bluuebunny/crossref_metadata_2025 huggingface dataset:
The Strategic and Tactical Implications of Convenience in Consumer Product Marketing
Authors: Brown Lew G.
Published: May 2006

Suggests that the construct of convenience has not been clearly
defined and operationalized. Proposes a conceptual framework which can
be used to examine the convenience of consumer products, involving five
dimensions: time, place, acquisition, use and execution. Discusses the
implications for managers and recommends that marketers gain an improved
understanding of convenience given the predicted growth of the sector.
An Exploratory Report of Sales Promotion Management
Authors: Kimball Robert
Published: May 2006

Investigates the role and management of sales promotion in US
companies. Reports on a study intended to identify factors that
influence sales promotion management. Concludes that the product
category and the firm′s position within the category are related to
sales promotion behaviour, with similarity in sales promotion behaviour
among firms in similar product marketing environments.
Banking on Total Quality
Authors: Edwards Sue , Smith Steve
Published: May 2006

Examines how US and British financial institutions are implementing TQM to differentiate themselves from the competition. Discusses how customer satisfaction is achieved through customer care programmes, quality action teams, improved internal and external communications, and quality performance standards. Contends that an emerging trend in the sector is that of quality performance standard setting, measuring and monitoring. States that the financial sector is responding to this challenge by concentrating its focus on providing quality services to its customers. Concludes that customer care programmes, action teams and improved communications are the first step; the next step in maintaining the competitive edge is the establishment of quality performance standards, and devising systems for measuring and monitoring their effectiveness.
Healthcare: Is Total Quality Relevant?
Authors: Keyser William
Published: May 2006

Examines some of the quality initiatives occurring in the UK National Health Service. Contrasts quality practices in healthcare with TQM in industry and discusses the implications of adopting total quality in the NHS. Looks at current quality activity and discusses the key components to participative management and quantitative methods. Proposes a model for total quality in healthcare. Concludes that everyone be encouraged to make “breakthroughs” ‐ this means no one can be left out of the process.
Selling a Promise
Authors: Chase Rory
Published: May 2006

Discusses how, by incorporating the principles of TQM from the outset, State Farm Insurance has achieved a leadership position in its industry. Examines State Farm′s “good neighbour” approach to service. Asserts that the company′s management philosophy is simple:total commitment to the policyholder. Contends that agents are the key. Concludes by describing how the trainee agents become independent contractors working with other agents and the agency manager.
Management of Quality ‐ Quality of Management
Authors: von Rutte Richard
Published: May 2006

Discusses that for TQM to succeed, management must be prepared to lead and motivate the workforce. Asserts this is accomplished by creating a corporate vision of quality, training employees to understand the concept of the quality chains and empowering workers to assume individual responsibility for each quality process. Looks at the mastered process as quality criterion. Concludes that the most effective compensation for an employee is having his/her proposals listened to, discussed and implemented where appropriate.
A Blueprint for Quality
Authors: Nakamura Hiromichi
Published: May 2006

Describes how, in the face of severe competition from home and abroad, a new production improvement system was implemented which improved quality, reduced lead times and cut work‐in‐process by 40 per cent at Mitsubishi Aluminium′s Fuji Plant. Discusses the implementation of the programme over a two year period. Summarizes the results. Concludes that the MAF Production Improvement System has laid the groundwork for the continuous improvement of goods and services.
Theories of Sexual Stratification: Toward an Analytics of the Sexual Field and a Theory of Sexual Capital
Authors: Martin John Levi , George Matt
Published: May 2006

The American tradition of action theory failed to produce a useful theory of the possible existence of trans-individual consistencies in sexual desirability. Instead, most sociological theorists have relied on market metaphors to account for the logic of sexual action. Through a critical survey of sociological attempts to explain the social organization of sexual desiring, this article demonstrates that the market approach is inadequate, and that its inadequacies can be remedied by studying sexual action as occurring within a specifically sexual field (in Bourdieu's sense), with a correlative sexual capital. Such a conception allows for historical and comparative analysis of changes in the organization of sexual action that are impeded by the use of a market metaphor, and also points to difficulties in Bourdieu's own treatment of the body qua body.
Digital Desire in the Daydream Machine
Authors: Doane Randal
Published: May 2006

This article analyzes the sociality of illegal file sharing as one domain of teletechnology, using poststructural theory to conceptualize the file-sharing setting. It reveals the assumptions about file sharing in popular media, and demonstrates how the persis-tence of illegal file sharing across racial, economic, and status lines might be attrib-uted to psychological and neurophysiological causes. To conclude, I consider the implications of poststructuralism for extension and synthesis in future social theory.
How to Punch Someone and Stay Friends: An Inductive Theory of Simulation
Authors: Hoffman Steve G.
Published: May 2006

One way to study ontology is to assess how people differentiate real activities from others, and a good case is how groups organize simulation. However, social scientists have tended to discuss simulation in more limited ways, either as a symptom of postmodernism or as an instrumental artifact. Missing is how groups organize simulations to prepare for the future. First, I formulate a definition of simulation as a group-level technique, which includes the qualities of everyday ontology, playfulness, risk and consequence reduction, constrained innovation, and transportability. Next, I use ethnographic data collected at an amateur boxing gym to argue that simulations simplify the most risky, unpredictable, and interpersonal aspects of a consequential performance. The problem is that a simulation can rarely proceed exactly like the reality it is derived from. For example, boxers hold back in sparring but should not in competition. The effectiveness of a simulation therefore depends on how robust the model is and how well members translate the imperfect fit between the contextual norms of the simulation and its reality.
Multifunctional teasing as a resource for identity construction in the talk of British Bangladeshi girls1
Authors: Pichler Pia
Published: May 2006

This paper explores how multifunctional teasing is used as a resource for the construction of linguistic identities, establishing a link between previous research on teasing and the field of language/discourse and identity. I draw on a corpus of 38 episodes of teasing contained in 80 minutes of spontaneous talk between five adolescent Bangladeshi girls who formed a friendship group at their comprehensive school in East London. The qualitative analysis of the data reveals that the teasing in this group can serve four main functions: an accomplishment of fun‐based solidarity; a release of underlying tensions; a display of toughness; but also a display of respect for other speakers’ dispreference for taboo subjects. Building onOchs’(1992)notion of indirect indexicality my discussion of the data will focus on the social meanings of these different functions of teasing which range from maintaining and managing friendship to (re)negotiating class and culture‐related identities. I shall argue that the identity work achieved by and in the teasing needs to be seen in relation to stereotypical notions and ideologies about class, gender and culture‐specific (language) practices which shape the girls’ construction of themselves as British Bangladeshi working‐class adolescents.
Patients’ perceptions and experiences of ‘continuity of care’ in diabetes
Authors: Naithani Smriti , Gulliford Martin , Morgan Myfanwy
Published: May 2006

Background  ‘Continuity of care’ is an important aspect of quality. However, definitions are broad and existing models of continuity are not well grounded in empirical data.

Objective  To identify patients’ experiences and values with respect to continuity in diabetes care.

Methods  In‐depth semi‐structured interviews with 25 type 2 diabetic patients from 14 general practices in two inner London boroughs. Interviews were transcribed and responses analysed thematically and grouped into dimensions of continuity of care.

Results  Patients’ accounts identified aspects of care they valued that were consistent with four dimensions of experienced continuity of care. These were receiving regular reviews with clinical testing and provision of advice over time (longitudinal continuity); having a relationship with a usual care provider who knew and understood them, was concerned and interested, and took time to listen and explain (relational continuity); flexibility of service provision in response to changing needs or situations (flexible continuity); and consistency and co‐ordination between different members of staff, and between hospital and general practice or community settings (team and cross‐boundary continuity). Problems of a lack of experienced continuity mainly occurred at transitions between sites of care, between providers, or with major changes in patients’ needs.

Conclusions  The study develops a patient‐based framework for assessing continuity of care in chronic disease management and identifies key transition points with problems of lack of continuity. It is important that service ‘redesign’ and developments in vertically integrated services for chronic disease management take account of impacts on patients’ experience of continuity of care.
Pharmacological inhibition of TRα1 receptor potentiates the thyroxine effect on body weight reduction in rats: potential therapeutic implications in controlling body weight
Authors: Pantos C. , Mourouzis I. , Paizis I. , Malliopoulou V. , Xinaris Ch. , Moraitis P. , Cokkinos A. D. , Cokkinos D. V.
Published: May 2006

It has been previously reported that thyroid hormone receptor α1 (TRα1) is involved in the regulation of food intake and heart rhythm. Herein, we show that pharmacological inhibition of TRα1 by dronedarone, an amiodarone like compound (shown to antagonize thyroid hormone binding to TRα1), prevented the thyroid hormone induced increase in food intake and heart rate acceleration in rats. This resulted in a marked reduction in body weight. It is likely that thyroid analogs may prove potential therapeutic agents for controlling body weight.
Social Capital, Resource Mobilization and Origins of the Civil Rights Movement
Authors: LING PETER
Published: May 2006

Abstract  This article critiques the contradictory claims of Robert Putnam and Aldon Morris in relation to the American civil rights movement. Putnam identifies the South as the American region most lacking in social capital, and argues more generally that the 1960s marked a watershed beyond which social capital in the United States declined in all regions. Morris identifies the indigenous resources of southern African American communities as fundamental to the civil rights movement’s emergence in the late 1950s and sees the social networks and cultural assets of the African American church in particular as central to the movement. The article disputes Putnam’s negative judgment of the South by highlighting the role played by various types of social capital in the movement’s launch. It also challenges Morris’s over‐emphasis on the ability of charismatic, black church leadership to deliver mass support and re‐affirms the role played by female lay figures, such as beauticians.
Endogenous Pollution Havens: Does FDI Influence Environmental Regulations?*
Authors: Cole Matthew A. , Elliott Robert J. R. , Fredriksson Per G.
Published: May 2006

We suggest a novel perspective on the relationship between the stringency of environmental policies and foreign direct investment (FDI). We develop a political economy model with imperfect product market competition where local and foreign firms jointly lobby the local government for a favorable pollution tax. FDI is found to affect environmental policy, and the effect is conditional on the local government's degree of corruptibility. If the degree of corruptibility is sufficiently high (low), FDI leads to less (more) stringent environmental policy, and FDI thus contributes to (mitigates) the creation of a pollution haven. Our empirical results using panel data from 33 countries support the predictions of the model.
The Labour Market Impact of the Working Families' Tax Credit
Authors: BLUNDELL RICHARD , DUNCAN ALAN , McCRAE JULIAN , MEGHIR COSTAS
Published: May 2006

In October 1999, the working families' tax credit (WFTC) replaced family credit as the main package of in‐work support for families with children. Among a range of stated aims, the WFTC is intended to‘… improve work incentives, encouraging people without work to move into employment'. In this paper, we consider the impact of WFTC on hours and participation. To simulate labour supply responses, we use a discrete behavioural model of household labour supply with controls for fixed and childcare costs, and unobserved heterogeneity. In simulation, we experiment with a number of scenarios regarding the take‐up of the credit, entry wage level and hourly childcare price. We find participation rates among single mothers to increase by around 2.2 percentage points for the base‐case scenario, while for married women participation rates are modelled to fall. Our simulation results indicate a small increase in overall participation of around 30,000 individuals.
VacA‐Associated Inhibition of T‐cell Function: Reviewed and Reconsidered
Authors: Schmees Christian , Gerhard Markus , Treptau Tilman , Voland Petra , Schwendy Susanne , Rad Roland , Prinz Christian
Published: May 2006

Chronic Helicobacter pylori infection is characterized by dense infiltration of the mucosa with neutrophilic granulocytes, lymphocytes, and monocytes/macrophages. Among these different cell types, T‐lymphocytes are the most intriguing and crucial cells for the elimination of the bacteria. Previous studies have elucidated possible mechanisms on how bacteria could interfere with the human immune response and claimed that especially the secreted vacuolating toxin VacA may be responsible for the chronic persistence of the bacteria. Some of these results have to be interpreted with caution and may just describe in vitro phenomena; others may reveal promising facts.
Gelcasting of Zirconia Using Agarose
Authors: Adolfsson Erik
Published: May 2006

Gelcasting of zirconia with agarose as a gelling agent was evaluated, and the rheological behavior of the suspensions was studied. For certain compositions, a viscosity low enough for the suspensions to be processed as well as a sufficient wet green strength to avoid deformation of cast components due to mechanical stresses was obtained. Futhermore, it was possible to increase the storage modulus of the cast material by a reduction of the gelation temperature, which facilitated demolding. Sintered densities above 99% were achieved and high bending strength was obtained. The results show that the shaping technique has the potential to be used for fabrication of advanced zirconia materials.
‘Saving the Solomons’: a New Geopolitics in the ‘Arc of Instability’?
Authors: CONNELL JOHN
Published: May 2006

The recent crisis in the Solomon Islands is reviewed in the context of historical and regional antecedents. In the past two decades political and ethnic disputes have flared in several parts of Melanesia and nearby parts of the ‘arc of instability’. Tensions and violence in the Solomon Islands, based on social, economic and political issues, exemplify regional development concerns. The collapse of the economy and civil order resulted in the Solomon Islands being characterised as a ‘failed State’. Localised warfare brought external military intervention, with a regional assistance mission led by Australia, which paralleled other involvement in the region. Involvement has emphasised renewed Australian interest in the region, in the light of global geopolitical shifts, and a more controversial approach to regional security and development.
Geographical Takes on Three Decades of Economic Reform in Australia
Authors: O’NEILL PHILLIP , FAGAN BOB
Published: May 2006

The idea of an economy taking a geographical journey highlights the importance of changing spatialities and how these shape and result from economic change. It also focuses on the geographical scaling of key processes. Using these insights, this paper explores three decades of economic change in Australia in which the nation State has played a central role in the operation of markets and accumulation processes, albeit with dramatic shifts in the qualitative nature of that role. Such shifts have been crucial during the emergence of Australia's particular variety of neoliberalism. The paper explores the liberalisation of Australia's financial and corporate environment, trade policies and the industrial relations environment. The three cases suggest contradictions inherent in the State's adherence to a neoliberal reform agenda, in the name of globalisation, while facing: first, political needs to retain sovereignty over national security and tighten border protection; and second, multi‐scaled political processes including clashes with State governments grappling with regional and local impacts of change. There has been no simple roll‐out of neoliberalism in Australia since the mid 1990s. Geographical scales, constructed contingently by social and political agents, have contributed in fundamental ways to the power and direction of economic reform. Despite powerful re‐scalings to both global and local levels over the past three decades, there is no evidence of a diminished role for the nation State.
Characterization and Differential Nuclear Localization of Nopp140 and a Novel Nopp140-Like Protein in Trypanosomes
Authors: Kelly S. , Singleton W. , Wickstead B. , Ersfeld K. , Gull K.
Published: May 2006

Trypanosomatids possess two homologues of Nopp140: a canonical Nopp140 and a Nopp140-like protein (TbNoLP) in which a GAR domain replaces the C-terminal SRP40 domain. Both are phosphorylated and coimmunoprecipitate with RNA polymerase I. Each paralogue has a distinct subnuclear localization, and depletion of TbNoLP produces an enlarged nucleolus in which TbNopp140-containing regions disperse. The restricted occurrence pattern of NoLP proteins reflects an intriguing convergence in evolution, suggestive of a function in nucleoplasmic small nucleolar ribonucleoprotein shuttling.
The heat of formation of N2H2 and the proton affinity of N2
Authors: Willis C. , Lossing F. P. , Back R. A.
Published: May 2006

Measurements of the heat of formation of N2H2 from the appearance potential for m/e 30 ions from N2H4 give irreproducible results. Using N2H2, reproducible values for the appearance potentials of m/e 30, 29, and 28 ions were obtained. These values yield an ionization potential of N2H2, IP(N2H2) = 9.7 ± 0.1 V, a heat of formation of N2H2, ΔHf(N2H2) = 36 ± 2 kcal/mol and a proton affinity of N2, PA(N2) = 5.6 eV. An estimate of the ionization potential of N2H radical, IP(N2H) = 7.6 V, was also obtained.
Isotope effect on the thermodynamic quantities of gaseous uranium hexafluoride
Authors: Bron Jan
Published: May 2006

For gaseous UF6 changes in the thermodynamic quantifies ΔG (= ΔA), ΔH (= ΔU), ΔCp (= ΔCv), and ΔS upon isotopic substitution can be determined by using the spectroscopically determined geometry and force field. The differences ΔG etc. are defined as (G238 – Gx), where 238 and x (x = 235, 234, 233, and 232) are the masses of the central uranium atom. The changes in the thermodynamic quantities are related to the logarithm of the partition function ratio of the UF6 species compared. The logarithm of the partition function ratio can be conveniently expressed as a series in temperature and hence, by using statistical mechanical relationships, the changes in thermodynamic quantities can be expressed as a series in temperature.Since these changes form examples of heavy isotope effects the validity and utility of the first quantum correction can be investigated. Uncertainties and trends in the magnitudes of the differences in the thermodynamic quantities due to uncertainties or changes in spectroscopic parameters are discussed by means of the first quantum correction. It has been found that the first quantum correction has little quantitative value in the lower temperature region, but it can be used in that range to explain some observed trends in the isotope effects. Some of the conclusions can also be applied to kinetic and equilibrium heavy isotope effects.
Etude des complexes aqueux d'uranium(IV) en milieu acide par résonance magnétique nucléaire
Authors: Kiener C. , Folcher G. , Rigny P. , Virlet J.
Published: May 2006

The hydration of tetravalent uranium in acid solutions has been studied by proton magnetic resonance. Longitudinal and transversal relaxation rates of water are reported as a function of temperature, acidity, and added ions. The relaxation rates observed in perchloric solutions at high temperature are governed by the exchange process of water molecules between the inner coordination sphere of uranium(IV) and the bulk water. The bound proton's lifetime τM lies between 10 ms and 1 s. At pH > 0, the exchange rate depends upon acidity according to the law 1/τM ≈ A + B/[H+]. At high concentrations of diamagnetic ions the exchange rate depends linearly upon water activity. At low temperature, the proton relaxation rates are dominated by an outer sphere effect and the electronic relaxation time of uranium(IV) is found to be about 10−13 s. No signal is observed from protons of the water molecules in the first sphere, firmly bound to uranium(IV), which undergo rapid relaxation. The chemical shift of the proton absorption signal in hydrochloric solutions arise from tightly bound water molecules in paramagnetic interaction with uranium(IV) in a second sphere, and in fast exchange with the bulk water. Above a chlorine concentration of 6 M, the monochloro complex of uranium(IV) contributes to the chemical shift.
Aqueous trifluoroacetic acid as a medium for organic reactions. I. Acidity functions and the identity of the manganese(VII) species found in powerfully acidic media
Authors: Spitzer Udo A. , Toone Trevor W. , Stewart Ross
Published: May 2006

The HR acidity function has been determined for the trifluoroacetic acid–water system, and extended beyond 100% acid by the addition of trifluoroacetic anhydride, to 99.5 wt.% anhydride. The existing H0 acidity function is corrected and extended to 100% trifluoroacetic acid, confirming Eaborn's observation that H0 attains a minimum value at approximately 97% acid. Comparison of the acidity functions shows that although trifluoroacetic acid is only weakly protonating, it is a strongly protonating-dehydrating medium. Changes in the uv–visible spectrum of potassium permanganate produced by changing acid concentration are used to calculate the degree of further ionization of the permanganate ion; the correlation of this with the HR acidity function further suggests the presence of the permanganyl cation, MnO3+, or its trifluoroacetate complex or ester, MnO3•O2CCF3, in these solutions. A cryoscopic investigation into the mode of ionization of permanganate in trifluoroacetic acid reveals that extensive ion-pair formation occurs in this solvent. Although this effect prevents an unequivocal determination of the number of solute particles being made the results are consistent with the presence of a permanganyl species in solution.
Synthesis of some long-chain spiropyranindolines
Authors: Gruda Ilona , Leblanc Roger M.
Published: May 2006

Nine new spiropyranindolines containing an n-hexadecyl substituent at the 1′ or 3′ position have been synthesized. Their spectral properties (nmr, uv, visible) are described.The equilibrium constant between the colored and colorless species of some of the compounds have been measured. The results show that the presence of a long aliphatic chain promotes the colored form.
A re-examination of the adiabatic correction term for the hydrogen molecule
Authors: Pritchard Huw O. , Wolniewicz Lutosław
Published: May 2006

The adiabatic coupling correction term [Formula: see text] has been evaluated by two methods, the one used by Kołos and Wolniewicz in 1964 and the one suggested by Kari, Chan, Hunter, and Pritchard in 1973. The difference between the two procedures for H2 amounts to 0.04 cm−1 and is almost independent of internuclear separation in the range R = 1.0–1.8 a.u. Thus, the method of computing the ΔR-term does not affect the vibrational energy level spacings.
The sign of the 'through-space' spin–spin coupling between methyl protons and the fluorine nucleus in 2,6-dimethylbenzoyl fluoride
Authors: Schaefer Ted , Chum Kalvin , Marat Kirk , Wasylishen Roderick E.
Published: May 2006

The spin–spin coupling constant over five formal bonds between 19F and methyl protons, [Formula: see text], in 2,6-dimethylbenzoyl fluoride is −3.1 Hz. Observation of a nonzero [Formula: see text] indicates an out-of-plane conformation for the carbonyl fluoride group and implies substantial nonbonded repulsions between the methyl and carbonyl fluoride groups. It is argued that [Formula: see text] is as small as −7 Hz when the C—F bond lies cis to a methyl group and that its magnitude is a consequence of the so-called 'through-space' coupling mechanisms. On the basis of INDO–MO–FPT computations, it is suggested that such observed couplings are a composite of large contributions of either sign and, therefore, that observed through-space 1H,19F couplings may be of either sign if conformational averaging occurs.
Molecular orbitals from group orbitals. I. A perturbational molecular orbital treatment of the electronic structures, shapes and conformations of AHmBHn Systems
Authors: Whangbo Myung-Hwan , Wolfe Saul
Published: May 2006

A procedure is proposed which allows the group orbitals of a fragment AHm—to be obtained from the molecular orbitals of the molecule AHm—H. Orbital interaction diagrams constructed from these group orbitals have been found useful in the description of the electronic structures and conformations of a variety of molecular systems of the type AHmBHn. The molecules that have been treated by this procedure include ethane, hydrazine, diphosphine, aminophosphine, aminoborane, and sulfonium and phosphonium ylids.
The reactions of atomic oxygen with methanol and ethanol
Authors: Owens Cynthia M. , Roscoe John M.
Published: May 2006

The reactions of O(3P) with CH3OH and C2H5OH were studied as a function of temperature. The absolute rate constants for these reactions fit the following expressions:[Formula: see text](Activation energies are in kJ/mol. Rate constants are in 1 mol−1 s−1.) The data support abstraction of the α-H atom as the primary step. The α-C—H bond in ethanol is apparently weaker than that in methanol, and this alters the nature of subsequent steps in the mechanisms for these reactions. The presence of oxygen alters the stoichiometric coefficients for these reactions and produces the corresponding carboxylic acid.
The lithium–indium system
Authors: Alexander W. A. , Calvert L. D. , Gamble R. H. , Schinzel K.
Published: May 2006

A re-examination of the Li–In system, based on thermal and X-ray diffraction analysis of 42 alloys, shows it to be more complex than originally reported. This complexity is more consistent with the analogous Li–Tl and Li–Ga systems. The solid solubility of Li in In is about 1.5 at% Li, while that of In in Li appears to be very low. The homogeneous Li–In phase extends from about 46 at% to between 55 and 63 at% Li, depending on the temperature. Of the 11 new phases, 5 with the nominal compositions Li7In4, Li2In, Li8In3, Li3In, and Li4In(λ) are stable at room temperature, while Li5In2, Li73In27(η), Li11In4, Li4In(κ), Li6In and Li12In occur at higher temperatures.
Ion pairs and heat capacity of activation for 2,2-disubstituted cyclopropyl bromides
Authors: Singh Surendra , Robertson Ross Elmore
Published: May 2006

The temperature dependence of the rates of hydrolysis of 2,2-dimethylcyclopropyl bromide, 2,2-cis-vinyl-trans-methylcyclopropyl bromide and 2,2-cis-methyl-trans-vinylcyclopropyl bromide have been determined in water. The temperature coefficient of the enthalpy of activation (ΔCp≠) for these compounds was determined to be −52, −27 and −37 cal deg−1 mol−1 respectively. The relative rate ratios for hydrolysis of the 2,2-methylvinylcyclopropyl bromides with respect to the appropriate 2-vinylcyclopropyl bromide isomer indicate a considerable progress towards allyl cations at the transition state in contrast to the indications of the ΔCp≠ values.The ΔCp≠ term for such reactions in water depends to an important degree on the external effects of charge development on water structure but is insensitive to internal electrostatic effects. In the three examples of ΔCp≠ reported in this study, all tend to show small external effects in spite of evidence which might suggest larger. The differences in ΔCp≠ are attributed to the particular shape and charge distribution of the quasi-ion pair.
Trajectory study of atomic recombination reactions. VII. Recombination of I and Br atoms
Authors: Chang D. T. , Burns George
Published: May 2006

Classical 3-D trajectory investigation of bromine and iodine atom recombination reactions in He, Ar, and Xe, performed earlier, are extended, using an improved sampling technique, to include a larger number of trajectories and a wider temperature range (200–1500 K). The three body potential energy surfaces used were assumed to be nearly additive, but otherwise were defined by the existing molecular beam and spectroscopic data and contained essentially no arbitrary parameters. The agreement between computed and experimental rate constants is reasonable, and is best if the third body is heavy and reaction proceeds via a bound complex, such as IXe. Orbiting inert gas – recombining atom intermediate dimers, XM*, where X = I or Br, contribute to the overall recombination reaction via XM* + X → X2 + M reaction, provided M is heavy. If M = He, this reaction path is negligible at all temperatures studied, again provided that X = I or Br.
Absolute gas-phase acidities of CH3NH2, C2H5NH2, (CH3)2 NH, and (CH3)3N
Authors: Mackay Gervase I. , Hemsworth Ronald S. , Bohme Diethard K.
Published: May 2006

The flowing afterglow technique has been employed in measurements of the rate and equilibrium constants at 296 ± 2 K for reactions of the type[Formula: see text]and[Formula: see text]where R1 and R2 may be H, CH3, or C2H5. The equilibrium constant measurements provided absolute values for the intrinsic (gas-phase) acidities of the Brønsted acids CH3NH2, C2H5NH2, (CH3)2NH, and (CH3)3N, the heats of formation of their conjugate bases, and the electron affinities of the corresponding radicals R1R2N. Proton removal energies, ΔG0298/(kcal mol−1), were determined to be 395.7 ± 0.7 for [Formula: see text] 391.7 ± 0.7 for [Formula: see text] 389.2 ± 0.6 for [Formula: see text] and > 396 for [Formula: see text] Heats of formation, ΔH0f.,298, were determined to be 30.5 ± 1.5 for CH3NH−, 21.2 ± 1.5 for C2H5NH−, and 24.7 ± 1.4 for (CH3)2N−. Electron affinities (in kcal mol−1) were determined to be 13.1 ± 3.5 for CH3NH, 17 ± 4 for C2H5NH, and 14.3 ± 3.4 for (CH3)2N. These results quantify earlier conclusions regarding the intrinsic effects of substituents on the gas-phase acidity of amines and provide an experimental assessment of recent molecular orbital calculations of proton removal energies for alkylamines.
Formation of tert-butyl cation in methane
Authors: Hiraoka K. , Kebarle P.
Published: May 2006

The reactions of CH3+ with pure methane in the torr range show an interesting temperature dependence. C2H5+ is formed at all temperatures by the well known reaction: CH3+ + CH4 = C2H5+ + H2. In the lowest temperature interval studied (105–125 K) C2H5+ adds two CH4 molecules to give a C4H13+ species. At higher temperatures only one CH4 molecule is added on. The resulting C3H9+ then reacts with one more CH4 molecule according to reaction 6.[Formula: see text]The rate constant k6 is found to be second order and has a positive temperature dependence. An Arrhenius plot gives:[Formula: see text]At temperatures above 200 K reaction 6 ceases to occur since C3H9+, being unstable at high temperatures, decomposes to s-C3H7+ + H2.The reactions were studied using ultra pure methane irradiated with electrons in a pulsed beam high ion source pressure mass spectrometer.The gas phase reaction mechanism for the formation of t-C4H9+ is found to bear close re-semblance to the probable mechanism by which the t-C4H9+ ion is formed from methane dissolved in superacid media.
Equilibria in the liquid system V2O5–V2O4 at temperatures up to 1130 K
Authors: Block-Bolten Andrew
Published: May 2006

The equilibrium oxygen pressure in the V2O–V2O4 system from temperatures near melting, up to 1130 K has been measured. A closed system solid electrolyte cell with a Ni/NiO reference electrode was used. The results of the present investigation for liquid solutions consistently extend those reported for solid solutions.
On the interpretation of measured rotational and vibrational relaxation times. II. Sudden change experiments
Authors: Pritchard Huw Owen
Published: May 2006

This paper examines, in terms of the normal-mode analysis developed earlier (Part I), the nature of relaxations in which a diatomic gas, highly diluted in a heat bath of inert gas atoms, is subjected to a sudden change as in shock-wave excitation or laser schlieren experiments.It is shown in detail how the observed relaxation time in a shock-wave excitation to a fixed final temperature depends on the initial temperature. At the same time, it is confirmed that the characterisation as 'mainly rotational' of the measured relaxation time in H2 when it is heated from room temperature to 1500 K in a shock wave is perfectly plausible.On the other hand, the calculations show that in laser schlieren experiments in which the v = 1, J = 1 level of H2 is overpopulated, the vibrational relaxation time of H2 at the temperature in question is recovered, although interesting effects should appear if other J levels were populated initially, or if the experiments were carried out at much higher ambient temperatures.The calculations also demonstrate that it is not generally possible to derive relaxation times by following the variation in population of any particular level of the molecule: multiple overshoots sometimes occur, and apparent relaxation times both longer or shorter than the true relaxation times could often result from attempts to follow level populations as a function of time.
Infrared study of the C—H stretching region of five-membered heterocyclic compounds
Authors: Cataliotti Rosario , Paliani Giulio
Published: May 2006

An infrared analysis of the C—H stretching region of some five-membered heterocyclic molecules (pyrrole, furan, thiophene, selenophene, and tellurophene) has been carried out. Spectra were obtained for gas, liquid, solution (CCl4), and crystal samples. Polarised infrared radiation was employed for crystalline oriented films. Band profiles in the gas phase and polarisation values for the crystal spectra have been used in order to get new assignments for this spectral region.
Metals intercalated in graphite. IV. Intercalation from CCl4 solution and extraction of intercalated species
Authors: Lalancette Jean Marc , Roy Linda , Lafontaine Jeannine
Published: May 2006

Some chlorides, mainly of transition elements, can be intercalated in graphite from a solution of carbon tetrachloride if their solubility is in the range of 1 to 4 mg/ml in CCl4, at reflux temperature, in the presence of chlorine.The rate of extraction of intercalated salts with solvents has been compared to the rate of solution of these salts in the same solvents.
Molecular reorientation in crystalline thiophene and furan
Authors: Sanford W. E. , Boyd R. K.
Published: May 2006

Molecular reorientation processes in crystalline thiophene and furan have been studied using pulse nmr techniques, over a range of temperature. The results obtained have been evaluated in the context of literature data on the heat capacities and crystal structures of these systems; this evaluation has been facilitated by the use of potential energy calculations for a molecule in the crystal lattice, based upon the empirical atom–atom approximation for the intermolecular interactions. In the case of furan, all available data can be reconciled in a self-consistent picture of the dynamic structure of the crystal. In the case of thiophene, however, various inconsistencies suggest that the published crystal structure determination should be repeated, and that further work on the pulse nmr at lower temperatures is necessary.
Studies in the usnic acid series. I. The condensation of (+)-usnic acid with aliphatic and aromatic amines
Authors: Kutney James P. , Sanchez Ignacio H.
Published: May 2006

Detailed investigations concerned with the reaction of usnic acid (1) and dihydrousnic acid (14) with a variety of aliphatic and aromatic amines are described. Extensive analyses of the characteristic spectroscopic data allow structural assignments for all the isolated products. The correctness of these assignments is established by an X-ray analysis of one of the products resulting from the reaction of usnic acid with ammonia.
The trifluoroacetic acid solvent system. Part V. Cryoscopic measurements
Authors: Harriss Michael G. , Milne John B.
Published: May 2006

Measurement of freezing point depressions for the non-electrolytes, CCl4. CH3SO2F, and (CF3CO)2O permit calculation of the cryoscopic constant for trifluoroacetic acid, HOTFA. Water is shown to give freezing point depressions lower than those for non-electrolytes and this is attributed to association. Freezing point depressions for NaOTFA, KOTFA, and CsOTFA have been measured and accounted for in terms of ion-pair dissociation constants previously determined from electrical conductivity measurements. The results cast doubt on the existence of triple ions in this solvent.
The acid cleavage of triphenylvinylmercuric salts
Authors: Lee Choi Chuck , Smith Peter J.
Published: May 2006

An attempted solvolytic demercuration of triphenylvinylmercuric acetate or bromide (1-HgOAc or 1-HgBr) in HOAc in the presence of HClO4 failed to give the triphenylvinyl cation, but instead gave a high yield of triphenylethylene (2). Kinetic studies showed that the formation of 2 from the reaction of 1-HgOAc with HClO4 in CH3OH was first order with respect to the substrate and second order with respect to HClO4. Mechanistic implications of these findings are discussed.
Substituent effects on the ionization constants of phenylazobenzaldoximes
Authors: Shawali Ahmad S. , Altahou Baheega M.
Published: May 2006

Ionization constants, pKa, for a set of 12 phenylazobenzaldoximes (1) have been determined in 50 vol% ethanol–water medium at 25 ± 0.1 °C and a μ of 0.1. Excellent linear correlations are obtained when pKa values are plotted against the substituent constant, σx, and the polar substituent constant, σ*XC6H4, for substituted phenyl groups. The regression lines are: pKa = 9.905–0.737σX; and pKa = 10.489 − 1.01σ* XC6H4 respectively. The pKa values have also been correlated with the extended Hammett equation. The correlation follows the equation: PKa =9.987 − 0.713σI,X−0.734 σR,X. It is concluded that EE and ZE forms of 1 exist in equilibrium in solution phase.
Estimation of the stereoselectivity of reduction of 3,3,5,5-tetramethylcyclohexanone by sodium borohydride
Authors: Wigfield Donald C. , Buchanan Gerald W. , Ashley Catherine A. , Feiner Steve
Published: May 2006

4-(1-Hydroxyethyl)-3,3,5,5-tetramethylcyclohexanone has been prepared to serve as a model for 3,3,5,5-tetramethylcyclohexanone on which the reduction stereochemical product ratio may be experimentally determined. Reduction with sodium borohydride in 2-propanol gives two epimers in a 95.5:4.5 ratio. The major isomer is shown to be the less stable by equilibration over Raney nickel. Proton and 13C nmr spectra confirm that this major epimer is cis-4-(1-hydroxyethyl)-3,3,5,5-tetramethylcyclohexanol and show that this compound exists predominantly in the conformation with an axial hydroxyethyl group and an equatorial hydroxyl group. It is concluded that reduction of this model compound proceeds at least 95.5% by equatorial attack.
The cis–trans isomerization of the radical anion of biacetyl
Authors: Elliot A. John , Wan Jeffrey K. S.
Published: May 2006

The equilibrium between the cis and the trans isomers of the biacetyl radical anion has been studied by esr spectroscopy. The dependence of this equilibrium on the solvent composition and temperature was followed.
Excess volumes of an alcohol + methylethylketone
Authors: Reddy Kalluru S. , Naidu Puligundla R.
Published: May 2006

Excess volume data for mixtures of 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol with methylethylketone were determined at 303.15 and 313.15 K. These volumes are negative with 1-propanol and increasingly positive with the higher homologs, suggesting that the structure-making effect of the ketone outweighs the structure-breaking effect in the first mixture of the series while the structure-breaking effect dominates in the other three mixtures. Further, the temperature coefficient of VE was found to be positive in all four mixtures.
The silver–pyrazole electrode and its application to determine the stability of Cd(II), Zn(II), Ni(II), Co(II) pyrazole complexes
Authors: Blais Marie-José , Berthon Guy
Published: May 2006

The silver–pyrazole metal-complex electrode was investigated and used to determine free concentrations of pyrazole in the presence of Cd2+, Zn2+, Ni2+, or Co2+ ion, under different pyrazole/divalent metal concentration ratios. The stability constants of the complexes formed between these ions and pyrazole were calculated.
Structure and stability of vitamin E – lecithin and phytanic acid – lecithin bilayers studied by 13C and 31P nuclear magnetic resonance
Authors: Cushley Robert J. , Forrest Bruce J.
Published: May 2006

13C spin–lattice relaxation studies on lecithin bilayers indicate a marked destabilization of the bilayer structure by incorporated vitamin E (d,l-α-tocopherol) and phytanic acid, phytanic acid causing the greatest perturbation.Kinetic analysis of paramagnetic praseodymium infusion into the lecithin vesicles containing various phytyl compounds has been performed using 31P nmr. Relative rates of Pr3+ leakage through the mixed lecithin – phytyl compound bilayer compared with pure lecithin (relative rate = 1.00) were: phytol = 7.8, vitamin E = 47.7, and phytanic acid = 2897.
Eiectrophilic additions of bromonium nitrate to unsaturated substrates
Authors: Lown J. William , Joshua Alummoottil V.
Published: May 2006

Bromonium nitrate (generated in situ by the reaction of bromine with silver nitrate in chloroform–pyridine) reacts trans-stereospecifically and regiospecifically in eiectrophilic additions to a series of Z–E pairs of alkenes to give bromoalkyl nitrate esters and bromoalkyl pyridinium nitrates. Addition to the less hindered (Z)-[β-2H]-styrene is also stereospecific, eliminating the possibility of restricted rotation during addition. Reaction with conjugated dienes gives rise to bipyridinium salts from 1,4-conjugate addition and displacement. The accompanying alkyl bromonitrate esters rearrange readily to the more stable 1,4-bromonitrates in the liquid phase. In contrast to the behavior of iodonium nitrate, bromonium nitrate reacts with 3,3,3-triphenylpropene to give an allylic pyridinium nitrate, which results from phenyl migration, the structure of which was proven by synthesis. Bromonium nitrate reacts with pent-4-en-1-ol to give 2-bromomethyltetrahydrofuran. Similar reaction with cyclohex-2-en-1-ol provides products corresponding to the addition of the bromonium ion both cis and trans to the hydroxyl group, unlike iodonium nitrate where specific interaction between the hydroxyl and the pyridine group leads exclusively to cis addition.
Studies on the iodide–triiodide equilibrium
Authors: Benoit Robert L. , Wilson Michael F. , Lam Sing-Yeung
Published: May 2006

The solvent effect on the iodide–triiodide equilibrium has been investigated by means of calorimetric and potentiometric measurements. The aprotic solvents studied were nitromethane, nitrobenzene, sulfolane, acetonitrile, propylene carbonate, acetophenone, dimethylformamide, dimethylsulfoxide, and o-dichlorobenzene. The resulting enthalpy and free energy changes imply that the variations of the enthalpies and free energies of transfer of the iodide and triiodide ions probably are small and that there is an important non-coulombic contribution to these transfer parameters. Values were obtained for the enthalpy of formation of two solid triiodides, which together with values for other triiodides, cast doubt on reported calculated lattice enthalpies of triiodides and formation enthalpy of I3− ion in the gas phase. This latter formation enthalpy is found to be, from our solution data, more negative than −22 kcal mol−1.
The kinetics of the solid state transformation of racemic to optically active 1,1′-binaphthyl
Authors: Wilson Keith R. , Pincock Richard E.
Published: May 2006

Rates of the solid state reaction which thermally converts racemic to optically active 1,1′-binaphthyl (mp 158 °C) have been determined at temperatures between 105 and 135 °C using polycrystalline samples. The presence of a sufficiently uniform distribution of enantiomorphic seed crystals results in a smooth conversion of the racemate to the eutectic crystal forms of binaphthyl. Although it is possible to force the resolution reaction almost to completion at higher temperatures (150 °C) where the melt phase is an intermediate, lower final specific rotations are obtained when only solid phases are involved (below 145 °C) because of the independent nucleation of racemic material from the reacting crystals. Both spontaneous nucleation and reaction rates in the solid state were increased by grinding the initially prepared samples and were decreased by the storage of samples. The Arrhenius activation energy of this phase transformation giving optically active product is ca. 60 kcal/mol in a variety of different samples. This is consistent with a mechanism in which a molecule of 1,1′-binaphthyl attains considerable freedom from the racemic solid in order to interconvert to its enantiomer and add to the growing optically active phase.
The reflection method in predissociation
Authors: Bandrauk André D. , Laplante Jean-Pierre
Published: May 2006

The reflection method is used to calculate energy shifts and linewidths in predissociation by a linear continuum. The analytic results of this method are compared to the exact analytic calculations. It is found that, as in semiclassical calculations, energy shifts and linewidths usually vanish at the same energies. The spectroscopic implications of this finding are pointed out.