bluuebunny/crossref_metadata_2025 huggingface dataset:
Performance Tests for Visual Servo Control Systems, with Application to Partitioned Approaches to Visual Servo Control
Authors: Gans Nicholas R. , Hutchinson Seth A. , Corke Peter I.
Published: October 2003

Visual servoing has been a viable method of robot manipulator control for more than a decade. Initial developments involved position-based visual servoing (PBVS), in which the control signal exists in Cartesian space. The younger method, image-based visual servoing (IBVS), has seen considerable development in recent years. PBVS and IBVS offer tradeoffs in performance, and neither can solve all tasks that may confront a robot. In response to these issues, several methods have been devised that partition the control scheme, allowing some motions to be performed in the manner of a PBVS system, while the remaining motions are performed using an IBVS approach.

To date, there has been little research that explores the relative strengths and weaknesses of these methods. In this paper we present such an evaluation. We have chosen three recent visual servo approaches for evaluation in addition to the traditional PBVS and IBVS approaches. We posit a set of performance metrics that mea sure quantitatively the performance of a visual servo controller for a specific task. We then evaluate each of the candidate visual servo methods for four canonical tasks with simulations and with experiments in a robotic work cell.
The Drugs Don't Work
Authors: Hedgecoe Adam , Martin Paul
Published: October 2003

This article examines one particular set of technologies arising from developments in human genetics, those aimed at improving the targeting, design and use of conventional small molecule drugs - pharmacogenetics. Much of the debate about the applications and consequences of pharmacogenetics has been highly speculative, since little or no working technology is yet on the market. This article provides a novel analysis of the development of pharmacogenetics, and the social and ethical issues it raises, based on the sociology of technological expectations. In particular, it outlines how two alternative visions for the development of the technology are being articulated and embedded in a range of heterogeneous discourses, artefacts, actor strategies and practices, including: competing scientific research agendas, experimental technologies, emerging industrial structures and new ethical discourses. Expectations of how pharmacogenetics might emerge in each of these arenas are actively shaping the trajectory of this nascent technology and its potential socio-economic consequences.
The Discursive Climate of Singleness: The Consequences for Women's Negotiation of a Single Identity
Authors: Reynolds Jill , Wetherell Margaret
Published: October 2003

The privileging of marriage and long-term partnerships contributes to the marginalization of single women. This article explores the ways in which women defined as single work with the typical constructions of their identity available in the public arena. We view `singleness' as a discursively constructed social category. Using data from interviews with 30 women, we examine the identity that women construct for themselves through their talk. We present the four main interpretative repertoires that women draw on and look at two patterns of identity work commonly used to deal with the highly polarized repertoires. Singleness is a troubled category, and yet the positive and idealized repertoires available seem to make other aspects of women's lives and expectations pathological. We argue for a feminist psychology of singleness based on critical discursive psychology: the focus needs to be on the patterning of ideology rather than the supposed dysfunction of single women.
Institutional Strength, Social Control and Neighborhood Crime Rates
Authors: Triplett Ruth A. , Gainey Randy R. , Sun Ivan Y.
Published: October 2003

While the systemic model that today's theories of social disorganization are based on acknowledges that neighborhood-based institutions may vary in their ability to contribute to effective social control, relatively little attention has been given to their role in understanding neighborhood rates of crime. At the same time, there is contradictory evidence about the role of social networks, which have been the focus of much research attention. This article builds upon past work to present a model of neighborhood-based institutional social control to address this lack of attention. The model centers on a conceptualization of institutional strength that distinguishes between the dimensions of institutional strength, and the causes and effects of variation in institutional strength.
Masters of their Conditions: At the Crossroads of Health, Culture and Performance
Authors: Arpin Jacques
Published: October 2003

Achieving one's cultural or clinical identity is a matter of performance. The performing body is made through a series of apprentice-ships that lead to mastery and then transmission. Performance, like culture and medicine, has its systems of learning, i.e. in the professions of the performing arts. This article examines the methodology of theater anthropology and other aspects of performance studies. Applications to intercultural work are described that make it possible for patient and healer to collaborate to master the condition.
A Vietnamese Man with Selective Mutism: The Relevance of Multiple Interacting `Cultures' in Clinical Psychiatry
Authors: Hollifiel Michael , Geppert Cynthia , Johnson Yuam , Fryer Carol
Published: October 2003

Multiple cultural variables have effects on the psychobiology and behavioral manifestations of illness, as do patient and physician perceptions of illness. The interaction among these variables is at the heart of clinical psychiatry. This case of a Vietnamese man with selective mutism under-scores the relevance of the `cultures' of medicine, psychiatry, and war and trauma on the manifestations of illness and illness perceptions by patient and physician. The discussion focuses on how these cultures interact and play a crucial role in formulating diagnosis and treatment planning. Sugges-tions are given for shifts in medical education that will encourage relevant cultural paradigms to make their way into educational and clinical systems, which in turn should improve cultural competence in clinical psychiatry.
`Hit by the Wind' and Temperature-Shift Panic among Vietnamese Refugees
Authors: Hinton Devon , Hinton Susan , Pham Thang , Chau Ha , Tran Minh
Published: October 2003

Surveying 60 Vietnamese patients with either current or past post-traumatic stress disorder, this article aims to phenomenologically characterize the syndrome of `hit by the wind' in a multidimensional manner. This includes determining the patient conceptualization of the disorder, profiling `hit by the wind' episodes suffered by patients in the previous month, and presenting case vignettes. Eighteen of the 60 patients (30%) suffered at least one episode of `hit by the wind' in the last month; all 18 patients had at least one episode of `hit by the wind' in the last month that met panic attack criteria. For the 18 patients, 33 episodes of `hit by the wind' that met panic attack criteria were experienced in the previous month. For these 33 episodes, the most frequently reported DSM-IV panic attack symptoms were chills (100%; 33/33) and dizziness (88%; 29/33). Flashbacks played a role in the `hit by the wind' episodes for 5 of the 18 patients (28%). In the discussion, a model of how the syndrome of `hit by the wind' generates panic is adduced; also, possible Chinese origins of the disorder are discussed.
Prevalence of Bulimic Behaviours and Eating Attitudes in Schoolgirls from Trinidad and Barbados
Authors: Bhugra Dinesh , Mastrogianni Anastasia , Maharajh Hari , Harvey Sharon
Published: October 2003

We investigated eating attitudes and the prevalence of bulimic disorders in a group of 362 schoolgirls from the islands of Trinidad and Barbados using key questions from the Bulimia Investigatory Test, Edinburgh (BITE) and additional questions for the exploration of eating attitudes and dieting practices. A random sample of 92 girls were interviewed using the DSM-III-R Bulimia Diagnostic Interview. Only three subjects (0.8%) scored over the cut-off point on the BITE. None of the interviewees was diagnosed as having bulimia nervosa. Two hundred and forty-five girls (67.7%) reported being terrified of becoming fat and fat-fear was associated with higher Body Mass Index, dieting and exercising for losing weight. Girls of African origin were found to have a more unusual eating pattern and more concerns about their eating habits. The prevalence of bulimic disorders in Caribbean schoolgirls is still very low, but they are a population at increasing risk since they share the western ideals of slimness and engage in dieting behaviours.
Unspeakable Bodies
Authors: Ferreday Debra
Published: October 2003

In this article, I explore the extent to which the `virtual community' has been imagined as coming into being through acts of erasure that create unmarked citizens. In contrast, `pro-ana' websites that celebrate eating disorders aim to create a community in which a sense of collectivity is constituted precisely through the body, specifically the anorexic body. By encouraging members to speak out, these communities aim to subvert the economy of difference through which the anorexic body is always positioned as `other', as the body that `has' difference. I argue that the public outcry surrounding pro-ana communities represents an appeal to censorship as a means by which, as Kristeva argues, outsiders might be `ejected beyond the scope of the possible, the tolerable, the thinkable' in order to reinstate the notion of consensus through the suppression of some forms of difference.
The Ethics of Indifference
Authors: Tonkiss Fran
Published: October 2003

Modern social theory has frequently represented city life as isolating, as degrading of social ties and as inimical to community. In another register, however, urban contexts have also been primary sites for imagining and re-imagining forms of community, especially on the basis of shared social spaces or elective identities. The discussion in this article explores this relation between solitude and community in the city. While a language of community has been important for articulating various politics of difference, I suggest that an ethics of indifference also opens up certain rights to the city. The point, however, is not simply to set a conception of indifference or anonymity against one of community or visibility, but rather to think about dissociation as a certain kind of social relation, to consider the solitude of cities as a common, if ambivalent, property. The discussion begins by addressing the nature of indifference and anonymity in urban contexts before turning to New York as the site for recent narratives of a private urban life, and a more public death, in order to explore the complex interplay of difference and indifference, community and solitude, in the city.
What's that Smell?
Authors: Halberstam Judith
Published: October 2003

This article is drawn from a book-length study of the explosion of queer urban subcultures in the last decade. My larger purpose is to examine how many queer communities experience and spend time in ways that are very different from their heterosexual counterparts. Queer uses of time and space develop in opposition to the institutions of family, heterosexuality and reproduction, and queer subcultures develop as alternatives to kinship-based notions of community. In my work on subcultures, I explore the stretched out adolescences of queer culture-makers and posit an `epistemology of youth' that disrupts conventional accounts of subculture, youth culture, adulthood, race, class and maturity. This article charts new developments in the theories of subcultures and youth cultures and argues that we should look now at the forms of stylistic resistance embedded in queer subcultural worlds.
Through their Eyes
Authors: Willnat Lars , Weaver David
Published: October 2003

This study, based on a mail survey conducted in early 2000, investigates the professional norms and values, personal backgrounds, daily routines and work-related problems of foreign correspondents working in the United States. The analysis assumes that the correspondents' professional values are related to what is reported about the United States around the world - and that this news coverage matters in terms of world public opinion and policies. The study identifies how foreign correspondents perceive their professional values and provides an in-depth analysis of where foreign journalists come from, how they think about their work and how they perceive their professional roles. Professional values analyzed in this study include perceptions of the importance of different journalistic roles, opinions on the importance of different aspects of the job and journalists' images of their readers, viewers and listeners. Professional norms include opinions about which questionable reporting methods might be justifiable. The main objective is to provide a detailed analysis of who foreign correspondents are, how they cope with their daily work, what specific problems they face in obtaining information from official and private sources and how they manage to adjust their professional work to American culture and customs. Some findings of this study are compared to similar studies of US journalists to provide a comparative context.
Poetry on the Margins
Authors: Ehrlich Matthew C.
Published: October 2003

A recent wave of radio documentaries has been credited with sparking a new approach to American journalism. This article critically examines two seminal documentaries, Ghetto Life 101 and Remorse: The 14 Stories of Eric Morse. They were co-created by independent producer David Isay and two African American teenagers from inner-city Chicago, LeAlan Jones and Lloyd Newman. While their work won a raft of awards, it also was criticized for irresponsibly perpetuating racist stereotypes. This article suggests that such documentaries are limited in the degree to which they counter stereotypes and demand accountability and justice. However, as a form of autoethnography, they make room for other voices in promoting social solidarity and empathy while serving as a model for journalism as a whole.
News: Ephemera, Data, Artefacts and... Quality Control - Iraq now and then
Authors: Palmer Michael
Published: October 2003

Quality control mechanisms exist in leading international news agencies. Monitoring the news output day-by-day or news-cycle by news-cycle so as to help improve performance `to-morrow', they are `hands-on' exercises in dissecting failures and comparing output with that of rival news-feeds and organizations - whether via text (in the form of figures and words), sound or image (news-films, still photos, computer graphics, etc.). Working from the assumption that journalists are their own severest critics and observing how they seek and note feedback from customers (both media and non-media), we look at Reuters' control mechanisms. The period observed is that of the Iraq `regime change', the US/UK offensive against Saddam Hussein, in March-April 2003. This case study illustrates attempts to identify elements of `the alchemy of news', while reviewing the logistics of coverage of one of the top international news stories of 2003.
The Secular Holy Scriptures
Authors: Neiger Motti , Roeh Itzhak
Published: October 2003

This article investigates the tension between the sacred and the secular in the modern press, by examining the role of the holiday literary supplements. It analyzed a sample of 1050 supplements, published in seven main newspapers in Israel over a period of 52 years, since the establishment of the state of Israel in 1948. In addition, a dozen interviews were conducted with present and former editors of the literary supplements. The main argument is that the literary supplements constitute a secular ritual. Speaking broadly we may call these literary supplements `The Secular Holy Scriptures'. This argument stems from the timing of publishing these supplements (every holiday eve); the writers featured (first-rank authors); the themes and subjects dealt with ('festive' and `high culture' topics); and the significance they acquire, over and above the weekday issues and other sections of holiday editions.

Although the case study focuses on Israeli daily newspapers, we believe that, with some adjustments, the main arguments can be usefully applied to other cultures as well, to throw light on the role of the media in the creation of modern culture and civil religion.
Philip Rieff's Moral Vision of Sociology
Authors: Manning Philip
Published: October 2003

In this article I present Rieff as a theorist and moralist of cultural change. The trajectory of his work is from the elusively descriptive to the elusively prescriptive. Descriptively, Rieff identifies the elements of what he calls our current `negative communities' and contrasts them with moribund `positive communities' and their `therapies of commitment'. He believes that, among others, Weber and Freud both recognized that negative communities emerge once positive communities are recognized as illusory. Prescriptively, while still accepting the intellectual justification for negative communities, Rieff became transparently critical of their byproducts: a `remissive' culture incapable of distinguishing `god-terms' from `transgressive depths'. This culture produces a relativist, permissive culture, a version of the cult of the individual, alienation, consumerism and indifference to tradition. In most of his work, Rieff acknowledged the inevitability of negative community but not the inevitability of its byproducts. In his most recent work he has tried to preserve the monotheistic `second culture' and oppose the approaching `third culture' of modernity. Through his teaching and scholarship, Rieff has tried to envisage what a contemporary model of the sacred might be like in a negative community. In doing so, he has been drawn back to the positive communities that he had believed were no longer viable. Rieff's dilemma is that the sacred order that he wishes to preserve can only be defined by what it forbids. Therefore, any effort to specify it is self-defeating. It is preserved not through celebrations but by the negative and in his view vital emotion of guilt.
The Therapeutic Ideology of Moral Freedom
Authors: Woolfolk Alan
Published: October 2003

Philip Rieff's theory of culture remains as relevant today for assessing the state of Western cultures as it was in the 1960s when it was initially formulated. As Rieff predicted, therapeutic culture has gone beyond `the analytic attitude' to form its own set of remissive `controls' that are implicit in the tolerance and moderation described by Alan Wolfe in his study of the `impossible idea of moral freedom'. The contemporary ideology of moral freedom is most closely linked with what is commonly termed `the new class'. As what Alvin Gouldner calls a `cultural bourgeoisie', this class has not simply material but also therapeutic interests in defending the idea of moral freedom. In addition, the moderation of the contemporary quest for moral freedom must be understood as having resulted from the cultural and sociopsychological strains that grew out of the quest for freedom and autonomy, which both Rieff and Gouldner trace back to the modern intellectual, and which became widespread in the 1960s. However, the reforms of the therapeutic revolution do not resolve the basic contradictions of a culture that has fewer and fewer interdictory controls. Even the doctrine of human rights as ably defended by Michael Ignatieff fails to explain what will restrain the human desire to be and express everything. As perhaps the noblest expression of the quest for moral freedom, this doctrine reveals the shortcomings of merely defending human agency, while neglecting the limitation of human possibilities upon which civilized existence and inner development of the personality depend.
Rieff's Freud and the Tyranny of Psychology
Authors: Kaye Howard L.
Published: October 2003

When Philip Rieff's magisterial Freud: The Mind of the Moralist was first published in 1959, Freud's status as a scientific authority was at its height. Even within sociology, Freud was considered to be one of the discipline's essential theorists. At such a time, Rieff's text was clearly indispensable for its illuminating accounts of Freud's thought and of its social, moral and political implications. Today, Freud's status as scientist and social theorist has fallen to an all-time low. Nevertheless, his demise has left the value of Rieff's Freud unaffected. In fact, a re-reading of The Mind of the Moralist is a powerful reminder of what makes Freud so central as a cultural figure, and Rieff so essential as a social theorist of the present age. While Rieff highlights those aspects of Freud's thought that remain valuable and sociologically relevant, the real purpose of Rieff's book is to examine its cultural impact. In Rieff's view, Freud's anatomy of the soul and his reductionistic account of the dynamics of culture have proven to be dangerously antinomian and nihilistic in their effects, despite Freud's avowed positions. The `ethic of honesty' espoused by Freud for therapeutic reasons veered dangerously close to a `therapy of barbarism' and to a disenchantment of the inner life that has proven to be more oppressive than liberating. To find a way out from this `tyranny of psychology' became the focus of Rieff's subsequent theoretical work.
Philip Rieff's Mission
Authors: Langman Lauren
Published: October 2003

The work of Philip Rieff remains seminal for sociological concerns with morality and values. Informed by Freudian theory, noting the impact of Freud in fostering a `therapeutic culture' in which `psychological man' places `feeling good' over community-based, transcendental systems of meaning and value, Rieff, like many intellectuals of his age, defended the importance of repression for maintaining civilization in face of the growth of mass-mediated popular culture, which, as a moment of consumerism, was complicit in under-mining repression and eroding the standards of taste. His analysis is still especially cogent as we face two challenges to Western civilization. In the first place, we have seen a `carnivalization of society' in which the `culture industries' offer more and more tasteless transgressions that foster a `regression in the service of consumer-ism' to encourage consumerism, shopping-mall selfhood and indifference to the political. Second, in face of the social stresses and strains of globalization in general, and the privatized, erotic hedonism of the carnival, we have seen worldwide proliferation of fundamentalisms mixing stern, austere restraint and repression with primary-process magical thought that would ameliorate the problems of the world through prayer, ritual and faith. Both represent expressions of anti-intellectualism and disdain of elites; neither sustains the values of civilization and civility that Rieff would defend.
Schumpeter and Weber on the Institutions of Capitalism
Authors: Ingham Geoffrey
Published: October 2003

In a `new introduction' to their work, Richard Swedberg (2002) argues that Weber and Schumpeter's `economic sociology of capitalism' contains a `puzzle'. Weber and Schumpeter are said to believe that a vigorous capitalism requires `something else' in addition to the institutions outlined in their respective ideal types and theories. Dynamic capitalism requires individuals who possess a distinctive `mentality' or `inner motivation' - that is, a `capitalist or entrepreneurial spirit'. This new introduction is entirely consistent with the tenor of existing sociological interpretations of Weber and Schumpeter. But, more importantly, both Swedberg and the sociological tradition of which he is critical completely ignore the institutional source of dynamism that is central to Schumpeter's Theory of Economic Development and figures in Weber's General Economic History. Both saw that a differentia specifica of capitalism is the production of an elastic supply of credit-money by banks and states, without which entrepreneurial activity could not take place.
Resources, Power and Systematic Luck: A Response to Barry
Authors: Dowding Keith
Published: October 2003

Brian Barry attacks the `resource account' of power providing a set of definitions through which power should be analysed. While there might be different, equally good, ways of defining power, I argue that the formulations provided by Dowding are superior to those of Barry as they produce fewer anomalies and provide a better foundation for empirical research. The article defends the resource account against Barry's criticisms and argues for the utility of the ideas of luck and `systematic luck'.
Capitalists Rule. OK? A Commentary on Keith Dowding
Authors: Barry Brian
Published: October 2003

In response to criticisms made by Keith Dowding (hereafter KD) of `Capitalists Rule OK', this article argues (1) that there is a genuine structural conflict of interest between consumers and producers, voters and politicians, and capitalists and governments, and (2) that only by ad hoc and arbitrary limitations on the scope of the concept of power can it be denied that consumers collectively have power over producers and capitalists (collectively) have power over government. KD accepts that voters (collectively) have power over governments. Ironically, however, this is by far the most tenuous and generally problematic of the three putative power relations. Furthermore, there is no plausible way of conceding that voters (collectively) have power over politicians without also having to accept the validity of a power relation in the other two cases. The implication is that the thesis that is supposed to justify the standard North American or western European politico-economic system, according to which consumers and voters have power but capitalists do not, is nothing more than ideology, in Marx's sense of a fantastical picture of the world designed by the beneficiaries of the status quo to protect their privileged positions against legitimate demands for revolutionary change. The article concludes by taking up KD's primary objection to `Capitalists Rule', which is its rejection of the proposal to equate power with resources. According to KD's official definition, `resources' are the means of raising and lowering others' utilities. I pointed out in `Capitalists Rule' that KD himself acknowledges the inadequacy of this definition, since he almost immediately goes on to say that people do not necessarily have the power that is attributed to them. Obviously, `power' in this new sense must be something different, and is, in fact, the ability to get people to do what you want them to do or to refrain from doing things you do not want them to do. This is precisely my own proposed definition in `Capitalists Rule'. The only remaining disagreement arises from KD's wish to turn everything that lies between power in his first sense and power in his second (and my) sense into a further `resource'. I argue that this is obfuscatory and, in any case, infeasible.
Assumptions of Rationality and Equilibrium in Strategy Research: The Limits of Traditional Economic Analysis
Authors: Bromiley Philip , Papenhausen Chris
Published: October 2003

We argue that two core assumptions of economic analysis - managers and employees make optimal decisions and markets operate in equilibrium - have undesirable implications in strategic management research. To show how these assumptions lead to dubious implications, we analyze two exemplars of the rigorous application of these assumptions in strategic management research: Barney's (1986a) `Types of competition and the theory of strategy: toward an integrative framework' and Mosakowski's (1998) `Managerial prescriptions under the resource-based view of strategy: the example of motivational techniques'. We also introduce the basics of a behavioral theory of the firm, which we claim is prefer-able to traditional economic analysis and its severely limiting assumptions. Finally, we argue that most research in strategic management takes an implicitly behavioral view and would benefit from making that view explicit.
Assay of Nucleic Acids at the Water/Tetrachloromethane Interface with Cetyltrimethylammonium Bromide by Total Internal Reflected Resonance Light Scattering
Authors: Pang Xiao Bing , Huang Cheng Zhi , Li Yuan Fang , Lu Wei
Published: October 2003

In this contribution, nucleic acids, including calf thymus DNA (ctDNA), fish sperm DNA (fsDNA), and yeast RNA (yRNA), have been determined with good selectivity and sensitivity at the water/tetrachloromethane (H2O/CCl4) interface by a total internal reflected resonance light scattering (TIR-RLS) technique. Under optimal conditions, amphiphilic complexes produced by nucleic acids and cetyltrimethylammonium bromide (CTMAB) are absorbed at the H2O/CCl4 interface, resulting in a good separation of nucleic acids from the coexisting foreign substances in the aqueous phase and enrichment of nucleic acids at the interface. All of these induce significantly enhanced TIR-RLS signals with the maximum peak located at 370.0 nm at the interface. It was found that the enhanced TIR-RLS intensity is in good proportion to the concentration of nucleic acids in the range of 0.06–2.5, 0.015–3.5, and 0.046–3.5 μg mL−1 for ctDND, fsDNA, and yRNA, respectively, and their limits of detection (3σ) are 6.0 ng mL−1, 1.5 ng mL−1 and 4.6 ng mL−1 correspondingly. Artificial samples with complicated and highly interfering backgrounds were analyzed satisfactorily.
Interaction of Dicationic Bis(imidazoliumyl)porphyrinatometals with DNA
Authors: Yamamoto Tomoko , Tjahjono Daryono Hadi , Yoshioka Naoki , Inoue Hidenari
Published: October 2003

A pair of dicationic metalloporphyrins with only two meso-substituents, i.e. copper(II) and zinc(II) complexes of 5,15-bis(1,3-dimethylimidazolium-2-yl)porphyrin (H2-1), have been synthesized by insertion reaction of the metal ions. Interactions of [5,15-bis(1,3-dimethylimidazolium-2-yl)porphyrinato]copper(II) (Cu-1) and [5,15-bis(1,3-dimethylimidazolium-2-yl)porphyrinato]zinc(II) (Zn-1) with calf thymus DNA (CT-DNA) and double-helical synthetic polynucleotides ( [poly(dA–dT)]2 and [poly(dG–dC)]2 ) have been studied by melting temperature, viscometric, visible absorption, CD and MCD spectroscopic measurements. The copper(II) complex, Cu-1, intercalates into the base pairs of DNA such as CT-DNA, [poly(dA–dT)]2 and [poly(dG–dC)]2 to stabilize the DNA duplex due to its high affinity for them. In contrast, the zinc(II) complex, Zn-1, binds edge-on to CT-DNA, [poly(dA–dT)]2 and [poly(dG–dC)]2 as an outside binder. The binding constant of Cu-1 to DNA is in the order of 106 M−1 in a phosphate buffer (pH 6.8) at 25 °C, while that of Zn-1 ranges from 104 to 105 M−1 under the same experimental conditions. The binding of Cu-1 and Zn-1 to DNA is entropically driven, although that of H2-1 is enthalpically driven. As a result, it has been revealed that the kind of central metal ions in dicationic metalloporphyrins influences the binding properties of the dicationic porphyrin to DNA.
Mechanism for Aerobic Oxidation of 3,5-Di-tert-butylcatechol to 3,5-Di-tert-butyl-o-benzoquinone Catalyzed by Di-μ-hydroxo-dicopper(II) Complexes of Peralkylated Ethylelnediamine Ligands
Authors: Kodera Masahito , Kawata Tomohisa , Kano Koji , Tachi Yoshimitsu , Itoh Shinobu , Kojo Shosuke
Published: October 2003

The aerobic oxidation of 3,5-di-tert-butylcatechol (H2dbc) to the corresponding quinone (dbq), catalyzed by di-μ-hydroxo-dicopper(II) complexes [Cu2(OH)2L2](ClO4)2 [L = N,N′-tetramethylethylenediamine (tmeda) (1) and N,N′-tetraethylethylenediamine (teeda) (2)], has been spectroscopically and kinetically studied to gain some insight into the reaction mechanisms. The ESR spectra show that catecholato complexes [Cu(dbc)L] [L = tmeda (3) or teeda (4)] are formed upon reactions of 1 or 2 with H2dbc, respectively. The UV–vis and ESI mass spectra show that 3 is converted to a semiquinonato complex [Cu(dbsq)tmeda]+ (5) in the aerobic oxidation, while [Cu(dbsq)teeda]+ (6) is only a minor species. In the presence of acid, 3 and 4 are aerobically oxidized to dbq quantitatively. Kinetic studies show that rate constants for the catalytic aerobic oxidation of H2dbc are proportional to the second or the first order with 1 or 2, respectively, and to the first-order with the O2-partial pressure. Based on these data, different reaction mechanisms are proposed for 1 and 2, and may be caused by the steric hindrances around the copper center of 1 and 2.
Heck Reaction over Pd-Loaded ETS-10 Molecular Sieve
Authors: Waghmode Suresh Babasaheb , Wagholikar Smita Girish , Sivasanker Subramanian
Published: October 2003

A palladium-loaded ETS-10 molecular sieve has been used as a catalyst in Heck reaction. The catalyst exhibits high activity and selectivity towards the carbon–carbon coupling of aryl halides with olefins, even at low concentrations of Pd (0.009 to 1.4 mol% with respect to the substrate). In the case of the coupling of ethyl acrylate with iodobenzene, 96% conversion of iodobenzene with greater than 98% selectivity could be obtained within 1 h over a 0.2 wt % Pd-loaded catalyst. The catalyst activates aryl bromide and chloride substrates, and appears to be heterogeneous. The reaction has been investigated with different alkyl halides, olefins and bases.
Synthesis of Dihydropyrrole and Pyrrole Derivatives by Radical Cyclization of γ,δ-Unsaturated Ketone O-Acetyloximes
Authors: Yoshida Masayuki , Kitamura Mitsuru , Narasaka Koichi
Published: October 2003

Treatment of γ,δ-unsaturated ketone O-acetyloximes with a catalytic amount of 1,5-naphthalenediol or hydroquinone, acetic acid, and 1,4-cyclohexadiene affords various dihydropyrrole and pyrrole derivatives via radical cyclization induced by one-electron reduction of the oximes.
Intramolecular Substitution Reaction of Lithium Alkylidene Carbenoids. Regioselective Synthesis of Indenes
Authors: Yanagisawa Hideyuki , Miura Kasei , Kitamura Mitsuru , Narasaka Koichi , Ando Kaori
Published: October 2003

When 4,4-dibromo-3-alkenols are treated with butyllithium, an intramolecular substitution reaction with alkoxide moiety occurs at the lithium alkylidene carbenoid center to give dihydrofurans. The reaction mechanism of this intramolecular substitution reaction is studied by B3LYP density functional calculations with the 6-31+G(d) basis set, and the substitution is found to proceed in a concerted manner. This substitution reaction is applied to the regioselective preparation of indene derivatives. That is, treatment of 3-(o-bromophenyl)-1,1-dibromopropene derivatives 23 with butyllithium results in the formation of intramolecular substitution intermediates, 3-indenyllithiums D, which are trapped with electrophiles to afford substituted indenes regioselectively.
A Facile Preparation and Properties of (2E,4E,6E,8E)-1-(3-Guaiazulenyl)-3,7-dimethyl-9-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6,8-nonatetraen-1-ylium Hexafluorophosphate
Authors: Nakamura Masaru , Sasaki Masato , Takekuma Hideko , Minematsu Toshie , Takekuma Shin-ichi
Published: October 2003

Reactions of guaiazulene (1) with all-trans- and 13-cis-retinals (2a and 2b) in methanol in the presence of hexafluorophosphoric acid at −10 °C for 1 h afforded the title monocarbocation compound 3 in 87–91% yield, respectively.
Selection of the simplest RNA that binds isoleucine
Authors: LOZUPONE CATHERINE , CHANGAYIL SHANKAR , MAJERFELD IRENE , YARUS MICHAEL
Published: October 2003

We have identified the simplest RNA binding site for isoleucine using selection-amplification (SELEX), by shrinking the size of the randomized region until affinity selection is extinguished. Such a protocol can be useful because selection does not necessarily make the simplest active motif most prominent, as is often assumed. We find an isoleucine binding site that behaves exactly as predicted for the site that requires fewest nucleotides. This UAUU motif (16 highly conserved positions; 27 total), is also the most abundant site in successful selections on short random tracts. The UAUU site, now isolated independently at least 63 times, is a small asymmetric internal loop. Conserved loop sequences include isoleucine codon and anticodon triplets, whose nucleotides are required for amino acid binding. This reproducible association between isoleucine and its coding sequences supports the idea that the genetic code is, at least in part, a stereochemical residue of the most easily isolated RNA–amino acid binding structures.
Ribosomal dynamics inferred from variations in experimental measurements
Authors: GABASHVILI IRENE S. , WHIRL-CARRILLO MICHELLE , BADA MICHAEL , BANATAO D. REY , ALTMAN RUSS B.
Published: October 2003

The crystal structures of the ribosome reveal remarkable complexity and provide a starting set of snapshots with which to understand the dynamics of translation. To augment the static crystallographic models with dynamic information present in crosslink, footprint, and cleavage data, we examined 2691 proximity measurements and focused on the subset that was apparently incompatible with >40 published crystal structures. The measurements from this subset generally involve regions of the structure that are functionally conserved and structurally flexible. Local movements in the crystallographic states of the ribosome that would satisfy biochemical proximity measurements show coherent patterns suggesting alternative conformations of the ribosome. Three different types of data obtained for the two subunits display similar “mismatching” patterns, suggesting that the signals are robust and real. In particular, there is an indication of coherent motion in the decoding region within the 30S subunit and central protuberance and surrounding areas of the 50S subunit. Directions of rearrangements fluctuate around the proposed path of tRNA translocation and the plane parallel to the interface of the two subunits. Our results demonstrate that systematic combination and analysis of noisy, apparently incompatible data sources can provide biologically useful signals about structural dynamics.
Modafinil for Remitted Bipolar Depression with Hypersomnia
Authors: Fernandes Praveen P , Petty Frederick
Published: October 2003

OBJECTIVE:

To report 2 cases of bipolar disorder with recent depression in remission with prominent residual hypersomnia, responding well to the addition of the psychostimulant modafinil.

CASE SUMMARIES:

Two patients with bipolar disorder with recent depressive episodes in remission are presented. Despite the absence of prominent depressive symptoms, both patients had significant hypersomnia, with scores ranging from 15 to 20 (maximum 24) on the Epworth Sleepiness Scale. The addition of modafinil to their medication regimen resulted in a decrease in hypersomnia and improvement in their level of functioning.

DISCUSSION:

This is the first report (MEDLINE search, October 7, 2003) demonstrating the use of modafinil in the treatment of hypersomnia in bipolar disorder while mood symptoms were in remission. Hypersomnia frequently occurs in depressive episodes and can be disabling when severe. The patients had optimal mood stabilization with mood stabilizers and antidepressants, but continued to experience excessive daytime sleepiness. Conventional stimulants were not considered because of the risk of triggering mania. The addition of the selective psychostimulant modafinil resulted in significant improvement in the hypersomnia, with improvement in functioning. No adverse effects or mood changes were noted.

CONCLUSIONS:

Modafinil may be a well-tolerated and effective alternative to conventional stimulants in the treatment of hypersomnia, especially in bipolar disorder, where there is considerable risk of switch to mania with stimulant medications. Modafinil may be useful even when depressive symptoms are not prominent.
Effect of modified layered silicates and compatibilizer on properties of PMP/clay nanocomposites
Authors: Wanjale Santosh D. , Jog J.P.
Published: October 2003

The preparation and properties of poly(4‐methyl‐1‐pentene) (PMP)/clay nano‐composites are described for the first time. The effect of clay modification and compatibilizer on the formation and properties of the nanocomposites is studied. Layered silicates modified with two types of quaternary ammonium salts are used. The X‐ray diffraction results indicate intercalation of the polymer into the intergallery spacing of the clay. Thermogravimetric analysis shows a delay in the degradation process. Dynamic mechanical analysis shows an increase in the storage modulus for the nanocomposites. The use of compatibilizer containing maleic anhydride and acrylic ester groups is explored. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3233–3238, 2003
Preparation of new polymers from heterocyclic compounds and reactive solvents of melamine
Authors: Lubczak Jacek , Lubczak Renata , Zarzyka‐Niemiec Iwona
Published: October 2003

Reactive solvents were obtained from reactions of acetone with formaldehyde. They were used for the dissolution of some heterocyclic compounds. When the dissolution of the obtained compounds was not possible, the structures of these compounds were modified to increase their solubility. The oligomers cured at 80–120°C in the presence of an acidic catalyst. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3390–3401, 2003
γ‐Irradiation preparation of poly(acrylic acid)–chitosan hydrogels for in vitro drug release
Authors: Shim Jae‐Woon , Nho Young‐Chang
Published: October 2003

Biocompatible and biodegradable pH‐responsive hydrogels based on poly(acrylic acid) and chitosan were prepared for controlled drug delivery. These interpolymeric hydrogels were synthesized by a γ‐irradiation polymerization technique. The degree of gelation was over 96% and increased as the chitosan or acrylic acid (AAc) content increased. The equilibrium swelling studies of hydrogels prepared under various conditions were carried out in an aqueous solution, and the pH sensitivity in a range of pH 1–12 was investigated. The AAc/chitosan hydrogels showed the highest water content when 30 vol % AAc and 0.1 wt % chitosan were irradiated with a 30 kGy dose of radiation. In addition, an increase of the degree of swelling with an increase in the pH was noticed and it had the highest value at pH 12. The drug 5‐fluorouracil was loaded into these hydrogels and the release studies were carried out in simulated gastric and intestinal fluids. The in vitro release profiles of the drugs showed that more than 90% of the loaded drugs were released in the first 1 h at intestinal pH and the rest of the drug was released slowly. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3270–3277, 2003
Poly(vinyl alcohol) nanocomposites with different clays: Pristine clays and organoclays
Authors: Chang Jin‐Hae , Jang Tae‐Gab , Ihn Kyo Jin , Lee Won‐Ki , Sur Gil Soo
Published: October 2003

Poly(vinyl alcohol) (PVA)/clay nanocomposites were synthesized using the solution intercalation method. Na ion‐exchanged clays [Na+–saponite (SPT) and Na+–montmorillonite (MMT)] and alkyl ammonium ion‐exchanged clays (C12–MMT and C12OOH–MMT) were used for the PVA nanocomposites. From the morphological studies, the Na ion‐exchanged clay is more easily dispersed in a PVA matrix than is the alkyl ammonium ion‐exchanged clay. Attempts were also made to improve both the thermal stabilities and the tensile properties of PVA/clay nanocomposite films, and it was found that the addition of only a small amount of clay was sufficient for that purpose. Both the ultimate tensile strength and the initial modulus for the nanocomposites increased gradually with clay loading up to 8 wt %. In C12OOH–MMT, the maximum enhancement of the ultimate tensile strength and the initial modulus for the nanocomposites was observed for blends containing 6 wt % organoclay. Na ion‐exchanged clays have higher tensile strengths than those of organic alkyl‐exchanged clays in PVA nanocomposites films. On the other hand, organic alkyl‐exchanged clays have initial moduli that are better than those of Na ion‐exchanged clays. Overall, the content of clay particles in the polymer matrix affect both the thermal stability and the tensile properties of the polymer/clay nanocomposites. However, a change in thermal stability with clay was not significant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3208–3214, 2003
Isothermal crystallization of metallocene‐based polypropylenes with different isotacticity and regioregularity
Authors: Xu Jun‐Ting , Guan Fang‐Xiao , Yasin Tariq , Fan Zhi‐Qiang
Published: October 2003

Three polypropylenes with various isotacticities and regioregularities were prepared with metallocene catalysts at different polymerization temperatures. WAXD results showed that the relative content of γ crystals in polypropylenes increased as isotacticity decreased. It was found that the γ crystal overcame the α crystal and became predominant in polypropylene of low isotacticity and high regioerrors. More γ crystals were also formed at higher crystallization temperatures. The isothermal crystallization kinetics of α and γ crystals were compared and the metastability of these two crystal phases was interpreted in terms of the crystallization kinetics. It was observed that the α crystal has a faster crystallization rate than that of the γ crystal and, thus, higher stability at low temperature. By contrast, the γ crystal tends to have a faster crystallization rate and becomes more stable at high temperature. The metallocene‐based polypropylenes with different isotacticities have similar Avrami exponents. As the content of the γ crystal increases, double melting peaks become more evident. Equilibrium melting temperatures were derived from Hoffman–Weeks analysis and very close equilibrium melting temperatures were obtained, 185.5 and 184.0°C, for two metallocene‐based polypropylenes containing major α crystals and one of 182.5°C for the polypropylene with predominant γ crystals. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3215–3221, 2003
Preparation and properties of novel polyimides with side chains containing biphenyl units
Authors: Liu Xikui , Xiang Hai , Yang Jin , Gu Yi
Published: October 2003

Novel polyimides with side chains containing various methylene spacers and biphenyl end groups were prepared. They were characterized by the inherent viscosity, mechanical properties, and solubility and by Fourier transform infrared, 1H‐nuclear magnetic resonance, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. All the polyimides with biphenyl side groups could be formed into tough films. WAXD showed that all the films were apparently amorphous. By incorporating side chains, the solubility was greatly enhanced and all the polyimides with side chains showed good solubility in polar aprotic solvents, while the high moduli and strength of typical polyimides were maintained and even improved. However, the heat‐resistant properties such as the thermal stability and glass transition temperature were generally decreased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3291–3298, 2003