2 J mol−1 T−1 for CdpGd. The activation parameters, ΔH≠app and ΔS≠app, for the oligonucleotides increased with the length of the surrounding sequence of -C3′pGd-; this fact clearly demonstrates the existence of the influence of the surrounding sequence for the stability of the target ribose phosphodiester bond. Based on a kinetic analysis, the reaction mechanism of the degradation of the ribose phosphodiester bond at high temperatures is discussed. Furthermore, possible pathways of the chemical evolution of RNA are discussed from the viewpoint of the hydrothermal origin of life.
Substituent Effects in the 1,1-Diphenylcarbenium Systems: Hydration and Bromination of 1,1-Diphenylethylenes
Authors: Fujio Mizue , Rappoport Zvi , Uddin Md Khabir , Kim Hyun-Joong , Tsuno Yuho
Published: January 2003

Substituent effects log (kXY/kHH)Br on the bromination of 1,1-diarylethylenes were analyzed in comparison with those log (kXY/kHH)OPNB in the solvolysis of 1,1-diarylethyl p-nitrobenzoates. The non-linearity and non-additivity were significant in both cases. While an extended Brønsted relationship against ΔpKBH+ for diarylethylenes holds in the latter process, of particular importance is the finding of a precise linear correlation between the bromination and solvolysis for the whole substituents; log (kXY/kHH)OPNB = 1.07 log (kXY/kHH)Br − 0.83 ΔσR+, where the ΔσR+ is the Yukawa–Tsuno resonance parameter. This relationship can be rewritten in the form of an extended Brønsted correlation: log (kXY/kHH)Br = α [log KXY/KHH]Br, where [log KXY/KHH]Br = −ΔpKBH+ + 0.81 ΔσR+, for the thermodynamic stabilities of the intermediate in the bromination. The constant α coefficient should suffice as convincing evidence for the absence of a coordinate shift of the transition state that is induced by varying substituents in the bromination process. The additional contribution of 0.81 ΔσR+ should be ascribed to the differential cationic charge at the benzylic position in the bromination transition state; a constant coefficient indicates a fixed position of the bromination transition state, irrespective of the fixed-Y subset.
Preparation of Hexakis(6-O-mesitylsulfonyl)cyclomaltooctaoses and Structural Validation of the Four Isomers Using Heteronuclear Multiple Bond Correlation Spectroscopy
Authors: Yamamura Hatsuo , Miyachi Sadaichi , Kano Kazuaki , Araki Shuki , Lee Kenichi , Kawai Masao , Ueyama Norikazu
Published: January 2003

Four cyclomaltooctaose derivatives 1a–d, which possess six mesitylsulfonyloxy groups on their C(6) atoms, were prepared. The assignment of the regiosiomers was performed by observing the long-range coupling through a glycoside linkage between H(1′) –C(4) and C(1′) –H(4) using a heteronuclear multiple-bond correlation (HMBC) method.
Biotransformation of Cycloalkanediones by Caragana chamlagu
Authors: Chai Wen , Sakamaki Hiroshi , Kitanaka Susumu , Horiuchi C Akira
Published: January 2003

The biotransformation of alkylcycloalkanediones using suspension plant cultured-cells of Caragana chamlagu gave oxo carboxylic acids by oxidative cleavage. 5,6-Dioxoheptanoic acid was obtained in high yield (95%) in a short time (7 h) from 2-methyl-1,3-cyclohexanedione. However, 1,2- and 1,4-cycloalkanediones were reduced stereoselectively and trans-1,2-cyclohexanediol and trans-1,4-cyclohexanediol were obtained, respectively. The mechanism of the oxidative cleavage of alkylcycloalkanediones is also discussed.
Synthesis and β-Hydrogen Elimination of Water-Soluble Dialkylplatinum(II) Complexes in Water
Authors: Komiya Sanshiro , Ikuine Miho , Komine Nobuyuki , Hirano Masafumi
Published: January 2003

Water-soluble cis-dialkylplatinum(II) complexes cis-[PtR2L2] (L2 = 2 TPPTS, 2 THMP, DHMPE; R = Me, Et, Ph) have been prepared by ligand displacement reactions of [PtR2(1,5-COD)] with L2. They are stable in water; the diethylplatinum(II) complexes cis-[PtEt2(TPPTS)2] undergo preferential disproportionation of the ethyl groups in water, giving ethylene and ethane in 1 : 1 ratio via β-hydrogen elimination in preference to protonolysis at 80 °C. A retardation effect of added free TPPTS on the reaction rate and a deuterium labelling study suggest a mechanism involving prior dissociation of TPPTS for reversible β-hydrogen elimination.
Asymmetric Cyclopropanation and Aziridination Reactions of Olefins Catalyzed by Cu(I)-Binaphthyldiimine Complexes
Authors: Suga Hiroyuki , Kakehi Akikazu , Ito Suketaka , Ibata Toshikazu , Fudo Tomomi , Watanabe Yuzuru , Kinoshita Yoshinori
Published: January 2003

The chiral Cu(I)-N,N′-bis(2,6-dichlorobenzylidene)-1,1′-binaphthyl-2,2′-diamine complex was found to be an efficient catalyst for asymmetric cyclopropanation and aziridination reactions of olefins with l-menthyl diazoacetate and [N-(p-tolylsulfonyl)imino]phenyliodinane, respectively. Among mono- and disubstituted olefins, 1,1-diarylethylenes showed extremely high enantioselectivities (up to 98% ee) in the cyclopropanation reactions in the presence of a chiral Cu(I)-catalyst (2 mol%). In the case of aziridination reactions catalyzed by the same Cu(I)-catalyst (10 mol%), the reaction of trans-substituted 3-aryl-2-propenoates and 1-substituted trans-3-aryl-2-propen-1-ones showed satisfactory results in term of the enantioselectivities (up to 98% ee).
Photodeoxygenation and α-Cleavage Reactions of Selenoxides
Authors: Yamazaki Yuko , Tsuchiya Takahiro , Hasegawa Tadashi
Published: January 2003

Upon UV-irradiation, diphenyl and dibenzyl selenoxides underwent deoxygenation and α-cleavage competitively to give selenides, and diselenides and others, respectively. A mechanism of bimolecular photodeoxygenation is proposed, since the yields of the photoproducts were dependent on the initial concentration of the selenoxides.
A Novel Approach to Furopyrimidinones Using Dry Media
Authors: Kidwai Mazaahir , Rastogi Shweta , Venkataramanan R
Published: January 2003

An environmentally benign approach to the synthesis of furopyrimidin-4(3H)-one under microwave irradiation (MWI) using an inorganic solid support for catalytic activity as well as an energy-transfer medium is described. The reaction time can be decreased from hours to minutes along with a yield enhancement. In addition, the differential activity of various solid supports was studied for a reaction which enables one to accomplish the one-pot synthesis of the required product via the 2-aminofuran-3-carbonitrile intermediate.
First Syntheses of Iodinated 1,6-Dithiapyrene Derivatives
Authors: Morita Yasushi , Miyazaki Eigo , Toyoda Jiro , Nakasuji Kazuhiro
Published: January 2003

An improved synthetic method of 1,6-dithiapyrene (DTPY) was found with a practical yield in a reproducible manner. Iodinated DTPY derivatives were prepared as new donor molecules, and the crystal structure of 2,7-diiodoDTPY was clarified by an X-ray structure analysis.
Electrooxidative Formation of 1,2-Diaroylcyclopropanes from 1,3-Diaroylpropanes in the Presence of KI
Authors: Okimoto Mitsuhiro , Takahashi Yukio , Kakuchi Toyoji
Published: January 2003

Various 1,2-diaroylcyclopropanes were obtained in good yields by the indirect electrochemical oxidation of 1,3-diaroylpropanes in the presence of catalytic amounts of KI under very mild conditions.
Cation Complexation, Photochromism, and Aggregation of Copolymers Carrying Crown Ether and Spirobenzopyran Moieties at the Side Chains
Authors: Keiichi Kimura , Nakamura Makoto , Sakamoto Hidefumi , Uda Ryoko Mizutani , Sumida Miwa , Yokoyama Masaaki
Published: January 2003

Methacrylate monomers containing monoaza-12-crown-4 and spirobenzopyran moieties were copolymerized to obtain polymers carrying their moieties at the side chains. The crown ether-spiropyran polymers can bind alkali metal ions with their crown ether moiety in the selectivity order of Na+ > K+ > Li+. The spirobenzopyran moiety, on the other hand, undergoes UV-light-induced isomerization from its spiropyran to the merocyanine form, leading to merocyanine aggregate formation. The metal-ion complexation of the crown ether moiety enhanced interpolymer merocyanine aggregation by extending the polymer chain on the basis of the electrostatic repulsion between the complexed metal ions. Thus, tetrahydrofuran solutions of a crown ether-spiropyran copolymer with 1 : 1 composition of the moieties led to significant polymer precipitation on UV irradiation in the presence of an alkali metal ion, especially Li+. The photochromism and aggregate formation were studied in detail by absorption and fluorescence spectrometry and by light scattering measurements.
Fe2O3 Particles Coated with Silica Using TEOS
Authors: Sato Satoshi , Takahashi Ryoji , Sodesawa Toshiaki , Tanaka Rieko
Published: January 2003

Fine particles of SiO2-coated Fe2O3 were prepared by depositing silica on an iron(III) hydroxide precipitate using tetraethoxysilane (TEOS). The silica deposition proceeded under mild conditions at 20 °C; crystallization hardly occurred and silica loading was controlled by the amount of TEOS charged, whereas the precipitate crystallized to a mixture of FeO(OH) and α-Fe2O3 under hydrothermal conditions. The specific surface area of the SiO2-coated Fe2O3 increased with silica loading, and exceeded 280 m2 g−1 even after calcination at 500 °C. The silicate species deposited on the precipitate of iron(III) hydroxide prevented the primary particles from agglomerating during calcination, resulting in the high surface area and hard reducibility of the SiO2-Fe2O3.
Enantioselective Carbonyl-Ene Reaction of Glyoxal Derivatives Catalyzed by Cationic 3-Oxobutylideneaminatocobalt(III) Complexes
Authors: Kezuka Satoko , Kogami Youichi , Ikeno Taketo , Yamada Tohru
Published: January 2003

Optically active 3-oxobutylideneaminatocobalt(III) complexes were designed for the catalytic enantioselective carbonyl-ene reaction. Varieties of counter anions of cationic cobalt(III) complexes were screened and hexafluoroantimonate was found to be the most effective. In the presence of cobalt(III) hexafluoroantimonate complex 1f, the enantioselective carbonyl-ene reaction of various alkenes with glyoxal derivatives was carried out to afford the corresponding homoallylic alcohols in high yields and with high enantioselectivities. Even in the presence of 0.2 mol% cobalt(III) complexes, the reaction proceeded in high yield and with maintained high enantioselectivity. The absolute configuration of the optically active product was determined and a reasonable explanation for the enantioselection in the present carbonyl-ene reaction catalyzed by the cobalt complex was proposed.
An Extended Fano–DeVoe Polarizability Theory Similar to the Bayley–Nielsen–Schellman Secular Matrix Method: CD Calculations of Polypeptides Having α-Helix, β -Sheet, and β -Turn Structures
Authors: Ito Hirotoshi
Published: January 2003

We have expanded the previous Bayley–Nielsen–Schellman type polarizability theory so as to involve a new diagonal type of CAE (Condon, Alter, Eyring) interaction energy as {(the previous diagonal type of CAE interaction energy) − (the electrostatically corrected ground state energy)}, which corresponds to the term pointed out by Misra in his review article. For the CD and UV band shape functions which were previously derived in a different way, we have newly rederived the polymer CD and UV band shape functions by making use of the Green’s function method, starting from the well-known text book by Eyring et al. For a monomer polarizability tensor, the two most often used Lorentzian and Gaussian band approximations will be studied together with practically necessary relationships on the bandwidths.

The theory has been applied to the CD and UV absorption calculations on polypeptides. Previously, unless one scaled the earlier diagonal type of CAE interaction energy, poor predictions were then obtained, especially for the β-sheet polypeptides as well as the small α-helix and β-turn tripeptides. Now, using the new diagonal type of CAE interaction energies, promising CD results have been obtained together with reasonable UV spectral shifts.
Equation of State for Free Energy of Homogeneous Nucleation Derived by Monte Carlo Simulations
Authors: Yamada Yuri , Kataoka Yosuke
Published: January 2003

We performed Monte Carlo simulations for the homogeneous nucleation on supersaturated Lennard–Jones vapor phase to estimate the equation of state for free energy of the nucleation. The calculations were performed on each system with a fixed number of particles. The initial configuration was distorted cubic lattice. The sample was cooled to low temperature, where all particles become a cluster. In the second stage it was heated enough to vaporize; the monomer phase was obtained. In the third run, the stabilized cluster was heated under the condition that the cluster was not allowed to decompose. In the last run, the system was cooled from initial monomer phase with a condition that the particles were not allowed to make any connections. Helmholtz free energies of the cluster and the monomer phase were obtained by thermodynamic integration. The obtained size of critical nucleus was comparable to the results of the molecular dynamics simulation.
Ethylenedioxy-Containing Tetrathiapentalene Derivative with Ethylthio Chains, C2TEO-TTP
Authors: Kimura Shinya , Nii Hirofumi , Kurai Hiroyuki , Takeuchi Tomoaki , Katsuhara Mao , Mori Takehiko
Published: January 2003

A new oxygen-containing π-electron donor having ethylthio chains, C2TEO-TTP (2-[4,5-bis(ethylthio)-1,3-dithiol-2-ylidene]-5-(4,5-ethylenedithio-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene), has been synthesized. Single-component C2TEO-TTP forms a β′-like dimerized structure. The 2 : 1 salts with PF6−, ClO4−, and AsF6− have a uniform β-type structure isostructual to the ethylenedithio analog, (C2TET-TTP)2ClO4, and are metallic down to liquid helium temperatures. On the other hand, (C2TEO-TTP)2Au(CN)2 has dimeric donor arrangement, and shows hysteretic temperature dependence of the conductivity.
Structural and Electrical Properties of Novel Molecular Conductors Based on Extended-TTF Donors BDT-TTP and I− Anions
Authors: Cui HengBo , Otsuka Takeo , Kobayashi Akiko , Misaki Yohji , Kobayashi Hayao
Published: January 2003

With the aim of developing organic conductors with new types of molecular arrangements, some organic conductors composed of elongated π donors BDT-TTP (2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene) and simple I− anions were prepared by electrocystallization. The crystal of (BDT-TTP)3I has a very unique three-dimensional donor arrangement, where six BDT-TTP molecules are crystallographically independent. Despite the three-dimensional intermolecular short S···S network, the examination of C=C bond lengths of six BDT-TTP molecules indicates an inhomogeneous charge distribution, which is unfavorable for the formation of metallic bands. The resistivity measurements showed the system to be a semiconductor with a very small activation energy. On the other hand, the needle-shaped crystal has β-type donor arrangement and 2 : 1 stoichiometry. The crystal of β-(BDT-TTP)2I retains its metallic state down to 2 K. Though an open Fermi surface was obtained by tight-binding band calculation, the fairly strong two-dimensionality of the electronic structure was suggested.
Anatomy of The Anatomy of Racial Inequality
Authors: Raphael Steven
Published: January 2003

In this review, I summarize and offer thoughts about two arguments key to Glenn Loury's analysis of the anatomy of racial inequality. The first concerns the idea that many negative stereotypes held about blacks in the United States are self-fulfilling, despite little evidence of inherent differences between the races in human potential. The second argument concerns the proposition that the racial stigmatization of blacks is deeply embedded in the public consciousness and that such stigma racially biases socially cognitive processes to the severe detriment of African-Americans.
Review of Shleifer's Inefficient Markets
Authors: Zwiebel Jeffrey
Published: January 2003

This excellent book provides the reader with a broad introduction to, and a powerful advocacy of, behavioral finance. In the tradition of the best of the Clarendon Lecture Series, Andrei Shleifer provides a clear context and motivation for a collection of his influential ideas in this field, emphasizing central themes that link together the wide scope of this work. Topics include: investor sentiment, the limits of arbitrage, the closed-end fund puzzle, positive feedback investment, and both market overreaction and underreaction to news, as well as general discussions on the motivation for this research and promising future directions.
Review of Grossman and Helpman's Special Interest Politics
Authors: Baron David P
Published: January 2003

In Special Interest Politics Gene Grossman and Elhanan Helpman examine how special-interest groups influence political outcomes for the benefit of their members. The authors take interest groups seriously by considering a range of theories and supporting evidence on interest group activity. Their book provides perspectives on how to study interest group politics and a set of methods for that study. Although the authors present a number of standard models, the book contains much that is new. The reader takes away a multitude of results, tools, models, and new research ideas. The result is an outstanding book full of insight, useful methods, and perspective.
Phosphorylation of eIF4E attenuates its interaction with mRNA 5′ cap analogs by electrostatic repulsion: Intein-mediated protein ligation strategy to obtain phosphorylated protein
Authors: ZUBEREK JOANNA , WYSLOUCH-CIESZYNSKA ALEKSANDRA , NIEDZWIECKA ANNA , DADLEZ MICHAL , STEPINSKI JANUSZ , AUGUSTYNIAK WOJCIECH , GINGRAS ANNE-CLAUDE , ZHANG ZHIBO , BURLEY STEPHEN K. , SONENBERG NAHUM , STOLARSKI RYSZARD , DARZYNKIEWICZ EDWARD
Published: January 2003

Phosphorylation of the eukaryotic initiation factor eIF4E in response to mitogenic stimuli and cytokines is implicated in the regulation of the initiation step of translation. It still remains unclear how the phosphorylation of eIF4E regulates the translation. To address this problem, we applied a unique technique in protein engineering, intein-mediated protein ligation, to synthesize eIF4E, which is selectively phosphorylated at Ser 209. Using selectively chosen synthetic cap analogs, we compared quantitatively the cap affinity for phosphorylated and unphosphorylated eIF4E by a fluorometric time-synchronized titration method. A 1.5- to 4.5-fold reduction of the cap affinity for phosphorylated eIF4E was observed, depending on the negative charge of the 5′-to-5′ phosphate chains as well as the presence of a longer tetraribonucleotide strand. Possible implications for understanding the regulation of eIF4E functioning, cap complex formation, and stability, are discussed.
Mechanism of molecular interactions for tRNAVal recognition by valyl-tRNA synthetase
Authors: FUKAI SHUYA , NUREKI OSAMU , SEKINE SHUN-ICHI , SHIMADA ATSUSHI , VASSYLYEV DMITRY G. , YOKOYAMA SHIGEYUKI
Published: January 2003

The molecular interactions between valyl-tRNA synthetase (ValRS) and tRNAVal, with the C34-A35-C36 anticodon, from Thermus thermophilus were studied by crystallographic analysis and structure-based mutagenesis. In the ValRS-bound structure of tRNAVal, the successive A35-C36 residues (the major identity elements) of tRNAVal are base-stacked upon each other, and fit into a pocket on the α-helix bundle domain of ValRS. Hydrogen bonds are formed between ValRS and A35-C36 of tRNAVal in a base-specific manner. The C-terminal coiled-coil domain of ValRS interacts electrostatically with A20 and hydrophobically with the G19•C56 tertiary base pair. The loss of these interactions by the deletion of the coiled-coil domain of ValRS increased the KM value for tRNAVal 28-fold and decreased the kcat value 19-fold in the aminoacylation. The tRNAValKM and kcat values were increased 21-fold and decreased 32-fold, respectively, by the disruption of the G18•U55 and G19•C56 tertiary base pairs, which associate the D- and T-loops for the formation of the L-shaped tRNA structure. Therefore, the coiled-coil domain of ValRS is likely to stabilize the L-shaped tRNA structure during the aminoacylation reaction.
Nuclear protein synthesis: A re-evaluation
Authors: NATHANSON LUBOV , XIA TIANLI , DEUTSCHER MURRAY P.
Published: January 2003

It has been reported that nuclei from HeLa cells are responsible for ∼10%–15% of total cellular protein synthesis. We show here that isolated Chinese hamster ovary (CHO) and HeLa cell nuclei are essentially inactive for translation, and that the earlier results were most likely due to cytoplasmic contamination. Moreover, we suggest that the nascent polypeptides observed in nuclei of permeabilized cells may have been due to “overpermeabilization” and consequent damage to the cells. Based on this information, we conclude that nuclear protein synthesis, if it exists, is limited to less than 1% of that in cells.