bluuebunny/crossref_metadata_2025 huggingface dataset:
Business Ethics, Accounting and the Fear of Melancholy
Authors: Bos René ten
Published: July 2003

In the article, I address the strained relationship between business, the ethics of business and working life, on the one hand, and what is sometimes referred to as melancholy, on the other. I take issue with the age-old claim that one should keep to the books if one is to prevent melancholy. I argue that this claim, half-forgotten as it may be, is still implicit in many texts on business ethics. Much of what I have to say is grounded in a different, explicitly `anti-bourgeois' understanding of melancholy. To pave the way for such a different understanding, I will bring in ideas stemming from a wide and rather unusual range of sources (for example, Aristotle, Ficino, Defoe, Lepenies, Tarkowskij and, perhaps most importantly, Benjamin). The point is that these sources allow us to understand that one objective of business ethics is to help management and organizations to block off certain experiences that are, for various reasons, deemed to be unwelcome.
Caring for a Child with Spina Bifida: Understanding the Child and Carer
Authors: Zipitis Christos S. , Paschalides Constantinos
Published: July 2003

Spina bifida is a common congenital abnormality, which causes significant physical and psychological morbidity in affected children and which also affects their carers. This small-scale study looked at the health problems of a child with a myelomeningocoele. It also addresses the psychosocial problems that his mother, his main carer, faced and the social networks involved in his care. The evidence supporting various aspects of spina bifida prevention and management is explored. Furthermore, a literature review is included, with regards to physical and psychological issues for child and carer. This study aims to raise awareness of the problems faced by children with myelomeningocoele and their families. In particular, we aim to educate health care professionals on the importance of perceived stress by carers of such children, and suggest ways to reduce psychosocial morbidity.
Skills or Skilled? Children's Nursing in the Context of the Current Debate Around Nursing Skills
Authors: Kenny Gerard
Published: July 2003

This article seeks to demonstrate how the current debate around nursing skills is derived from an economic model of care and competency that has been based on the needs of the adult population. The professional perspective of children's nursing has been unheard in policy and decision-making circles concerning the skills agenda debate within educational and clinical practice. As a consequence, the need of children's nurses has been assumed to be the same as those of general/adult nursing. This article argues that children's nursing has followed a different historical and professional pathway on its progression to maturity. These differences call for alternative educational and clinical solutions for children's nurses in the issue of skills acquisition. In the children's nursing context, this is the difference between having a skill and being skilled. Recognition of this could ensure that children's nursing has a valuable contribution to make to the debate from its unique perspective.
Nietzsche, Freedom and Power
Authors: Mandalios John
Published: July 2003

In contradistinction to a common misconception of Nietzsche as a theoretician who only concerned himself with power, it is argued Nietzsche can be understood as a philosopher who conceived of power in relation to will, freedom, cause and effect, and responsibility. His conception of freedom poses a challenge to mainstream liberal and juridico-rights based political philosophies; it arguably also challenges some of the claims propounded by today's foremost critical theorist, Jürgen Habermas. What is overlooked, due to an unduly deconstructive restriction, is the saliency of freedom in Nietzsche's thought which, moreover, is linked to an abiding interest in responsibility - a point overlooked by Foucault, Habermas and critics of Nietzsche.
Unhastening Science
Authors: Pels Dick
Published: July 2003

What is so special about science? Taking up the old epistemological challenge, this article seeks to rephrase the question of scientific autonomy beyond conventional essentialist criteria of demarcation between science and society. The specificity of science is primarily sought in its studied `lack of haste', its socially sanctioned withdrawal from the swift pace of everyday life and from `faster' cultures such a politics and business. This `unhastened' quality defines science's peculiar delaying tactics, which systematically slow down and objectify ordinary conversations, actions, and conflicts, attracting `slow' personalities who read and write more and talk less than the `fast cats' who are attracted to more decisionist, stress-driven and hasty cultures. Such a description, rather than claiming performative innocence, simultaneously expresses the ambition to strengthen what it characterizes, i.e. to liberate science from the stress and haste which are increasingly imposed upon it by the `external' pressures and performance criteria of enterprise culture and political correctness, and by the growing impact of media publicity and the academic celebrity system. In this fashion, the article simultaneously advances a new factual description of the specificity of scientific practice and a new normative/political project to enhance scientific and intellectual autonomy.
Teacher Education for Muslim Women
Authors: Scott-Baumann Alison
Published: June 2003

In order to manage our daily lives, we make many decisions based on empirical evidence derived from instrumental action. At the other extreme, we are often attracted by a so-called postmodern solution that invites us to make arbitrary choices. In the education system, the pressing dilemma should not be a choice between standards of competence or unthinking relativism, but how to take action towards intercultural tolerance. Establishing a small teacher training course for a group of British Muslims has shown that communicative action informed by understanding can be disabled by the instrumentality of positivist frameworks, such as those used by government inspectors. In philosophy, Ricoeur offers a provisional dialectic of hope that can be used to show why neither positivist methods, rational analytic philosophy, postmodernity nor any one belief system for interpreting the world should be allowed to exert hegemonic control. The ethicopractical philosophy of Ricoeur also offers a reconstructive view of reality that helps us to rehabilitate belief in human nature and encourages us to seek solutions to conflicts of interpretation in understanding others. It is applied, in this instance, to project work with Muslim women in the UK, in which an ontology of action shows the power of working collaboratively towards an understanding of oneself as another.
Extrathoracic angiomyolipomas in lymphangioleiomyomatosis
Authors: Maziak DE , Kesten S , Rappaport DC , Maurer J
Published: June 2003

Pulmonary lymphangioleiomyomatosis (LAM) is a rare disorder that affects women and can lead to serious respiratory impairment. Since Bourneville's tuberous sclerosis (TS) was first reported, the striking similarities between the two entities have led many to believe that LAM is a forme fruste of TS. This is suggested by reports that angiomyolipomas, rare tumours in themselves, are reported in 40-80% of TS patients and occur in 15-30% of LAM patients. A retrospective chart review was conducted of 14 patients that presented to our institution with a diagnosis of LAM. We sought to document the clinical manifestations, particularly the incidence and location of extrathoracic tumours, in order to further support the hypothesis that LAM is a forme fruste of TS. Twelve patients had premenopausal onset of symptoms and two postmenopausal. The diagnosis was confirmed histologically (n = 12) and/or by computed tomography (CT) scan of the thorax (n = 12). Imaging investigations revealed extrathoracic tumours in 12 of 14 patients (86%). Eight of the 14 patients (57%) had renal tumours consistent with angiomyolipomas (bilateral in five patients). Only one patient had renal symptoms (flank pain and haematuria). All had normal serum creatinine, one had a reduced creatinine clearance. Extrathoracic nonrenal tumours were discovered in the pancreas, adrenals and uterus, findings previously unreported in LAM. In summary, the incidence of extrathoracic tumours in lymphangioleiomyomatosis patients is much higher than previously reported in the literature. This increased association supports the theory that lymphangioleiomyomatosis and tuberous sclerosis represent part of a spectrum of a similar disease process.
Evaluation of the solitary pulmonary nodule by positron emission tomography imaging
Authors: Bury T , Dowlati A , Paulus P , Corhay JL , Benoit T , Kayembe JM , Limet R , Rigo P , Radermecker M
Published: June 2003

Current noninvasive imaging methods are not sufficiently reliable for accurate detection of malignancy in most solitary pulmonary nodules (SPNs). Positron emission tomography (PET) using 18-fluorodeoxyglucose (FDG), showing increased FDG uptake and retention in malignant cells, has proved useful to differentiate malignant from benign tissue and could, therefore, contribute to the evaluation of the SPN. We performed a prospective study of 50 patients referred to the Pneumology Department with unclear diagnoses of SPN after conventional radiological screening. PET study was performed on each subject before an invasive procedure was proposed. Thirty three patients had a malignant nodule and 17 had a benign nodule. The mean size of malignant nodule was 3 cm (range 1.5-4.5 cm). All showed a marked increase in 18-FDG uptake. The mean size of benign nodule was 1.8 cm (range 0.5-3.5 cm). PET imaging showed the absence of 18-FDG uptake and correctly identified 15 of 17 benign nodules. There was two false-positive cases with a moderate increase in 18-FDG uptake (1 postprimary tuberculosis; and 1 anthracosilicotic nodule with nonspecific inflammation). At present, the sensitivity and specificity of the method are 100 and 88%, respectively. The positive and negative predictive values of PET imaging for SPNs are 94 and 100%, respectively. Our preliminary results demonstrate that PET-FDG imaging is a noninvasive technique, which appears highly accurate in differentiating malignant SPN from benign SPN.
Pulmonary function and exercise capacity after lung resection
Authors: Bolliger CT , Jordan P , Soler M , Stulz P , Tamm M , Wyser C , Gonon M , Perruchoud AP
Published: June 2003

The influence of pulmonary resection on functional capacity can be assessed in different ways. The aim of this study was to compare the effect of lobectomy and pneumonectomy on pulmonary function tests (PFT), exercise capacity and perception of symptoms. Sixty eight patients underwent functional assessment with PFT and exercise testing before (Preop), and 3 and 6 months after lung resection. In 50 (36 males and 14 females; mean age 61 yrs) a lobectomy was performed and in 18 (13 males and 5 females; mean age 59 yrs) a pneumonectomy was performed. Three months after lobectomy, forced vital capacity (FVC), forced expiratory volume in one second (FEV1), total lung capacity (TLC), transfer factor of the lungs for carbon monoxide (TL,CO) and maximal oxygen uptake (V'O2,max) were significantly lower than Preop values, increasing significantly from 3 to 6 months after resection. Three months after pneumonectomy, all parameters were significantly lower than Preop values and significantly lower than postlobectomy values and did not recover from 3 to 6 months after resection. At 6 months after resection significant deficits persisted in comparison with Preop: for FVC 7% and 36%, FEV1 9% and 34%, TLC 10% and 33% for lobectomy and pneumonectomy, respectively; and V'O2,max 20% after pneumonectomy only. Exercise was limited by leg muscle fatigue in 53% of all patients at Preop. This was not altered by lobectomy, but there was a switch to dyspnoea as the limiting factor after pneumonectomy (61% of patients at 3 months and 50% at 6 months after resection). Furthermore, pneumonectomy compared to lobectomy led to a significantly smaller breathing reserve (mean +/- SD) (28 +/- 13 vs 37 +/- 16% at 3 months; and 24 +/- 11% vs 33 +/- 12% at 6 months post resection) and lower arterial oxygen tension at peak exercise 10.1 +/- 1.5 vs 11.5 +/- 1.6 kPa (76 +/- 11 vs 86 +/- 12 mmHg) at 3 months; 10.1 +/- 1.3 vs 11.3 +/- 1.6 kPa (76 +/- 10 vs 85 +/- 12 mmHg) at 6 months postresection. We conclude that measurements of conventional pulmonary function tests alone overestimate the decrease in functional capacity after lung resection. Exercise capacity after lobectomy is unchanged, whereas pneumonectomy leads to a 20% decrease, probably due to the reduced area of gas exchange.
Involvement of endogenous tachykinins in LTD4-induced airway responses
Authors: Ishikawa J , Ichinose M , Miura M , Kageyama N , Yamauchi H , Tomaki M , Sasaki Y , Shirato K
Published: June 2003

Leukotriene D4-(LTD4) has been reported to cause tachykinin release from airway sensory nerves. However, the functional significance of endogenously released tachykinins in LTD4-mediated airway responses has not been fully clarified. The aim of this study was to investigate whether LTD4-induced airway responses are due, in part, to tachykinin release in guinea-pigs. Airway plasma exudation and bronchoconstriction were assessed by measuring extravasation of Evans blue dye and by mean pulmonary resistance (RL) in the presence of atropine (1 mg.kg-1 i.v.) and propranolol (1 mg.kg-1 i.v.), respectively. LTD4 (5 micrograms.mL-1 for 1 min) inhalation caused increase in plasma exudation and RL. Capsaicin pretreatment of animals to deplete sensory neuropeptides significantly inhibited LTD4-induced plasma exudation in the main bronchi, but not in the central (cIPA) and peripheral intrapulmonary airways (pIPA). Pretreatment with specific tachykinin neurokinin-1 (NK1)-receptor antagonists, FK 888 (10 mg.kg-1 i.v.) and CP 96345 (4 mg.kg-1 i.v.), also significantly reduced LTD4-induced plasma exudation in the main bronchi, and in the main bronchi and cIPA, respectively. However, these antagonists did not significantly affect the LTD4-induced increase in RL. In contrast, neurokinin-2 (NK2)-receptor antagonist, SR 48968 (0.3 mg.kg-1 i.v.), significantly inhibited the bronchoconstriction after LTD4-inhalation. These results suggest that leukotriene D4-induced bronchoconstriction and plasma exudation in guinea-pigs are, in part, due to tachykinin release from airway sensory nerves.
Fever and leucocytosis accompanying asthmatic reactions due to occupational agents: frequency and associated factors
Authors: Lemiere C , Gautrin D , Trudeau C , Ghezzo H , Desjardins A , Cartier A , Malo JL
Published: June 2003

Fever is sometimes associated with asthmatic reactions following specific inhalation challenges with occupational agents. Our aims were to estimate the prevalence of fever in subjects with occupational asthma confirmed by specific inhalation challenge and to examine the characteristics and clinical correlates of subjects who develop fever on specific inhalation challenge. We performed a retrospective analysis of 317 subjects who had positive specific inhalation challenge to occupational agents and a comparison of subjects who developed fever after specific inhalation challenge with a random sample of those who did not. Fifteen subjects (5%) developed fever associated with positive specific inhalation challenge. They were compared with a random sample of 60 subjects who did not develop fever. The fever group: 1) showed a larger increase in absolute number of blood neutrophils, and a larger decrease both of blood lymphocytes and forced vital capacity after specific inhalation challenge; 2) included fewer atopics; 3) had been exposed more frequently to low rather than high molecular compounds; and 4) always experienced a late reaction and had more atypical reactions. We conclude that after positive specific inhalation challenge; fever occurs infrequently, and is associated with an increase in blood neutrophils and a decrease in blood lymphocytes and forced vital capacity. Such reactions seem more likely to occur in nonatopic subjects exposed to low molecular weight agents.
The effects of recombinant human DNase on neutrophil elastase activity and interleukin-8 levels in the sputum of patients with cystic fibrosis
Authors: Shah PL , Scott SF , Knight RA , Hodson ME
Published: June 2003

In cystic fibrosis (CF), neutrophil-dominated airway inflammation results in high levels of neutrophil elastase (NE). Some of these proteases are sequestered by the large amounts of deoxyribonucleic acid (DNA) present in purulent sputum. Recombinant human deoxyribonuclease (rhDNase), a new treatment in CF, depolymerizes DNA. Our concerns were that this might release proteases bound to DNA, which could be potentially harmful. The in vitro and in vivo effects of rhDNase on NE and interleukin-8 (IL-8) were evaluated. The acute effects of rhDNase were evaluated in CF patients during the first 6 days of treatment. Medium-term effects were evaluated in stable CF patients observed in rhDNase over 6 months. Sputum samples were collected at regular intervals and NE activity was measured by a fluorimetric assay and IL-8 with a radioimmunoassay. In vitro addition of rhDNase resulted in a twofold increase in protease activity and this was reflected in an acute transient rise on initiation of treatment with rhDNase. Medium-term treatment was associated with a decline in NE activity and IL-8. These in vivo results are encouraging, since the increase in protease activity was transient and the trend over 6 months was a reduction in both inflammatory markers.
Management of chronic parotitis: a review
Authors: Motamed M. , Laugharne D. , Bradley P. J.
Published: July 2003

Chronic parotitis is an insidious inflammatory disorder, which is characterized by a recurrent, often painful, swelling of the gland or glands. Sialography remains the investigation of choice. Diagnostic siladenoscopy may complement or supersede sialography as the diagnostic procedure of choice, as more experience is gained in this technique and its use becomes more widespread. The management options are conservative or surgical, but controversy exists regarding the timing and method of surgical intervention. The surgical methods that have been described include injection of methyl violet – a sclerosing agent, ductal ligation, ductoplasty, tympanic neurectomy, and parotidectomy. Parotidectomy is considered the ultimate surgical option but because of its significant morbidity the exact technique and procedure that should be used remains contentious.
Botulinum toxin injection for failed tracheo-oesophageal voice in laryngectomees: the Sunderland experience
Authors: Ramachandran K. , Arunachalam P. S. , Hurren Anne , Marsh R. L. , Samuel P. R.
Published: July 2003

Spasm of the pharyngo-oesophageal segment is one of the important causes of tracheo-oesophageal voice failure. Traditionally it has been managed by either prolonged speech therapy, surgical pharyngeal myotomy or pharyngeal plexus neurectomy with varying degrees of success. Botulinum neurotoxin has been found to be effective in relieving pharyngo-oesophageal segment spasm. Since 1995, we have used botulinum toxin injection on 10 laryngectomees with either aphonia or hypertonicity due to pharyngo-oesophageal segment spasm. Early results were analysed by the Sunderland Surgical Voice Restoration Rating scale. Seven of the 10 patients, who were previously completely aphonic, developed voice following this therapy and are using their valve choice as their only method of communication. Out of the three patients who were treated for hypertonic voice, two did derive some benefit from the procedure. One patient developed a hypotonic voice, which lasted for a few months.
Superior semicircular canal dehiscence simulating otosclerosis
Authors: Halmagyi G. Michael , Aw Swee T. , McGarvie Leigh A. , Todd Michael J. , Bradshaw Andrew , Yavor Robyn A. , Fagan Paul A.
Published: July 2003

This is a report of a patient with an air-bone gap, thought 10 years ago to be a conductive hearing loss due to otosclerosis and treated with a stapedectomy. It now transpires that the patient actually had a conductive hearing gain due to superior semicircular canal dehiscence. In retrospect for as long as he could remember the patient had experienced cochlear hypersensitivity to bone-conducted sounds so that he could hear his own heart beat and joints move, as well as a tuning fork placed at his ankle. He also had vestibular hypersensitivity to air-conducted sounds with sound-induced eye movements (Tullio phenomenon), pressure-induced nystagmus and low-threshold, high-amplitude vestibular-evoked myogenic potentials. Furthermore some of his acoustic reflexes were preserved even after stapedectomy and two revisions. This case shows that if acoustic reflexes are preserved in a patient with an air-bone gap then the patient needs to be checked for sound- and pressure-induced nystagmus and needs to have vestibular-evoked myogenic potential testing. If there is sound- or pressure-induced nystagmus and if the vestibular-evoked myogenic potentials are also preserved, the problem is most likely in the floor of the middle fossa and not in the middle ear, and the patient needs a high-resolution spiral computed tomography (CT) of the temporal bones to show this.
Anomalies of the auditory organ in trisomy 18 syndrome: human temporal bone histopathological study
Authors: Tadaki Tohru , Kamiyama Ryosuke , Okamura Hiro-Oki , Ohtani Iwao
Published: July 2003

The purpose of this study was to define the histopathological changes in the temporal bone of a fetus with trisomy 18 syndrome, a stillborn due to perosplanchnia. Several anomalies were found including malformation of the auditory ossicles, residual mesenchyme in the middle ear, aberrant tensor tympani muscle, absence of stapedial tendon, aberrant lateral ampullary nerve and wide endolymphatic sinus. The incus body was deformed and separated from the long process by connective tissue and monocrural stapes was noted in the right ear. Three-dimensional reconstruction images provided a clear view of the auditory ossicle malformation. The abnormal findings in our case indicate that ear anomalies in this syndrome might be derived from the component around the first and second branchial arches.
Effectiveness of multifaceted implementation of guidelines in primary care
Authors: Wright John , Warren Erica , Reeves Jayne , Bibby John , Harrison Stephen , Dowswell George , Russell Ian , Russell Daphne
Published: June 2003

Objective: To evaluate the effectiveness of a tailored and multifaceted approach to the implementation of nationally recommended and evidence-based guidelines in primary care within existing systems and resources.

Methods: A non-randomised Latin square to compare guideline implementation in two neighbouring health districts covering 180 general practices. Evidence-based guidelines for the treatment of patients with asthma and angina were implemented actively in one district and passively disseminated in the other district. Outcome measures for asthma were smoking status and inhaler technique. For angina the outcome measures were: smoking status; blood pressure; aspirin prescribed, contraindicated or self-medicated; beta-blocker prescribed or contraindicated; routine hospital admission; prescribed drugs; self-reported change.

Results: There were improvements in all outcome criteria between baseline and follow-up audits, regardless of whether the guideline was actively implemented or passively disseminated. The estimated increase in the proportion of records complying with guidelines was 4% [95% confidence intervals (CI): 0, 8] and was higher in intervention than in control practices. Using only records not compliant at baseline, the corresponding difference was 15% (95% CI: 7, 24). The only significant improvement associated with active implementation was smoking status in angina patients. Both prescribing and hospital admission monthly totals changed during the period of the trial, but there was no significant difference between the pattern of changes in intervention and control districts. A significantly greater proportion of health professionals saw the intervention guideline compared with the control (75% versus 25%). There was a significant correlation between self-reported change and interventions steps ( P < 0.05).

Conclusions: Increases in quality markers occurred irrespective of the multifaceted implementation efforts. Some of this increase was due to the method of data collection. Nevertheless, national initiatives may have more influence than local implementation initiatives.
Learning from experience: privacy and the secondary use of data in health research
Authors: Lowrance William
Published: June 2003

Health services research must continually address the question: Under what conditions may data not collected specifically for research, such as primary medical data, be re-used for research without compromising the privacy of the data-subjects?

For secondary use of data in research there are basically three options. Option A: Use personal data with consent or other assent from the data-subjects. To make this both fairer and more practical, in many circumstances broader construals of consent, or permission or approval, need to be explored and instituted. Option B: Anonymise the data, then use them. For many studies, this is the most practical and desirable option. The craft of anonymisation, including reversible anonymisation, or key-coding, needs to be developed and more fully supported under law. Option C: Use personal data without explicit consent, under a public interest mandate. Whether and how the data should be anonymised will depend on the situation.

Public health mandates and protections deserve to be clarified, strengthened and extended for a variety of surveillance, registration, clinical audit, health services research and other types of investigation.

Safeguards are an integral part of the research promise to the public, offer crucial reassurance and should be emphasised. For health services research, databases are core resources, and their stewardship must be cultivated.
Health research and the Data Protection Act 1998
Authors: Boyd Phil
Published: June 2003

The 1998 Data Protection Act in the UK largely restates existing good practice: individuals have a right to know what data are held about them and why; and those processing data have a duty to proceed with fairness and transparency, maintain high data quality and keep data secure.

Some health researchers have criticised the Act, seeing it as a legal minefield, unnecessary bureaucracy and interference from the European Union. This is largely based on misconceptions. Recent guidance from the Information Commissioner aims to assist researchers by advising how legal requirements can be met through anonymisation of data, attention to data-processing methods and fair collection of data. The Act provides a clear framework of rights and responsibilities that should be embraced with enthusiasm rather than with the reluctance of a person forced to carry out a meaningless chore.
Increased realism in eyewitness confidence judgements: the effect of dyadic collaboration
Authors: Allwood Carl Martin , Granhag Pär Anders , Johansson Marcus
Published: June 2003

This study investigated to what extent, and under what circumstances, pair collaboration influences the realism in eyewitness confidence in event memory. The participants first saw a short film clip and then confidence rated their answers to questions on its content. A condition (the Individual–Pair condition) where individual effort preceded pair collaboration showed better calibration compared with a condition (the Simple Pair condition) where no individual effort took place. Furthermore, within the Individual–Pair condition, better calibration, and lower overconfidence, were found in the pair phase compared with the individual phase. The eyewitnesses in the Individual–Pair condition made more realistic judgements of the total number of questions answered correctly. In a control experiment no effect on realism in confidence was found when individuals performed the same task twice. The improved realism in the Individual–Pair condition may partly be explained in terms of the increased accuracy and lowered confidence found for such items where the pair members' had given different answers in the individual phase, and by a risky shift effect for such items where they had given the same answer. Copyright © 2003 John Wiley & Sons, Ltd.
Selective exposure to television programmes and advertising effectiveness
Authors: Norris Claire E. , Colman Andrew M. , Aleixo Paulo A.
Published: June 2003

This study focused on the influence of selective exposure within an experiment designed to investigate context effects on advertising effectiveness. In a semi‐natural viewing environment, 86 participants chose one of four television programmes to view. The programmes belonged to diverse genres: news and current affairs, light entertainment, sport, and action‐adventure. Each programme was interrupted by two commercial breaks containing unfamiliar advertisements for familiar product types. Self‐rated involvement, entertainment, and enjoyment of programmes correlated positively with subsequent measures of memory for and responses to the advertisements. The results support the hypothesis that the operation of selective exposure within an experimental situation may result in positive relationships between predictor variables and measures of advertisement effectiveness. Copyright © 2003 John Wiley & Sons, Ltd.
Structural behavior of nanometric carbohydrate films transduced by a resonant technique
Authors: Palkovits Roland , Mayer Christian , Bauer Georg , Winkler Heinz , Pittner Fritz , Schalkhammer Thomas
Published: June 2003

New optical nanoresonance effects enabled us to study the effect of ions on nanometric carbohydrate thin layers on chips. Immobilization was done via spin coating of the derivatized carbohydrate polymer at a metallized chip surface forming ultrathin films (about 50–300 nm thick) followed by photochemical cross‐linking. Deposition of metal‐nanoclusters, synthesized by chemical means and sputter coating on top of the polymer, induced an optical resonance effect, which transduced changes of polymer structure quantitatively into an optical signal that can be observed directly as resonance shift of a narrow optical peak. The response of the sensor chip even visible to the eye was quantified spectroscopically in the visible and ir range of the spectrum. The lifetime of thin film was good, and thus application as a sensor was limited only by the mechanical stability of the reactive matrix, but not by photobleaching or molecular leakage. Due to the inherent hydrophilic nature of the alginate polymer, the response time of this new sensor is governed by simple aqueous diffusion of the ionic calcium for up to 300 nm completed within less than one second. Monitoring of calcium fluctuations in a high background of magnesium and even serum was demonstrated with a dynamic range optimal for physiological measurements and a linear response up to 5 mM. Surface and alignment of polymer chain were influenced by the nanostructure of the supporting metal film—contrary to alginic acid, chitosan was deposited well aligned to the nanocrystals of the support. © 2003 Wiley Periodicals, Inc. Biopolymers 69: 333–342, 2003
Fourier transform IR spectroscopic appraisal of radiation damage in Micrococcus luteus
Authors: Perromat Annie , Melin Anne‐Marie , Lorin Chrystelle , Deleris Gerard
Published: June 2003

Fourier transform IR spectroscopy (FTIR) is used to analyze cells of Micrococcus luteus, the type species of the highly heterogeneous genus Micrococcus that belongs to the Micrococcaceae family. The cells of M. luteus, which is a Gram‐positive and yellow‐pigmented bacterium, are submitted to increasing doses of γ radiation. Irradiation leads to the generation of reactive oxygen species that induce biochemical changes as shown in spectral profiles. Beyond a dose of 0.70 kGy, significant differences between samples are observed, particularly in the 1485–900 cm−1 region, which contains information about membrane lipids, cell wall polysaccharides, and nucleic acids. After a dose of 16.50 kGy, M. luteus is reincubated for times ranging from 1 to 24 h. Postirradiation reincubated bacteria are found far from the control and irradiated cells (mainly in the 985–900 cm−1 range), suggesting that a biomolecular rearrangement occurs as soon as reincubation begins in the growth medium. Thus, FTIR spectroscopy appears to be a very useful technique for the rapid visualization of the alterations induced by both the radiation and mutagenic response during reincubation. The use of mathematical methods gives good insight into the biomolecular compounds involved in these two mechanisms. In view of these preliminary results, we hypothesize that it can be successfully applied to any type of tissue and that it may be a future interesting tool for evaluating the effects of radiation in humans. © 2003 Wiley Periodicals, Inc. Biopolymers (Biospectroscopy), 2003
Controlled hydrophobic/hydrophilicity of chitosan for spheres without specific processing technique
Authors: Yoksan Rangrong , Akashi Mitsuru , Hiwatari Ken‐ichiro , Chirachanchai Suwabun
Published: June 2003

Chitosan is functionalized with phthalic anhydride at the amino group and poly(ethylene glycol) methyl ether at the hydroxyl group via homogeneous reaction. The product regenerated forms particles in either aqueous solution or organic solvents. The particles are spheres with the size of few micrometers as observed from scanning electronmicroscopy. The present work demonstrates that by simply adjusting the hydrophilicity and hydrophobicity, we can directly obtain spheres without a specific processing technique. © 2003 Wiley Periodicals, Inc. Biopolymers 69: 386–390, 2003
IR spectroscopic studies of major cellular components. III. Hydration of protein, nucleic acid, and phospholipid films
Authors: Pevsner Alex , Diem Max
Published: June 2003

The IR absorption spectra of protein, DNA, RNA, and phospholipid films as a function of the water content are reported. We find that the hydration of protein films affects the peak intensity of amide I and amide II bands and the shape of the amide III band. For nucleic acids, the symmetric (νS PO) and antisymmetric (νAS PO) stretching vibrations of the phosphate linkage are the most affected by hydration, because both intensity changes and frequency shifts are observed. The spectra of phospholipid films are also sensitive to hydration, and they exhibit changes in the peak intensities and frequencies of both νS PO and νAS PO vibrations. We interpret the spectral differences between water saturated and dried films both in terms of structural changes and the change in the local dielectric in the vicinity of the polar and solvent exposed groups. In addition, we observe that the most significant change in the absorption intensity, frequency, and shape of the water sensitive vibrations occurs at high hydration levels. The principal component analysis of hydration results and the kinetics of water removal from sample films are also discussed. In addition, protein spectra acquired using film and KBr pellet sampling techniques are compared. © 2003 Wiley Periodicals, Inc. Biopolymers (Biospectroscopy), 2003
Rapid determination of rat plasma uridine levels by HPLC‐ESI‐MS utilizing the Captiva™ filter plates for sample preparation
Authors: Williams Marta G. , Palandra Joe , Shobe Eric M.
Published: June 2003

A rapid, accurate and precise HPLC‐ESI‐MS method for the determination of rat plasma uridine concentrations was developed and is described here. Sample preparation involves methanol precipitation of plasma proteins in a 96‐well Captiva™ protein precipitation filter plate. A clear extract is drawn through the filter plate with vacuum, followed by evaporation of the extract and subsequent reconstitution prior to chromatography on a reversed‐phase column with an aqueous mobile phase [0.1% (v/v) glacial acetic acid]. Detection was accomplished by positive‐ion electrospray ionization mass spectrometry. A calibration curve ranging in concentration from 0.78 to 25 µM was constructed by best‐fit, 1/x weighting linear regression analysis of the calibration standard concentrations vs peak height ratios of analyte with internal standard. The correlation coefficient was >0.995. The overall assay accuracy as shown by the back‐calculated concentrations of the calibration curve ranged from 96.6 to 103% with RSD ranging from 4.5 to 20%. While this assay method was developed for the determination of uridine in rat plasma, it could be readily adapted for determination of uridine in plasma from other species, such as human. Copyright © 2003 John Wiley & Sons, Ltd.
Simultaneous determination of aceclofenac and three of its metabolites in human plasma by high‐performance liquid chromatography
Authors: Hinz Burkhard , Auge Daniel , Rau Thomas , Rietbrock Stephan , Brune Kay , Werner Ulrike
Published: June 2003

Aceclofenac {[2‐(2′,6′‐dichlorophenyl)amino]phenylacetoxyacetic acid} is a phenylacetic acid derivative with potent analgesic and anti‐inflammatory properties and an improved gastro‐intestinal tolerance. In the present study, a liquid–liquid extraction‐based reversed‐phase HPLC method with UV detection was validated and applied for the analysis of aceclofenac and three of its metabolites (4′‐hydroxy‐aceclofenac, diclofenac, 4′‐hydroxy‐diclofenac) in human plasma. The analytes were separated using an acetonitrile–phosphate buffer gradient at a flow rate of 1 mL/min, and UV detection at 282 nm. The retention times for aceclofenac, diclofenac, 4′‐hydroxy‐aceclofenac, 4′‐hydroxy‐diclofenac and ketoprofen (internal standard) were 69.1, 60.9, 46.9, 28.4 and 21.2 min, respectively. The validated quantitation range of the method was 10–10,000 ng/mL for aceclofenac, 4′‐hydroxy‐aceclofenac and diclofenac, and 25–10,000 ng/mL for 4′‐hydroxy‐diclofenac. The developed procedure was applied to assess the pharmacokinetics of aceclofenac and its metabolites following administration of a single 100 mg oral dose of aceclofenac to three healthy male volunteers. Copyright © 2003 John Wiley & Sons, Ltd.
Generalized orthogonal multiple co‐inertia analysis(–PLS): new multiblock component and regression methods
Authors: Vivien Myrtille , Sabatier Robert
Published: June 2003

The purpose of this paper is to develop new component‐wise component and regression multiblock methods that overcome some of the difficulties traditionally associated with multiblocks, such as the step‐by‐step optimization and component orthogonalities. Generalized orthogonal multiple co‐inertia analysis (GOMCIA) and generalized orthogonal multiple co‐inertia analysis–partial least squares (GOMCIA–PLS) are proposed for modelling two sets of blocks measured on the same observations. We especially emphasize GOMCIA–PLS methods in which we consider one of the sets as predictive. All these methods are based on the step‐by‐step maximization of the same criterion under normalization constraints and produce orthogonal components or super‐components. The solutions of the problem have to be computed with an iterative algorithm (which we prove to be convergent). We also give some interesting special cases and discuss the differences compared with a few other multiblock and/or multiway methods. Finally, short examples of real data are processed to show how GOMCIA–PLS can be used and its properties. Copyright © 2003 John Wiley & Sons, Ltd.
N,N′‐Disubstituted Ureas: Influence of Substituents on the Formation of Supramolecular Polymers
Authors: Lortie Frédéric , Boileau Sylvie , Bouteiller Laurent
Published: June 2003

Symmetrical N,N′‐disubstituted ureas have been synthesized and characterized. Among them, the branched dialkylureas prepared are highly soluble in organic media. Moreover, the solutions obtained are very viscous in heptane, if the branched alkyl groups are not too bulky (i.e. a methyl group on the α carbon, or an ethyl group on the β carbon). Due to the strong, bifurcated hydrogen bonds between the urea moieties, linear supramolecular polymers are formed. The degree of association of these supramolecular polymers has been determined by FTIR spectroscopy.
Cover Picture: Cyclodextrin Phosphanes as First and Second Coordination Sphere Cavitands (Chem. Eur. J. 13/2003)
Authors: Engeldinger Eric , Armspach Dominique , Matt Dominique , Jones Peter G.
Published: June 2003

The cover picture shows metallo‐cavitands as coordination compounds which provide the opportunity to study host–guest interactions between metal‐bonded substrates and the inner part of a hollow molecule. Of particular interest are complexes in which the metal centre caps the entrance of an opened cavity, for instance a cone or a tube. Such systems are perfectly suited for forcing the cavity to behave as a second coordination sphere, the sequestered ligands being then subjected to restricted movement and their controlled positioning allowing specific, weak interactions to operate. The work reported by Matt et al. (see page 3091 ff.) describes how phosphine‐modified cyclodextrins selectively entrap metalchloride bonds. Furthermore the study provides evidence that cavities are able to stabilise unusual coordination modes and, for the first time, that ligand exchange processes occur inside an α‐CD receptor.
EPR Study of o‐Semiquinone‐Catecholate Cobalt Complexes with Bis(diphenylphosphanyl)ethane
Authors: Bubnov Michael P. , Teplova Irina A. , Cherkasov Vladimir K. , Abakumov Gleb A.
Published: June 2003

Three novel cobalt compounds with bis(diphenylphosphanyl)ethane (dppe) and semiquinone and catecholate ligands were synthesized and investigated by EPR spectroscopy in solution. They are: [(dppe)Co(3,6‐DBSQ)(CatClox)] (1), [(dppe)Co(3,6‐DBCat)(phen‐SQ)] (2), and [(dppe)Co(3,6‐DBSQ)2] (3), where 3,6‐DBSQ and 3,6‐DBCat are the radical anion and dianion of 3,6‐di‐tert‐butyl‐o‐benzoquinone, respectively, CatClox is the dianion of perchloroxanthrenequinone‐2,3, and phen‐SQ is the radical anion of phenanthrenequinone. According to the ratio of the redox potentials of the o‐quinone fragments, 1 and 2 are mixed semiquinone‐catecholate complexes, and the 3,6‐di‐tert‐butyl‐o‐quinone fragment appears as a semiquinone in 1 and as a catecholate in 2. Compound 3 exists as a mixture of redox isomers, namely semiquinone‐catecholate and bis‐semiquinone species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Order−Disorder Transitions and Magnetic Behaviour in Lithium Ferrites Li0.5+0.5xFe2.5−1.5xTixO4 (x = 1.28 and 1.50)
Authors: Arillo María Ángeles , López María Luisa , Pico Carlos , Veiga María Luisa , Campo Javier , Martínez José Luis , Santrich‐Badal Alejandro
Published: June 2003

We report the structural characterization and magnetic behaviour of the spinels with general formula Li0.5+0.5xFe2.5−1.5xTixO4, where x = 1.28 and 1.50. When the samples are cooled slowly, a 1:3 crystallographic order occurs, whereas a random disorder is observed when the samples are quenched. Neutron‐powder‐diffraction measurements were performed on the materials to characterize the structural transitions. Magnetic properties were studied by magnetic susceptibility (dc and ac), magnetisation and neutron‐diffraction data and the results can be interpreted on the basis of a spin‐glass behaviour. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Properties of Undoped and Ca‐Doped LaMnO3 − Non‐Stoichiometry and Defect Structure
Authors: Yahia Mondher , Batis Habib
Published: June 2003

Oxygen‐excessive LaMnO3+y samples with 0.02 ⩽ y ⩽ 0.26 have been prepared by thermal decomposition in air at 450 °C of a precursor obtained from an aqueous solution of lanthanum nitrate and manganese acetate (atomic ratio La/Mn = 1). The obtained solid is annealed at different temperatures from 700 to 1000 °C and under three oxygen pressures: 1.00, 0.21, and 10−4 atm. Samples with 0.14 ⩽ y ⩽ 0.26 are simple‐phased rhombohedral perovskites, the distortion of which decreases as the oxygen content (and Mn4+ content) increases. Samples with 0.02 ⩽ y ⩽ 0.09, obtained under low oxygen pressure (10−4 atm), have orthorhombic symmetry. In this case, the order of lattice parameters c/√2 < a < b, characteristic of O′‐perovskites, is a consequence of the Jahn−Teller distortion of the oxide octahedron around the d4 Mn4+ cation. The volume (Vf) per LaMnO3+y formula unit decreases regularly with increasing oxygen content (i.e., oxidation). Study has shown that the oxygen content is best described in terms of La and Mn vacancies, rather than of interstitial anions. Density measurements confirm the cation vacancy model involving equal amounts in La and Mn sub‐lattices. The infrared spectra of LaMnO3+y samples have been interpreted in connection with the structures of these solids. Correlations have been established between the spectral evolution and the crystal distortion of these compounds. La1−xCaxMnO3±y oxides with 0 < x ⩽ 1 have been synthesised by the same route, at 700 °C and under an oxygen pressure of 0.21 atm. It is shown that a negative correlation exists between the calcium content x and the degree of non‐stoichiometry: at low Ca content, the oxygen content is higher. The ability to form over‐stoichiometric compounds in air decreases with increasing Ca content and mostly disappears at x ⩾ 0.7. Samples with 0.1 ⩽ x ⩽ 0.4 are simple‐phased rhombohedral perovskites with constant Mn3+/Mn4+ ratios. Samples with 0.5 ⩽ x ⩽ 1 have orthorhombic symmetry. In this case, a linear variation of the Mn4+ content as a function of the Ca content is observed. The defect structure of these compounds is described in terms of La and Mn vacancies when 0 < x ⩽ 0.7 (0 ⩽ y ⩽ 0.19) and anion vacancies when 0.8 ⩽ x ⩽ 1 (−0.04 ⩽ y < 0). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Physicochemical Characterization of P760, a New Macromolecular Contrast Agent with High Relaxivity
Authors: Vander Elst Luce , Port Marc , Raynal Isabelle , Simonot Christian , Muller Robert N.
Published: June 2003

P760‐Gd, a hydrophilic derivative of DOTA‐Gd with a molecular mass of 5.6 kDa, has been characterized in various media: aqueous solution, protein‐containing solution, and Zn2+‐containing solution. Several investigations have been carried out, including the determination of the number of inner‐sphere water molecules by laser‐induced luminescence of the europium complex, water 1H nuclear magnetic relaxation rates as a function of field strength, and 17O relaxometry of water of the gadolinium complex, pulsed magnetic field gradient spin echo of proton, and 2H transverse relaxation rates of the labeled lanthanum analogue. The large proton relaxivity of P760‐Gd in water results from the long rotational correlation time of the hydrated complex (τR ≈︁ 2 ns at 310 K). As with DOTA‐Gd, no significant Zn2+ transmetallation process was observed by proton relaxometry. Finally, analysis of the non‐covalent binding of P760‐Gd to serum proteins by proton relaxometry showed that P760‐Gd does not interact with human serum albumin. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A New Thioether‐Based (N2S2)Copper(II/I) Complex Exhibiting a High Redox Potential
Authors: Torelli Stéphane , Belle Catherine , Philouze Christian , Pierre Jean‐Louis , Rammal Wassim , Saint‐Aman Eric
Published: June 2003

From the new ligand bis[2‐(tert‐butylthio)benzyl](2‐pyridylmethyl)amine [N2(StBu)2], the corresponding complexes [CuI{N2(StBu)2}]CF3SO3 (1) and [CuII{N2(StBu)2}](H2O)(CF3SO3)]CF3SO3 (2) were synthesized and characterized by X‐ray crystallography. The Cu−S bonds are unusually shortened in 1 and elongated for the axial thioether in 2. Redox studies show that 1 and 2 interconvert during the electron transfer with a high CuII/I potential of 0.79 V vs. SCE in CH2Cl2. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)