bluuebunny/crossref_metadata_2025 huggingface dataset:
Toward Effective International Cooperation on Climate Change: Numbers, Interests and Institutions
Authors: Victor David G.
Published: July 2006

Arild Underdal's “law of the least ambitious program” is properly pessimistic about the prospects for cooperation in the international system where nations must give their consent to be bound by meaningful commitments. Those pessimistic expectations are now being revealed in the collective efforts to address the problem of climate change, notably through the Kyoto Protocol. Over-coming Underdal's law requires narrowing the numbers of countries that participate in key climate agreements and tailoring membership so that just the most important countries are engaged and there are strong incentives to avoid defection. At the same time, the effectiveness of cooperative efforts would gain from fuller use of nonbinding instruments, review procedures and high level conferences—as were put to effective use in the North Sea cooperation, for example— in addition to legally binding international law through instruments such as the Kyoto Protocol. Sadly, most of the conventional wisdom runs the opposite direction, favoring binding treaties among large numbers of countries.
A study of the effect of term proximity on query expansion
Authors: Vechtomova Olga , Wang Ying
Published: July 2006

Query expansion terms are often used to enhance original query formulations in document retrieval. Such terms are usually selected from the entire documents or from windows or passages surrounding query term occurrences. Arguably, the semantic relatedness between terms weakens with the increase in the distance separating them. In this paper we report a study that was conducted to systematically evaluate different distance functions for selecting query expansion terms. We propose a distance factor that can be effectively combined with the statistical term association measure of mutual information for selecting query expansion terms. Evaluation of the TREC collection shows that distance-weighted mutual information is more effective than mutual information alone in selecting terms for query expansion.
A ‘Demented Work Ethic’ and a ‘Lifestyle Firm’: Discourse, Identity, and Workplace Time Commitments
Authors: Kuhn Timothy
Published: July 2006

One key to understanding the contours of late modernity is to examine workers’ allocations of time to their organizations. In this article, I frame workplace time commitments as the outcome of two forces: individuals’ efforts to portray a positive and distinctive identity (identity work) and the organizational and social discourses shaping those identities (identity regulation). Analysis of interviews with 53 employees from two distinct organizations shows that identity work and identity regulation related to workplace time commitments are not the result of totalizing managerial discourses, but are influenced by the arrays of discursive resources proffered by both locales and organizational practices. Importantly, these arrays tend to ‘tilt’ toward agency or structure in the conceptions of the individual–organization relationship they afford. Based on this finding, I argue that studies of workplace control and resistance should examine the features of such arrays of discursive resources, that understanding these assemblies of discursive resources can provide insight on the institutionalization of workplace practices, and that claims about modernity's totalizing influences on identity must be tempered by considering locale-specific discourses.
Neither Market nor Hierarchy nor Network: The Emergence of Bazaar Governance
Authors: Demil Benoît , Lecocq Xavier
Published: July 2006

A growing body of literature describes the open source phenomenon in the software industry. Drawing on transaction cost economics, we propose that open source projects illustrate a new generic governance structure — which we label bazaar governance — based on a specific legal contract: the open licence. We characterize this structure in terms of its strengths and weaknesses and compare it to market, firm and network forms. Low levels of control and weak incentives intensity are distinctive features of bazaar, lending a high uncertainty to governed transactions. However, bazaar governance promotes the openness of open source communities, which can generate strong positive network externalities and subsequent efficiency in cumulative transactions. Our theoretical developments offer a potential basis for future research.
Aggregation and the Role of Trusted Third Parties in SME E-Business Engagement
Authors: Lockett Nigel , Brown David H.
Published: July 2006

It is against the background of low engagement by SMEs in e-business that this article seeks to highlight the potential importance of aggregation and of the role of trusted third parties in facilitating higher levels of involvement. The article is based on an ongoing SME e-business research programme and reports on some recent research on SMEs that were using high complexity e-business applications; it explores the extent to which the research findings could address the core concern of low engagement. This qualitative case study based research includes analysis of data collected from 13 community intermediaries, acting as trusted third parties. It concludes that the role of community intermediaries appears to be central to the adoption of critical e-aggregation applications provided by service providers. For policymakers, this important role of critical e-aggregation applications in facilitating e-business engagement by SMEs has emerged as part of this research but there is limited evidence of policy initiatives that reflect this.
What is new in the ‘south’? Consumer culture and the vicissitudes of poor youth’s identity construction in urban Brazil
Authors: De Castro Lucia Rabello
Published: July 2006

This study analyses the specificities of youth identity construction in Brazil in the context of global transformations and the particularities of the Brazilian model of development. Poor urban Brazilian youngsters’ demands to consume, as a ‘mode of inclusion’ in society, achieve short-term gains that narrow down prospective visions of the self. A ‘logic of survival’ hypothesis is proposed to account for the process of identity construction whereby encapsulated and rigid, rather than hybridized and creative, identities are constituted. The hypothesis is illustrated with a discussion of the cases of the drug dealer, the religious fanatic and the labourer. New cultural forms of consumer culture also convey claims for recognition and justice, shown by the musical expressions coming from the peripheries of big cities. It remains to be seen whether musical and artistic expressions, as possible factors that can enhance self-respect and group solidarity among poor youth, will not be consumed just as a new item of the culture industry.
Recommunalization of the disenfranchised
Authors: Arrigo Bruce A. , Takahashi Yoshiko
Published: July 2006

This article examines the eight-stage model of recommunalizing the homeless in a Single Room Occupancy (SRO) as developed by Arrigo and its theoretical grounding, based on principles derived from critical criminology. In particular, by retrospectively identifying how several key concepts emanating from peacemaking, anarchist and cultural criminology are illustrated by the SRO’s formation and operation, the article demonstrates where and how the dynamics of identity formation, the development of collective residential power and evolving reforms function throughout the facility. The article concludes by tentatively exploring the relevance of the proposed model for the resocialization and community re-entry of other similarly disenfranchised constituencies.
Are Country and Culture Values Interchangeable?
Authors: Sawang Sukanlaya , Oei Tian P.S. , Goh Yong Wah
Published: July 2006

Cross cultural research in occupational stress and coping has produced a wealth of knowledge. Although advances have been made, there are still problems to be solved. One of these problems is the confusion generated in the literature by researchers claiming that nation or country represents cultural values, and the use of the two terms interchangeably. It remains unclear whether this practice is correct. The present article reported on this by using 511 full-time employees from Australia, Singapore and Sri Lanka to study occupational stress and coping. Results revealed that cultural value paradigms (i.e. Individualism–Collectivism) were distributed across the three nations such that over 60% of participants were either high or low in both I–C paradigms. The findings also indicated that the relationship between cultural value paradigm and country impacted on stress and coping differently. The study shows that significant differences exist within countries as well as between countries, such that any attempt to equate ‘culture’ with ‘country’ becomes problematic. Therefore these findings established that country or nation is not the same as culture values and cannot be used interchangeably.
Leader-Member Exchange Theory and Research: Accomplishments and Future Challenges
Authors: van Breukelen Wim , Schyns Birgit , Le Blanc Pascale
Published: July 2006

In the Leader-Member Exchange (LMX) theory of leadership, the quality of the exchange relationship between a leader and a particular member of a work unit, team or organization is the basic unit of analysis (dyad). In this article, we try to answer the question whether research on the various aspects of the exchange processes between leaders and their subordinates is consistent with the theoretical underpinnings of LMX theory. Our focus is on the similarities and differences between the theoretical assumptions of LMX theory and the way the core concepts are elaborated in empirical studies. Although LMX theory has resulted in a number of useful accomplishments, both theoretical and practical, it still faces a number of challenges. The main challenges are to carry out a thorough and consistent refinement of the measuring instruments used, and to gain more insight into the mutual behaviours, attributions, and evaluations which facilitate or inhibit the development of high-quality working relationships.
The character of penal control in Latin America
Authors: Birkbeck Christopher , Pérez-Santiago Neelie
Published: July 2006

While imprisonment is often referred to in Englis-speaking countries as ‘doing time’, in Venezuela this phrase is never used; people speak of ‘discharging the sentence’. This linguistic difference is a useful starting point for a reflection on cultural differences in the character of penal control. In this article, we examine the administration of sentence remissions in a Venezuelan prison during the six years following the enactment of the Sentence Remission Law (1993). Contrary to the active role envisioned by that law, penal bureaucracy assumed a passive role, converting remissions into a claims system for prisoners. Such claims were linked inefficiently to opportunities for early or full release, leading some offenders to spend more time than necessary in prison. Nonstandardized procedures for factoring remissions into the proportion of time served, together with frequent errors in date computation, also injected a random element into the flow of time. Time served in prison was therefore jointly determined by the offender's abilities as a claimant and by the random operation and errors of the penal timekeeping system. Remissions set the stage for a game of chance that is antithetical to the regularity, predictability and immutability that supposedly characterize penal sanctions.
Discovery of cancer vaccination protocols with a genetic algorithm driving an agent based simulator
Authors: Lollini Pier-Luigi , Motta Santo , Pappalardo Francesco
Published: July 2006

Background

Immunological prevention of cancer has been obtained in HER-2/neu transgenic mice using a vaccine that combines 3 different immune stimuli (Triplex vaccine) that is repeatedly administered for the entire lifespan of the host (Chronic protocol). Biological experiments leave open the question of whether the Chronic protocol is indeed the minimal vaccination schedule affording 100% protection, or whether shorter protocols could be applied that would result in the same efficacy. A biological solution would require an enormous number of experiments, each lasting at least one year. Therefore we approached this problem by developing a simulator (SimTriplex) which describes the immune response activated by Triplex vaccine. This simulator, tested againstin vivoexperiments on HER-2/neu mice, reproduces all the vaccination protocols used in thein vivoexperiments. The simulator should describe any vaccination protocol within the tested range. A possible solution to the former open question using a minimal search strategy based on a genetic algorithm is presented. This is the first step toward a more general approach of biological or clinical constraints for the search of an effective vaccination schedule.

Results

The results suggest that the Chronic protocol included a good number of redundant vaccine administrations, and that maximal protection could still be obtained with a number of vaccinations ~40% less than with the Chronic protocol.

Conclusion

This approach may have important connotations with regard to translation of cancer immunopreventive approaches to human situations, in which it is desirable to minimize the number of vaccinations. We are currently setting up experiments in mice to test whether the actual effectiveness of the vaccination protocol agrees with the genetic algorithm.
Quantification of functional weakness and abnormal synergy patterns in the lower limb of individuals with chronic stroke
Authors: Neckel Nathan , Pelliccio Marlena , Nichols Diane , Hidler Joseph
Published: July 2006

Background

The presence of abnormal muscle activation patterns is a well documented factor limiting the motor rehabilitation of patients following stroke. These abnormal muscle activation patterns, or synergies, have previously been quantified in the upper limbs. Presented here are the lower limb joint torque patterns measured in a standing position of sixteen chronic hemiparetic stroke subjects and sixteen age matched controls used to examine differences in strength and coordination between the two groups.

Methods

With the trunk stabilized, stroke subjects stood on their unaffected leg while their affected foot was attached to a 6-degree of freedom load cell (JR3, Woodland CA) which recorded forces and torques. The subjects were asked to generate a maximum torque about a given joint (hip abduction/adduction; hip, knee, and ankle flexion/extension) and provided feedback of the torque they generated for that primary joint axis. In parallel, EMG data from eight muscle groups were recorded, and secondary torques generated about the adjacent joints were calculated. Differences in mean primary torque, secondary torque, and EMG data were compared using a single factor ANOVA.

Results

The stroke group was significantly weaker in six of the eight directions tested. Analysis of the secondary torques showed that the control and stroke subjects used similar strategies to generate maximum torques during seven of the eight joint movements tested. The only time a different strategy was used was during maximal hip abduction exertions where stroke subjects tended to flex instead of extend their hip, which was consistent with the classically defined "flexion synergy." The EMG data of the stroke group was different than the control group in that there was a strong presence of co-contraction of antagonistic muscle groups, especially during ankle flexion and ankle and knee extension.

Conclusion

The results of this study indicate that in a standing position stroke subjects are significantly weaker in their affected leg when compared to age-matched controls, yet showed little evidence of the classic lower-limb abnormal synergy patterns previously reported. The findings here suggest that the primary contributor to isometric lower limb motor deficits in chronic stroke subjects is weakness.
Intraspecific variation in thermal tolerance and heat shock protein gene expression in common killifish,Fundulus heteroclitus
Authors: Fangue Nann A. , Hofmeister Myriam , Schulte Patricia M.
Published: July 2006

Populations of common killifish, Fundulus heteroclitus, are distributed along the Atlantic coast of North America through a steep latitudinal thermal gradient. We examined intraspecific variation in whole-animal thermal tolerance and its relationship to the heat shock response in killifish from the northern and southern extremes of the species range. Critical thermal maxima were significantly higher in southern than in northern fish by ∼1.5°C at a wide range of acclimation temperatures (from 2-34°C), and critical thermal minima differed by ∼1.5°C at acclimation temperatures above 22°C, converging on the freezing point of brackish water at lower acclimation temperatures. To determine whether these differences in whole-organism thermal tolerance were reflected in differences in either the sequence or regulation of the heat shock protein genes(hsps) we obtained complete cDNA sequences for hsc70, hsp70-1 and hsp70-2, and partial sequences of hsp90α and hsp90β. There were no fixed differences in amino acid sequence between populations in either hsp70-1 or hsp70-2, and only a single conservative substitution between populations in hsc70. By contrast, there were significant differences between populations in the expression of many, but not all, of these genes. Both northern and southern killifish significantly increased hsp70-2 levels above control values(Ton) at a heat shock temperature of 33°C, but the magnitude of this induction was greater in northern fish, suggesting that northern fish may be more susceptible to thermal damage than are southern fish. In contrast, hsp70-1 mRNA levels increased gradually and to the same extent in response to heat shock in both populations. Hsc70 mRNA levels were significantly elevated by heat shock in southern fish, but not in northern fish. Similarly, the more thermotolerant southern killifish had a Ton for hsp90α of 30°C, 2°C lower than that of northern fish. This observation combined with the ability of southern killifish to upregulate hsc70 in response to heat shock suggests a possible role for these hsps in whole-organism differences in thermal tolerance. These data highlight the importance of considering the complexity of the heat shock response across multiple isoforms when attempting to make linkages to whole-organism traits such as thermal tolerance.
Analytical Studies Using the Convection Electrode. XII. Anodic-stripping Voltammetry of Cadmium and Thallous Ions with the Pushed-out Mercury Drop Convection Electrode
Authors: Suzuki Junsuke
Published: July 2006

The investigation of the anodic-stripping voltammetry of cadmium or thallous ions in a 0.1 m potassium nitrate solution was carried out by using the pushed-out mercury Drop Convection Electrode (cf. J. Suzuki and T. Ozaki, This Bulletin, 37, 230 (1964)). The metals were deposited on the mercury electrode by rotating the disk at 600—1200 rpm, and the stripping was performed by a linearly-varying potential method. The anodic-stripping peak current was proportional to the square roots of the rotating rate of the disk and of the voltage scanning rate, and to the bulk concentration of cadmium or thallous ions. Using the present stripping procedure, it was possible to determine thallous and cadmium ions at concentrations as low as 1×107  m with a mean error of about ±2%.
ESR Studies of the Ion Pairs of the Terephthalonitrile Anion with Alkali Metal Cations
Authors: Nakamura Kazuo
Published: July 2006

The behavior of the alkali metal ions, Li, Na, and K, in solutions of terephthalonitrile in ethereal solvents was studied by means of the electron spin resonance of the anion radical. The metal ions formed ion pairs by association with the anion in solution at one of the two cyano groups; the rate at which the cation is transferred between these two groups determines the detailed structure of the ESR spectrum. Within the limits of slow transfer, the spectrum was interpreted in terms of splittings due to two sets of proton pairs and two non-equivalent nitrogens. As the transfer rate increased, the spectrum exhibited an alternating line width, until finally the splittings were averaged within the limits of the fast transfer rate. The transfer rate of cations in the same solvent was found to increase in the order of the size of cations. It also depended on the solvating power for the cation. At low concentrations and low temperatures, the ion pair tended to dissociate, thus giving free anions. The hyperfine interactions with the nuclear spin of the cations were also observed.
Calculation of the Electronic Structure of Cinnamic Acid by the Semi-empirical LCAO-SCF-MO Method
Authors: Nakamura Kenichiro , Kikuchi Shinichi
Published: July 2006

The photo-isomerization and photo-dimerization of cinnamic acid are discussed from the standpoint of the electronic structures in the ground and excited states. State energies, charge densities, bond orders and free valences are calculated by using the Pariser-Parr-Pople method, including the configuration interaction. The computed transition energies are in good agreement with the experimental results. It is found that the bond order between the α- and β-carbons of cinnamic acid decreases, while the free valences of the α- and β-carbons increases, upon the lowest electronic excitation. It is concluded that the photo-isomerization is due to the smaller bond order, and that the photo-dimerization is due to the larger free valences in the excited state of cinnamic acid.
Graphical Evaluation of the Rate Constants of the Elementary Reaction of the Non-stationary Polymerization
Authors: Kagiya Tsutomu , Izu Masatsugu , Machi Sueo , Fukui Kenichi
Published: July 2006

A graphical method for the interpretation of the kinetics of the non-stationary polymerization, and for the evaluation of the rate constants of elementary reactions, was proposed. It was shown that the rates of elementary reactions could be estimated with an extrapolating method using the kinetic data on the polymer yield and the number-average degree of polymerization of the polymer. The graphical method was then applied to some practical examples.
Charge Mobility of Organic Semiconductors under High Pressure. Anthracene
Authors: Kajiwara Takashi , Inokuchi Hiroo , Minomura Shigeru
Published: July 2006

The charge mobilities of anthracene single crystals were measured under high pressures up to 7.4 kbar. An experimental apparatus like Kepler’s was used. A sample holder was attached in a Drickamer-type high-pressure photocell, with kerosene employed as the pressure-transmitting fluid. The electron mobilities along the a and b crystal axes increased as the pressure applied increased; the values of the charge drift mobility at 7 kbar were 1.7 times as large as those at atmospheric pressure. The electron mobility along the c′ axis was nearly constant. The hole mobility, however, could not be measured, because the tail of the pulse signal, observed on the oscilloscope, was deformed.
Studies of the Electrolytic Reduction Mechanism of Anthracene, Benzophenone and Anthraquinone by the Use of Polarography and Electron Spin Resonance Spectroscopy
Authors: Umemoto Kisaburo
Published: July 2006

The electrochemical reduction mechanism of anthracene, benzophenone and anthraquinone was studied in N,N′-dimethylformamide (DMF) and/or its water mixture by means of polarography and electron spin resonance spectroscopy (ESR). The polarograms of these compounds consisted of two well-defined waves in anhydrous DMF: the first wave corresponds to the formation of the anion radical and the second wave to the reduction of the anion radical to the dinegative anion. When water was added, the limiting current of the first wave increased at the expense of the second wave. In order to elucidate the reduction mechanism of these molecules in DMF-water mixture, the kinetic behavior of the anion radical was studied by the ESR method. It has been found that the reduction of anthracene is understood by the protonation mechanism, but that of anthraquinone is not explained by the protonation mechanism at all; the disproportionation of the anion radical must be considered. For the reduction of benzophenone both the protonation and the disproportionation mechanism must be taken into consideration.
Mass Spectrometric Study of Photoionization. II. Mass Spectra by the Use of Resonance Lines of Argon and Helium
Authors: Omura Itiro , Doi Hiroshi
Published: July 2006

An emission line of He II was generated at 304 Å (40.80 eV) from a microwave plasma light source operated in the standing wave mode. On the other hand, the plasma without the standing wave mode emits only the resonance line of He I at 584 Å (21.21 eV). A resonance line of Ar I was emitted at 1048 Å (11.82 eV) by argon carrier gas flowing through a capillary tube. The mass spectra of propane, n-butane, propylene, benzene, and isoamyl acetate obtained by the use of the emission line of He II at 304 Å were not very different from those of the electron impact method at 50 eV. The positive-charge distribution on each atom of the ionized molecules is estimated from the total ion yield of the molecule. In the fragmentation processes of isoamyl acetate, the intensity of the fragment ion (CH3CO+) including carbonyl group rose rapidly with the increase in the photon energies obtained by the resonance lines of Ar I, He I, and He II. At these photon energies, the ratios of the fragment ion, CH3CO+ , to that of C5H10+ were 0.17, 0.43 and 2.0 respectively.
Microwave Spectra and Equilibrium Structure of Carbonyl Sulfide
Authors: Morino Yonezo , Matsumura Chi
Published: July 2006

Microwave spectra have been measured for various vibrationally excited states of the OCS molecule. The l-type doubling constants obtained for the excited states of the bending vibration, ν2, have led to the determination of the zero-order coupling constant, qe. It has been shown that the qe value thus obtained is useful for the evaluation of the harmonic force constants. The Fermi resonances have been discussed; they lead to the conclusion that the effect due to the cubic constant, k223, cannot be ignored, nor can that due to k122 With due consideration for this situation, the equilibrium structure has been found to be:

re(O–C)=1.1572±0.002 Å and re(C–S)=1.5606±0.002 Å.
Chemical Structures of Glasses of the NaBO2-NaPO3 System
Authors: Nakamura Terumasa , Ohashi Shigeru
Published: July 2006

Glasses of the NaBO2-NaPO3 system with P/B ratios in the range from 1.0 to 98.9 have been prepared from sodium metaphosphate and sodium metaborate by quenching melts of their mixtures. By the paper chromatographic analysis and the pH titration of the solutions of the glasses, it has been found that the glasses have the chain and branched structures consisting of P–O–P, P–O–B and B–O–B linkages. On the assumption that the glasses are composed of polypohsphate and polyborate chain blocks and branched BO3 units, the theoretical treatment has been made on the compositions of these blocks and units and compared with the experimental data. It has been concluded that (1) the glass with a P/B ratio of unity, i. e., a mole fraction of sodium metaphosphate m is 0.5, may be composed of chains of the P–O–P, P–O–B and B–O–B linkages, (2) with the increase of P/B ratios, the amount of the B–O–B linkages decreases, while the amount of the branched BO3 units increases and (3) in the glasses with P/B ratios larger than 4.0 (m>0.8), all boron atoms are present as the branched BO3 units.
Solvent Effects on the g-Value of Di-t-butyl Nitric Oxide
Authors: Kawamura Takashi , Matsunami Shoichi , Yonezawa Teijiro
Published: July 2006

The effects of solvents on the g-value of di-t-butyl nitric oxide (DTBNO) have been examined. Plots of the g-value vs. the hyperfine coupling constant of 14N of DTBNO in various solvents formed two different straight lines, for aprotic solvents and for protic solvents. An analysis of the solvent effects on the g-value has also been attempted. The solvent-dependent shifts of the g-value may be divided into three terms, resulting from the blue-shift of the n–π* transition, from the redistribution of the odd electron, and from the delocalization of the lone-pair orbital on the oxygen atom of DTBNO. The first term is calculated from the observed shift of the n–π* absorption in the visible ray spectrum, while the seond one is evaluated from the solvent shift of the g-value of DTBNO in aprotic solvents, where the delocalization of the lone-pair is excepted to be negligible The last term, the difference between the observed shift in the g-value and the sum of the former two terms, is estimated to be in the range from −4×10−5 to −10×10−5, which corresponds to the from 2% to 5% delocalization of the lone-pair electron.
Effects of the Double Layer Structure and the Ion Association on Electrode Processes of Some Substitution-inert Complex Ions
Authors: Ogino (née Ebata) Kazuko , Tanaka Nobuyuki
Published: July 2006

The current-potential curves of some substitution-inert complex ions are affected by the change in the composition of the supporting electrolyte. The change in the one-electron reduction wave of hexaquochromium(III) ions with the increase in the concentration of sodium perchlorate and sodium iodide is analyzed in terms of the effect of the structure of the electrical double layer. The addition of sodium sulfate at a constant ionic strength of 0.1 shifts the half-wave potentials of hexaquochromium(III), hexamminechromium(III) and hexamminecobalt(III) ions to more negative potentials. In the case of hexamminecobalt(III), the shift is much greater than in the cases of the former two complex ions. These phenomena are interpreted to be due to the effects of the double layer structure and of the ion association.
Equilibrium Studies of the Interaction of Vanadyl Ions with Catechol
Authors: Lal K , Agarwal R P
Published: July 2006

A quantitative study of the interaction of vanadyl ions with catechol (H2A) has been carried out by means of potentiometric titrations of vanadyl sulphate with potassium hydroxide in the presence of varying concentrations of catechol. The formation of 1 : 1 and 1 : 2 complexes has been indicated. The equilibrium constants for the VO2++H2A\ightleftarrowsVOA+2H+ and VOA+H2A\ightleftarrowsVOA22−+2H+ reactions have been found to be 1.41×10−6 and 7.76×10−9 respectively, giving the values of 1.90×1015 and 1.05×1013 for the formation constants of 1 : 1 and 1 : 2 chelates respectively. Above pH 4, the 1 : 1 complex has been shown to hydrolyze, and the equilibrium constant for the VOA+H2O\ightleftarrowsVO(OH)A−+H+ reaction has been found to be 7.94×10−6.
The Metal Ammine Cyanide Aromatics Clathrates. I. The Preparation and Stoichiometry of the Diamminemetal(II) Tetracyano-niccolate(II) Dibenzene and Dianiline
Authors: Iwamoto Toschitake , Miyoshi Tadahiko , Miyamoto Takeshi , Sasaki Yukiyoshi , Fujiwara Shizuo
Published: July 2006

Benzene and aniline clathrates of metal-complex host lattices with a general formula of M(II)(NH3)2Ni(CN)4·2G, in which M(II) was nickel, copper, or cadmium, and G, benzene or aniline as the guest molecule, were prepared. The stoichiometry was established through the analytical data and the structural information obtained from the powder X-ray diffractometric data. They are tetragonal with reasonable lattice parameters except for Cu(NH3)2Ni(CN)4·2C6H5NH2, which may be estimated to be orthorhombic or monoclinic. The host lattices of all the compounds have almost the same space character. The occupation of divalent metal M(II) at the octahedral site of the metal-complex host lattice was proved through the magnetic data.
The Reactions of Bis(acetylacetonato)beryllium with Bromine and Hydrogen Bromide in Dichloromethane
Authors: Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

The main product in the reaction of bis (acetylacetonato) beryllium with bromine in the mole ratio of one to two was found to be bis(3-bromoacetylacetonato)beryllium. The mass-spectrometric analysis of the product of the same reaction in the mole ratio of one to one revealed the coexistence of mono- and dibrominated chelates, but the quantitative information concerning the product distribution has not been obtained. In this reaction a small amount of white precipitate was produced as a minor product. The same compound was obtained in the reaction of bis-(acetylacetonato) beryllium with hydrogen bromide in dichloromethane containing water, and identified as diaquoacetylacetonatoberyIlium bromide on the bases of the elemental analysis, the anion exchange experiment and the infrared assay.
Roles of the Electron Donors in the Three-Component Polyolefin Catalysts
Authors: Takashi Yûkichi
Published: July 2006

The reactions of the three-component polyolefin catalysts consisting of titanium trichloride (α-type), triethylaluminum, and various electron donor compounds have been investigated. Electron donors in a certain range of reactant ratios were found to accelerate the alkylation of the titanium ion remarkably at a temperature suitable for the polymerization of α-olenns. The roles of the electron donors have been discussed on the basis of the reaction behavior of the catalyst components and of the properties of the complexes which are thought to be the reaction intermediates.
A New Method of Reducing Nitroarginine-peptide into Arginine-peptide, with Reference to the Synthesis of Poly-l-arginine Hydrochloride
Authors: Hayakawa Tadao , Fujiwara Yukihiko , Noguchi Junzo
Published: July 2006

With stannous chloride in formic acid, nitroarginine can be reduced to l-arginine hydrochloride quantitatively. This new method for the removal of the nitro group was applied successfully in the synthesis of poly-l-arginine hydrochloride from poly-l-nitroarginine, which had been prepared by the polymerization of N-carbothiophenyl-l-nitroarginine in dimethylsulfoxide at 120°C for 14 hr. The infrared absorption spectra of these polymers showed absorptions at 1708 cm−1 and 1766 cm−1, these absorptions might correspond to the C=O group in the hydantoin of the N-terminal. The poly-l-arginine hydrochloride showed positive Biuret and Sakaguchi reactions.
Thermal Transformation of Alkali Salts of Aromatic Carboxylic Acids. IV. Reaction of Potassium and Sodium Salts of Alkyl-and Phenylbenzoic Acids
Authors: Dozen Yasuhiko
Published: July 2006

The cadmium halides-catalyzed thermal transformation of potassium and sodium salts of isomeric methyl- and phenylbenzoic acids has been investigated. Potassium o-toluate gave toluene, 3-methylphthalic, and 4-methylisophthalic acids, whereas sodium o-toluate gave toluene, 3-, and 4-methylphthalic acids, as the main products. In the reaction of potassium m- and p-toluates, both of them gave toluene, 5-methylisophthalic, and 4-methylphthalic acids, whereas the sodium salt of these acids gave toluene and 4-methylphthalic acid, as the main products. Potassium and sodium isomeric dimethylbenzoates gave xylenes and dimethylphthalic acids, e. g., 3, 4- and 4, 5-dimethylphthalic acids from 2, 3- or 3, 4-dimethylbenzoates, 3, 5-dimethylphthalic acid from 2, 4-dimethylbenzoate, and 3, 6-dimethylphthalic acid from 2, 5-dimethylbenzoate. In the case of o-phenylbenzoate, potassium salt gave biphenyl, m- and p-phenylbenzoic, and biphenyl-p-p′-dicarboxylic acids, but sodium salt gave biphenyl, m- and p-phenylbenzoic, and 4-phenyl-phthalic acids. Sodium p-phenylbenzoate gave biphenyl and 4-phenylphthalic acid, but potassium p-phenylbenzoate was stable under the conditions used. These results may be interpreted by the ortho-, meta-, and para-directed disproportionation for the potassium salts and ortho-di-rected one for the sodium salts. These dibasic acid salts produced were decarboxylated to mono-carboxylates, which then underwent further disproportionation.
On the Composite Solid Propellant Impregnated with Metallic Foil
Authors: Yamazaki Kiroku , Tokui Harusuke
Published: July 2006

The control of the burning rate is one of the important aspects in the extension of the capability of a solid propellant. The burning rate of a composite propellant was found to be increased remarkably by the proper impregnation of metallic foil, and upon the addition of a few percent of aluminum, silver and copper (in weight), the burning rate jumped up to several times that of the original one, providing there had been suitable processing. The impregnation of metallic foil was performed by mixing a predetermined amount of finely-cut strips of foil into propellant dough or by laminating the latter with foils. The propellant grain impregnated at random with strips of foil increased the burning rate considerably, but the one laminated with metallic foils which were oriented perpendicular to the burning surface showed the highest burning rate. The increment of the burning rate evidently depended upon the thickness of the foil used; the distance between adjacent foils for lamination showed no remarkable effect. The role of the metallic foil on the augmentation of the burning rate seems to be attributable to the improvement of the heat transfer from the burning zone to the burning surface. However, in the case of copper, the burning rate exceeded that of silver, so the increment of the burning rate can not be explained only in terms of the thermal conductivity of the metallic foil. In the case of copper foil, the effective increase in the burning rate may be due to its catalytic action plus a good thermal conductivity. The mechanical properties of the propellant grain, such as tensile strength and elongation at the yield point, were expected to be improved with the impregnation of metallic foil. However, this coluld not be confirmed in the present tests.
Studies of Diarylalkanes. VI. The Cleavage of Diphenylmethanes and the Friedel-Crafts Benzylation
Authors: Tsuge Otohiko , Tashiro Masashi
Published: July 2006

The cleavage reaction of DPM and Me-DPM, and the benzylation of toluene, have been carried out under various conditions. On the basis of the results of this series, the correlations with the cleavage reaction of the DPM and with the Friedel-Crafts benzylation have been inclusively discussed. Furthermore, the mechanism of the isomerization of mono-substituted DPM under the influence of aluminum chloride has been suggested.
The Extraction of Inosine with Liquid Anion Exchangers
Authors: Hirahara Tsuneo , Mitsuki Koji , Suzuki Yoshihisa , Nakazawa Eiji , Nakamura Tadashi
Published: July 2006

Inosine can be extracted with a liquid anion exchanger. The most useful pH values are about 10 and over 10 for extraction with n-octylamine and with methyltrioctyl ammonium chloride respectively; this suggests that the extraction is principally due to electrostatic attraction. The extraction processes may, on the basis of the experimental results, be represented as follows:

HxR+2OA=HxR·2OA

HxR−+(Q+·Cl−)=(Q+·HxR−)+Cl−
Electronic Structures and Reactivities of Aliphatic Small Membered-Ring Compounds. II
Authors: Yonezawa Teijiro , Shimizu Kiyoshi , Kato Hiroshi
Published: July 2006

Extended Hückel MO investigations of the physico-chemical properties of cycloalkanes have been carried out. The calculated total energies of protonated cyclopropane and cyclopentane show that the most stable configuration of protonated cycloalkanes is the one with the conformation in which a proton exists in the ring plane. In cyclopropane, the changes in the total electronic energies and in the charge distributions caused by the protonation are almost the same as those in ethylene, while no remarkable changes in these quantities can be observed in protonated cyclopentane. It may be concluded that cyclopropane has unsaturated properties similar to those of the π-electron system in its ring plane. Further, the reaction mechanism and the reactivities of halogenocycloalkanes in the SN2-type reaction are discussed. It is shown that the theoretical results can successfully explain their chemical reactivities.
The Kinetics of the Vapor-Phase Ammoxidation of m-Xylene over a Vanadium Catalyst
Authors: Ito Masatomo , Sano Ken-ichi
Published: July 2006

The kinetics of the vapor-phase ammoxidation of m-xylene and m-tolunitrile over a vanadium oxide catalyst were studied in a flow system. The reaction rate data obtained were correlated by the rate equation based upon the Langmuir-Hinshelwood mechanism, where the adsorption of m-xylene was strong. From the result of the experiments it was suggested that the reaction scheme consisted of four parallel routes: (1) the step-by-step ammoxidation of m-xylene to isophthalonitrile via  m-tolunitrile; (2) the direct ammoxidation to isophthalonitrile from m-xylene; (3) the formation of carbon oxides and hydrogen cyanide via  m-tolunitrile and (4) the direct formation of carbon oxides and hydrogen cyanide from m-xylene. The activation energies for the reaction of m-xylene and m-tolunitrile were 43.7 and 31.2 kcal/mol respectively in the range from 396 to 420°C.
ESR Studies of the Ion-pairs of the Acenaphthylene Radical Anion and Alkali Metal Cations
Authors: Iwaizumi Masamoto , Suzuki Masayasu , Isobe Taro , Azumi Hiroshi
Published: July 2006

Two types of temperature dependence of the proton hyperfine splitting constants of the acenaphthylene radical anion are described. One is that for the radical anions which are in a state of rapid exchange between the ion-paired form and the free radical anion, and the other is that for the radical anions which exist as stable ion pairs with a relatively long lifetime. From the examination of the effects of the alkali ions in terms of the molecular orbital method, it is concluded that the most favored ion-pair configuration is that in which the alkali ion is placed above the five-membered ring. The equilibrium position of the alkali ion moves toward the position 11 with an increase in the radius of the alkali ion. In relation to this ion-pair structure, the temperature dependence of alkali-metal hyperfine splittings is also discussed.
Silent Discharge Reactions in Aqueous Solutions. V. Nitrogen Fixation in a Heterogeneous System of Nitrogen and Water
Authors: Yokohata Akira , Tsuda Satoru
Published: July 2006

Nitrogen fixation by silent discharge on heterogeneous systems of nitrogen or air and water has been investigated, together with that on homogeneous systems of nitrogen or air. Moreover, oxidations of ferrous ions in acidic aqueous solutions of ferrous ions and in a ferrous-cupric ion system have been pursued in a nitrogen atmosphere. These experiments were conducted under flowing gas conditions. It has been found in the present study that: (1) in heterogeneous systems of nitrogen or air and water, the fixation yield is much larger in water than in gas; (2) in homogeneous systems of moist nitrogen or air, the yield is very small; (3) the ferric ion yield is very small compared with that expected theoretically from the estimated values of the absorbed dose (≈3.2×107 R/hr) and the LET (≈ 8eV/Å), and (4) the effect of cupric ions on the ferric ion yield is negligible. Based on these findings, and in view of the actions of active nitrogen on radicals produced from water by slow electrons, the reaction mechanisms of nitrogen fixation have been suggested.
Organic Compounds of Niobium and Tantalum. Reactions of Niobium and Tantalum Pentaethoxides with Dibenzoylmethane
Authors: Kapoor R N , Prakash S , Kapoor P N
Published: July 2006

Following three types of new compounds have been isolated: M(OEt)4(Dbm), M(OEt)3(Dbm)2 and M(OEt)2(Dbm)3 (where M is niobium or tantalum) by the reactions of niboum and tantalum pentaethoxides with dibenzoylmethane. These derivatives interchange their ethoxy groups with tertiary butanol. The molecular weights of the few compounds have been determined ebullioscopically in benzene.
Rearrangements of Tertiary Amine Oxide. XVIII. The Reaction of 4-Substituted Pyridine N-Oxides with p-Nitrobenzenesulfenyl Chloride and p-Nitrobenzenesulfinyl Chloride
Authors: Oae Shigeru , Ikura Katuyata
Published: July 2006

When 4-nitropyridine N-oxide was allowed to react with p-nitrobenzenesulfenyl chloride, 4-pyridyl 4′-chloropyridinium chloride (V) and 4-(4′-pyridol)pyridine (IV) were obtained, along with p, p-dinitrodiphenyl disulfide, p-nitrobenzenesulfonic acid, and a salt, presumed to have a VI structure. Similar products were formed in the reaction between 4-chloropyridine N-oxide with p-nitrobenzenesulfenyl chloride. In the case of 4-methoxypyridine N-oxide, however, a simple reduction was the main reaction; thus 4-methoxypyridine was obtained, while the other products were the same. As in the case of pyridine- and α-picoline N-oxide, no ring-substituted product was isolated in the reactions of these N-oxides. Apparently, the reaction of these N-oxides with p-nitrobenzenesulfenyl chloride involves the initial formation of the salt, which has a N-sulfenoxy bond, (Remark: Graphics omitted.), which presumably cleaves homolytically in the succeeding step to give the final products.
Reaction Rates in Binary Mixed Solvents. II
Authors: Kondo Yasuhiko , Tokura Niichiro
Published: July 2006

In order to study the effects of solvents on reaction rates, the theoretical expression for the rate constant has been introduced using Henry’s constant. The Henry constant of the solute in a chemically-reacting mixture has been calculated thermodynamically. The theoretical expressions for the rate constants in mixed solvents have been derived on the basis of the molecular models; the application of these equations showed that one model accurately illustrates the behavior of the reaction rates in solvent mixtures.
The Nitro Valence Vibrations and Ultraviolet Spectra of cis- and trans-β-Nitrostyrenes
Authors: Watarai Setsuo , Yamamura Kimiaki , Kinugasa Toshio
Published: July 2006

The infrared spectra of NO2 symmetric and asymmetric stretching vibrations and ultraviolet spectra for a series of cis- and trans-β-nitrostyrene derivatives are examined and correlated with the stereochemical configuration of the structure, the planarity of the conjugated system, and the electronic properties of groups on the carbon bearing the nitro group. From these correlations, the cis-, and trans-isomers of β-nitrostyrene derivatives have been readily distinguished from each other.
The Tropylation of Polyhydric Phenols and the Dehydrogenation of Their Products
Authors: Takahashi Kazuko
Published: July 2006

The tropylation reaction of polyhydric phenols, such as guaiacol, catechol, resorcinol, hydroquinone, 2, 6-dimethoxyphenol, pyrogallol and phloroglucinol, has been carried out. These polyhydric phenols were quite reactive with ethyl tropyl ether or with tropylium ion, and gave mono-, di-, or sometimes tri-tropyl derivatives. The dehydrogenation of tropylpolyhydric phenol methyl ethers gave stable aryltropilium ions. The methoxyphenyltropones and the methoxyphenyl tropolones were also synthesized in good yields starting from the 4-methoxyphenyltropylium ion.
The Synthesis of Hydroxy- and Methoxy-derivatives of p-Benzoquinonetropides
Authors: Nozoe Tetsuo , Takahashi Kazuko
Published: July 2006

2-Methoxy- (10), 2-hydroxy- (15), and 2, 6-dimethoxy- (20) p-benzoquinonetropide were synthesized by the dehydrogenation of tropylated guaiacol, catechol, and pyrogallol dimethyl ether respectively. The electronic spectra of 10, 15, and 20 in water showed their long wavelength absorption maxima at 550–570 mμ. However, the spectra of these compounds in chloroform showed that the peaks had shifted to wavelengths shorter by 38–60 mμ than those in water. A solvent effect of this type can be understood as resulting from a transition to an excited state that is more polar than the ground state.
Aminocyclitols. XI. Studies on the Synthesis of muco-Inosadiamines and Inosatetraamine
Authors: Suami Tetsuo , Lichtenthaler Frieder W , Ogawa Seiichiro
Published: July 2006

muco-lnositol was synthesized from 1, 4, 5, 6-tetra-O-acetyl-3-O-sulfonyl-myo-inositol in a fairly good yield by a new synthetic route. When sulfonyloxy groups were replaced by azide ion in muco-inositol derivatives, muco-inosadiamine-3, 6, myo-4, 6 and muco-inosatetraamine-1, 2, 4, 5 were obtained. Their structures were established by means of proton magnetic resonance spectro-scopy. By an analogous reaction, 2, 4, 5, 6-tetra-O-acetyl-1, 3-di-O-p-toluenesulfonyl-myo-inositol gave muco-inosadiamine-1, 4.