bluuebunny/crossref_metadata_2025 huggingface dataset:
The measurement of methacholine responsiveness in 5 year old children: three methods compared
Authors: Wilson NM , Bridge P , Phagoo SB , Silverman M
Published: September 2003

The aim of this study was to compare the feasibility of three techniques for measuring the response to bronchial challenge in young children: a direct airway measurement, the forced oscillation technique (FOT) for determining respiratory system resistance at 6 and 8 Hz (Rrs6 and Rrs8), and two indirect methods, the change in transcutaneous oxygen tension (PtcO2) and the detection of wheeze on auscultation of the chest. Thirty children aged 5 yrs, with a history of wheeze, and six asymptomatic controls, took part in a bronchial challenge test using methacholine administered by Wright nebulizer by the tidal-breathing method. The provocative concentration which produced a 35% increase in Rrs6 (PC35Rrs6) and a 15% decreases in PtcO2 (PC15PtcO2) were determined by interpolation, and the chest was ausculated after each dose of methacholine. The FOT was found to be unreliable in this age group: in seven children, the data were technically unsatisfactory in the presence of induced bronchoconstriction, whilst in three children, changes in Rrs were inconsistent after challenge. The use of Rrs8 did not improve the detection of positive responses. PC15PtcO2 was measurable in 29 of 30 children, and in 18 of these PC35Rrs6 was also measurable. In no subject did a significant, sustained increase in Rrs occur during challenge in the absence of a significant change in PtcO2. Wheeze was audible in only 4 of 25 (16%) of the positive and in no negative challenges. With this protocol, we found the FOT to be unreliable and the auscultation method valueless and potentially dangerous, since marked falls in PtcO2 of up to 33% sometimes occurred in the absence of wheeze.(ABSTRACT TRUNCATED AT 250 WORDS)
Dose-dependent in vitro effect of recombinant human DNase on rheological and transport properties of cystic fibrosis respiratory mucus
Authors: Zahm JM , Girod de Bentzmann S , Deneuville E , Perrot-Minnot C , Dabadie A , Pennaforte F , Roussey M , Shak S , Puchelle E
Published: September 2003

Recombinant human deoxyribonuclease (rhDNase) has been demonstrated to reduce the viscosity of purulent cystic fibrosis (CF) respiratory mucus, to improve pulmonary function and to reduce the risk of respiratory tract infectious exacerbations, but its effect on mucus transportability has not so far been investigated. The dose-dependent effect of rhDNase was analysed in vitro on mucus transport rate (tr) by ciliary activity and by simulated cough (cough transport (ct)), as well as on mucus viscosity and surface properties. Purulent CF sputa (n = 15) were incubated for 30 min at 37 degrees C with either rhDNase at three different concentrations (final concentrations 0.2, 2 or 20 micrograms.ml-1 of mucus) or placebo. No significant dose-dependent effect of rhDNase on the mucociliary transport rate was observed when the samples wer statistically analysed together. However, in the larger group of mucus samples (n = 11) with a low initial mucociliary transport rate, the latter was improved at each rhDNase concentration (tr0.2 = 0.69, tr2 = 0.88 and tr20 = 0.87) as compared to placebo (trp = 0.58). In the smaller group of mucus samples (n = 4) with high initial transport rate, a decrease in mucociliary transport rate was observed, particularly at the highest concentration rhDNase assayed, i.e. 20 micrograms.ml-1 of mucus (tr20 = 0.58) as compared to placebo (trp = 0.86). The mucus cough transport was increased by rhDNase (ct0.2 = 25 mm, ct2 = 27.5 mm and ct20 = 31 mm) as compared to placebo (ctp = 23.5 mm).(ABSTRACT TRUNCATED AT 250 WORDS)
Activation of the transcription factor NF-kappa B in human tracheobronchial epithelial cells by inflammatory stimuli
Authors: Jany B , Betz R , Schreck R
Published: September 2003

Recent studies have shown that surface epithelial cells play a major role in the defence and inflammatory reactions of the airways. How extracellular stimuli lead to increased gene expression in these epithelial cells is not well known. In this study, we asked whether the multiunit transcription factor, nuclear factor (NF)-kappa B, which regulates the expression of genes involved in defense and immune processes, is activated in airway epithelial cells following stimulation with inflammatory mediators and hydrogen peroxide. In addition, we studied whether this would be followed by upregulation of the NF-kappa B target gene product granulocyte-macrophage colony-stimulating factor (GM-CSF). Activation of NF-kappa B in the SV40 transformed human tracheobronchial epithelial cell line 1HAEo- was measured by electrophoretic mobility shift assays. GM-CSF concentrations in cell culture supernatants were determined by enzyme-linked immunosorbent assays. NF-kappa B was rapidly activated by exposure of cells to interleukin-1 beta (IL-1 beta), phorbol myristate acetate (PMA), and tumour necrosis factor-alpha (TNF). Exposure to H2O2 platelet activating factor (PAF) and lipopolysaccharide (LPS) did not lead to increased NF-kappa B activation. Co-stimulation of IL-1 beta with H2O2 led to augmentation and prolongation of the effect on NF-kappa B activation compared to stimulation with IL-1 beta alone. GM-CSF concentrations increased following stimulation with IL-1 beta and H2O2, and the effect of IL-1 beta/H2O2 co-stimulation on GM-CSF concentrations was additive. These results suggest that NF-kappa B may represent an important transcription factor, controlling the expression of cytokine genes in airway epithelial cells.
Prognostic analysis and predictive rule for outcome of hospital-treated community-acquired pneumonia
Authors: Ewig S , Bauer T , Hasper E , Pizzulli L , Kubini R , Luderitz B
Published: September 2003

In community-acquired pneumonia (CAP) mortality may be reduced by early identification of patients requiring intensive care treatment. The purpose of this study was to determine prognostic factors of outcome in patients with CAP in order to establish a clinically applicable discriminant rule. Ninety three episodes of CAP in 92 patients were retrospectively reviewed with regard to epidemiological, clinical, laboratory and microbiological data. The prognostic analysis included a univariate as well as a multivariate approach, in order to identify parameters associated with death using the Cox regression hazard function in a backward stepwise selection model. The three parameters found to contribute most to the significance of the model were used in a discriminant rule for classification of outcome. The parameters found to be significantly different between survivors and non-survivors were heart rate, systolic and diastolic as well as mean blood pressures, leucocyte count, percentage of lymphocytes, and lactate dehydrogenase (LDH) values. The multivariate analysis revealed that heart rate, systolic arterial pressure, and LDH serum levels were most closely associated with fatal outcome. A prognostic rule composed of the variables heart rate > or = 90 beats.min-1, systolic arterial blood pressure < or = 80 mmHg, and LDH > or = 260 U.l-1 achieved a sensitivity of 77%, a specificity of 75%, and positive and negative predictive values of 42 and 93%, respectively. It was associated with a six fold increased risk of fatal outcome. In conclusion, heart rate, systolic blood pressure, and LDH values were most closely associated with death in a multivariate analysis.(ABSTRACT TRUNCATED AT 250 WORDS)
CYFRA 21-1 as a tumour marker for bronchogenic carcinoma
Authors: Rapellino M , Niklinski J , Pecchio F , Furman M , Baldi S , Chyczewski L , Ruffini E , Chyczewska E
Published: September 2003

Despite extensive research, the role of the commonly employed tumour markers in the diagnosis of lung carcinoma is yet to be clarified. The utility of a new marker, CYFRA 21-1, in the preoperative evaluation of patients with bronchogenic carcinoma was investigated. CYFRA 21-1 was determined with a radiometric assay in serum of 280 patients with lung cancer and 208 patients with various nonmalignant lung diseases. The levels of the marker were significantly higher in lung cancer patients. Among benign lung diseases, elevated CYFRA 21-1 levels were found in pulmonary fibrosis. Using a cut-off of 3.2 ng.ml-1 (95th percentile of levels obtained in benign lung disease), the total sensitivity of the marker was 48%. The best sensitivity was obtained in squamous cell lung cancer (60%). The highest values of CYFRA 21-1 were found in metastatic lung cancer, and the marker sensitivity was more elevated in stage IIIb and IV. On the other hand, 40% of patients with surgically resectable lung cancer had CYFRA 21-1 levels above the cut-off. We conclude that CYFRA 21-1 may be satisfactorily employed in the differential diagnosis between malignant and benign lung diseases in association with other clinical and radiological data.
Cyclic nucleotides and phosphodiesterases and airway function
Authors: Barnes PJ
Published: September 2003

The cyclic nucleotides, cyclic adenosine monophosphate (cAMP) and cyclic guanosine monophosphate (cGMP) play an important role in the regulation of airway smooth muscle tone and activation of inflammatory cells. Intracellular concentrations of these nucleotides are tightly regulated by phosphodiesterases (PDEs). Several families of PDEs are now recognized and, within each isoenzyme family, molecular cloning has revealed multiple members. PDE III and IV are important in the breakdown of cAMP; PDE III is involved in the regulation of airway smooth muscle tone, whereas PDE IV is more important in inflammatory cells, including mast cells, macrophages, eosinophils, T-lymphocytes and epithelial cells. PDE V is involved in the breakdown of cGMP in airway and vascular smooth muscle. Regulation of PDE expression in health and disease is now under investigation. Several selective PDE inhibitors have recently been developed, and experimental studies indicate that PDE IV inhibitors may be useful as anti-inflammatory treatments in asthma. Clinical trials in asthma are now in progress.
Occupational asthma, rhinitis and urticaria due to piperacillin sodium in a pharmaceutical worker
Authors: Moscato G , Galdi E , Scibilia J , Dellabianca A , Omodeo P , Vittadini G , Biscaldi GP
Published: September 2003

A 28 year old man with no history of atopy was referred to our hospital for possible work-related asthma. He had been employed in the production section of a pharmaceutical company for 2 yrs, and in the last 2 months he had complained of dyspnoea, wheezing, chest tightness, symptoms of rhinitis and a cutaneous rash when exposed to powdered antibiotics. Symptoms disappeared after being transferred to the packaging section. When the subject was admitted to our department he was asymptomatic. Basal lung function tests were in the normal range. Bronchial challenges with methacholine and with ultrasonically-nebulized distilled water were negative. Skin-prick test with piperacillin sodium gave a strong positive response at a very low concentration. Specific inhalation challenge with piperacillin sodium resulted in an immediate asthmatic reaction, and also reproduced rhinitis symptoms and the cutaneous rash. A control challenge with lactose, and the specific challenge test with cefuroxime sodium (another antibiotic to which the patient was exposed at the workplace) were negative. We conclude that piperacillin sodium is an agent that can cause occupational asthma.
Bronchiolitis obliterans organizing pneumonia secondary to amiodarone: a rare aetiology
Authors: Valle JM , Alvarez D , Antunez J , Valdes L
Published: September 2003

Bronchiolitis obliterans organizing pneumonia (BOOP) is a clinicopathological entity with well-defined diagnostic criteria, the aetiology of which is generally unknown. Among the adverse pulmonary effects of the drug amiodarone, BOOP is the least commonly reported in the literature. In this article we describe a case of amiodarone-induced BOOP.
Association of histologically proven rheumatoid arthritis with pulmonary sarcoidosis
Authors: Menard O , Petit N , Gillet P , Gaucher A , Martinet Y
Published: September 2003

The association of rheumatoid arthritis proven by means of synovial biopsy with pulmonary sarcoidosis proven by means of bronchial biopsy, occurred in a 58 year old woman. Corticosteroid therapy resulted in complete resolution of sarcoidosis but only slight improvement of the rheumatoid arthritis, which was secondarily treated with methotrexate with a successful outcome. Only two similar cases have been reported with simultaneous histological proofs of both diseases.
International Study of Asthma and Allergies in Childhood (ISAAC): rationale and methods
Authors: Asher MI , Keil U , Anderson HR , Beasley R , Crane J , Martinez F , Mitchell EA , Pearce N , Sibbald B , Stewart AW , et al.
Published: September 2003

The aetiology of asthma and allergic disease remains poorly understood, despite considerable research. The International Study of Asthma and Allergies in Childhood (ISAAC), was founded to maximize the value of epidemiological research into asthma and allergic disease, by establishing a standardized methodology and facilitating international collaboration. Its specific aims are: 1) to describe the prevalence and severity of asthma, rhinitis and eczema in children living in different centres, and to make comparisons within and between countries; 2) to obtain baseline measures for assessment of future trends in the prevalence and severity of these diseases; and 3) to provide a framework for further aetiological research into genetic, lifestyle, environmental, and medical care factors affecting these diseases. The ISAAC design comprises three phases. Phase 1 uses core questionnaires designed to assess the prevalence and severity of asthma and allergic disease in defined populations. Phase 2 will investigate possible aetiological factors, particularly those suggested by the findings of Phase 1. Phase 3 will be a repetition of Phase 1 to assess trends in prevalence.
Adsorption of Pollutants from Aqueous Solutions Using Activated and Non-Activated Oak Shells: Parametric and Fractional Factorial Design Study. Part I. Removal of Copper
Authors: Al-Asheh Sameer , Banat Fawzi , Al-Hamed Nagham
Published: September 2003

Non-activated and chemically activated oak shells were evaluated for their ability to remove Cu2+ ions from aqueous solutions. Batch adsorption experiments were conducted to investigate the effect of contact time, sorbent concentration, Cu2+ ion concentration and the pH of the solution on the sorption process. The Cu2+ ion uptake by oak shells increased with decreasing sorbent concentration or with an increase in Cu2+ ion concentration or solution pH.

The fractional factorial design technique was applied in order to determine the average Cu2+ ion uptake, the contribution of each operating variable to the value of the uptake and the interaction among the operating variables when the sorbent type, sorbent concentration, Cu2+ ion concentration, pH, contact time and salt were all varied from one level to another.

Application of this technique showed that the sorbent concentration had the largest influence on the value of the Cu2+ ion uptake followed by Cu2+ ion concentration and sorbent type. Interaction among the different operating variables played an important role in the adsorption process.
Pore Structures of ZSM-5 Synthesized in the Mesopore Spaces of a Carbon Aerogel
Authors: Tao Yousheng , Tanaka H. , Ohkubo T. , Kanoh H. , Kaneko K.
Published: September 2003

A mesoporous ZSM-5 monolith several millimetres in size has been synthesized employing the template method and using a carbon aerogel with uniform mesopores. Measurement of the pore-size distribution using nitrogen adsorption showed a bimodal pore system of mesopores and micropores whose average pore widths were 8 nm and 0.51 nm, and whose volumes were 0.09 cm3/g and 0.34 cm3/g, respectively.
Bayesian Fast Fourier Transform Approach for Modal Updating Using Ambient Data
Authors: Yuen Ka-Veng , Katafygiotis Lambros S.
Published: September 2003

The problem of identification of the modal parameters of a structural model using measured ambient response time histories is addressed. A Bayesian Fast Fourier Transform approach (BFFTA) for modal updating is presented which uses the statistical properties of the Fast Fourier transform (FFT) to obtain not only the optimal values of the updated modal parameters but also their associated uncertainties, calculated from their joint probability distribution. Calculation of the uncertainties of the identified modal parameters is very important when one plans to proceed with the updating of a theoretical finite element model based on modal estimates. The proposed approach requires only one set of response data in contrast to many of the existing frequency-based approaches which require averaging. It is found that the updated PDF can be well approximated by a Gaussian distribution centred at the optimal parameters at which the posterior PDF is maximized. Examples using simulated data are presented to illustrate the proposed method.
Tests and Analysis on the Temperature Field within Concrete Filled Steel Tubes with or without Protection Subjected to a Standard Fire
Authors: Han Lin-Hai , Xu Lei , Zhao Xiao-Ling
Published: September 2003

The temperature fields within twelve concrete filled steel tubular columns with or without fire protection when exposed to the ISO-834 standard fire curve (ISO-834, 1975) have been experimentally investigated and the results are presented in this paper. The main parameters varied in the tests are: (1)Sectional types, square and circular; (2) Sectional dimensions from 299mm to 800mm; (3) Thickness of fire protection coat from 14mm to 35mm. A derivation has been given for the surface temperature of concrete-filled tubular columns. Nonlinear finite element analysis has been carried out to calculate the temperature field for the members with and without fire protection. The theoretical predictions are in good agreement with the experimental data. It has been found that the increasing of tube dimensions results in a temperature reduction in the section. The effect of tube dimensions on temperature reduction is more significant for the core concrete than for the steel surface. Within a three-hour fire time, the reduction in temperature due to the increase in tube dimensions becomes less significant when the outer sectional dimension exceeds about 400 mm. The work in this paper provides a basis for further theoretical study on the fire resistance of concrete filled steel tubular columns.
Dynamic Analysis of Liquid Storage Tanks with Sliding Systems
Authors: Shrimali M. K. , Jangid R. S.
Published: September 2003

Dynamic response of liquid storage tanks isolated by the sliding systems is investigated under real earthquake ground motion. The frictional force of sliding systems is modelled by conventional and hysteretic models. The continuous liquid mass is lumped as convective mass, impulsive mass and rigid mass. The corresponding stiffness associated with these lumped masses is worked out depending upon the properties of the tank wall and liquid mass. The governing equations of motion of the tank with sliding system are derived and solved by Newmark's step-by-step method with iterations. The frictional force mobilized at the interface of the sliding system is assumed to be velocity dependent. For comparative study, the seismic response of isolated liquid storage tank obtained by the conventional model is compared with the corresponding response obtained by the hysteretic model. In order to measure the effectiveness of isolation system, the seismic response of isolated tank is compared with that of the non-isolated tank. A parametric study is also conducted to study the effects of aspect ratio of tank on the effectiveness of seismic isolation of liquid storage tanks. It is found that the sliding systems are quite effective in reducing the earthquake response of liquid storage tanks. In addition, the conventional and the hysteretic model of the sliding system predict the same seismic response of liquid storage tanks. However, the conventional model is relatively more computationally efficient as compared to the hysteretic model.
Dissociation as a mediator of the relationship between recalled parenting and the clinical correlates of auditory hallucinations
Authors: Offen Liz , Thomas Glyn , Waller Glenn
Published: September 2003

Background:This study of patients who experience auditory hallucinations examined the potential role of dissociation as a mediator in the relationship between memories of parental behaviours during childhood and psychopathology in adulthood.

Method:Thirty‐six patients who experienced auditory hallucinations completed standardized measures of recalled parental behaviours, beliefs about voices, depression and dissociation. Regression analyses were used to test for mediating effects.

Results:The findings support a model where dissociation mediates the relationship between paternal overprotection and depression. There were no significant findings regarding the relationship between recalled parenting and beliefs about voices.

Discussion:The clinical and research implications of the study are outlined, emphasizing dissociation as a potential treatment target.
Pure and guided self‐help for full and sub‐threshold bulimia nervosa and binge eating disorder
Authors: Ghaderi Ata , Scott Berit
Published: September 2003

Objective:The study compared the efficacy of self‐help without and with guidance (referred to as ‘pure’ and ‘guided’ self‐help), using a cognitive behavioral self‐help manual (Fairburn, 1995) for binge eating.

Design and methods:A sample of 31 participants with bulimia nervosa, subthreshold bulimia nervosa and binge‐eating disorder were assigned randomly to one of the self‐help levels for 16 weeks, after four weeks of baseline observations.

Results:The results indicated that both forms of self‐help treatments had a modestly positive and sustained effect on the participants' eating problems. Intention‐to‐treat analyses showed that participants reduced their mean number of objective bulimic episodes and purging behaviour by 33% and 17% over the course of the treatment. The corresponding reduction levels for the treatment completers (N = 18) were 58% and 61%, respectively. Furthermore, there were no significant differences between the pure and guided self‐help groups in terms of outcome, reflecting the probable insignificance of guidance for the broader group of individuals with binge‐eating problems. At follow‐up, no further significant improvement or deterioration was observed in the ensuing six months compared with the post‐treatment data.

Conclusion:Given the heterogeneity of the diagnostic groups in the present study, resulting in high external validity, and the conservative nature of the analyses, self‐help is discussed as a viable means of initial treatment for binge eating.
Exposure to chemical carcinogens and risk of cancer among Finnish laboratory workers
Authors: Kauppinen Timo , Pukkala Eero , Saalo Anja , Sasco Annie J.
Published: September 2003

Background

Laboratory workers have long been suspected of having increased risks of cancer due to their occupation. We evaluated occupational exposure and cancer incidence among Finnish laboratory workers.

Materials and Methods

The cohort was comprised of 4,722 laboratory workers reported to the Finnish Register of Workers Exposed to Carcinogens in 1979–1988. The standardized incidence ratios (SIR) for cancers and their 95% confidence intervals (CI) were calculated based on data of the Finnish Cancer Registry.

Results

The most common carcinogens, to which these workers were potentially exposed, were chromium (VI), carbon tetrachloride, cadmium, benzene, and chloroform. From this cohort, 174 persons were recorded with primary tumors in 1980–1999. The SIR for cancer of all sites combined was 0.99 (CI 0.85–1.14). None of the cancer‐specific SIRs were significantly elevated. Slight excesses were found, e.g., for non‐Hodgkin's lymphoma (seven observed, 4.8 expected) and leukemia (four observed, three expected).

Conclusions

This study did not suggest any major cancer risks among Finnish laboratory workers but the follow‐up time of the cohort was too short (on an average 15.7 years) to reveal possible cancer risks requiring a longer induction period. Am. J. Ind. Med. 44:343–350, 2003. © 2003 Wiley‐Liss, Inc.
Response to Zeka et al., Am J Ind Med 43: 286–290, 2003
Authors: Greaves Ian A.
Published: September 2003

Zeka et al. [2003] recently considered the role of underlying ventilatory obstruction (as measured by spirometry) in predicting short term airflow obstruction resulting in from inhalation of metal working fluid aerosols. The authors found no clear relationship between acute responses and pre‐existing ventilatory obstruction, in contrast to findings from an earlier study [Robins et al., 1997].
Aeroallergens, allergic rhinitis, and sedating antihistamines: Risk factors for traumatic occupational injury and economic impact
Authors: Hanrahan L.P. , Paramore L.C.
Published: September 2003

Background

The U.S. workplace injury burden is significant. Our objective was to assess the particular impact of aeroallergen, allergic rhinitis, and antihistamine exposures and side effects on the risk of traumatic work‐related injuries, and the associated economic impact.

Methods

This is an observational case‐control study with 1,223 acute traumatic injury cases that are compared to 1,202 chronic back injury controls. Structured telephone interviews were conducted in 1998 and 1999 on Workers' Compensation applicants injured in 1997. Antihistamine use and pollen levels were measured 2 weeks prior to the injury date.

Results

Sedating antihistamine exposures elevated acute injury risk (main effect OR: 2.93). A significant increase in traumatic injury risk was observed for combined sedating antihistamine and high pollen exposures among subjects with physician and self‐diagnosed allergic rhinitis (OR: 2.41). Direct medical costs associated with this increased risk were estimated at $143 million in 2001.

Conclusions

Workers with physician‐diagnosed allergic rhinitis have as high a reliance on sedating antihistamines as do self‐diagnosed and self‐medicating nasal allergy sufferers. High pollen exposures along with sedating antihistamine use may confer significant additional injury risks among allergic rhinitis sufferers. Medical management “best practices” of diagnosed allergic rhinitis should include avoidance of sedating antihistamines to minimize acute, traumatic injury risks. Am. J. Ind. Med. 44:438–446, 2003. © 2003 Wiley‐Liss, Inc.
Comparison of fatal occupational injury surveillance systems between the European Union and the United States
Authors: Benavides Fernando G. , Delclos George L. , Cooper Sharon P. , Benach Joan
Published: September 2003

Background

Comparison of workplace injury statistics among countries is often problematic, mainly because work injury statistics are based on different national recording and notification systems.

Methods

Definitions of fatal work‐related injuries, identification of the reference population, and rates of fatal work‐related injuries, from 1995 to 1998, were compared between the European Statistics on Accidents at Work (ESAW) and the United States (U.S.) Census of Fatal Occupational Injuries (CFOI).

Results

Similar definitions for workplace fatalities were found, but CFOI is based on an active search, and ESAW on passive notification. Daily fatal occupational injury numbers were similar in both: about 17 workers die per day, but average annual work‐related death rates were higher in the U.S.

Conclusions

There are enough differences to allow direct comparisons between both systems. CFOI is likely to be more comprehensive than ESAW. It is conceivable that the true number of fatal occupational injuries in the European Union (E.U.) could be higher, and thus the apparent difference in U.S. and E.U. fatal injury rates may be an artifact of the different surveillance systems. Am. J. Ind. Med. 44:385–391, 2003. © 2003 Wiley‐Liss, Inc.
Classification of working processes to facilitate occupational hazard coding on industrial trawlers
Authors: Jensen Olaf C. , Stage Søren , Noer Preben , Kaerlev Linda
Published: September 2003

Background

Commercial fishing is an extremely dangerous economic activity. In order to more accurately describe the risks involved, a specific injury coding based on the working process was developed.

Method

Observation on six different types of vessels was conducted and allowed a description and a classification of the principal working processes on all kinds of vessels and a detailed classification for industrial trawlers. In industrial trawling, fish are landed for processing purposes, for example, for the production of fish oil and fish meal. The classification was subsequently used to code the injuries reported to the Danish Maritime Authority over a 5‐year period.

Results

On industrial trawlers, 374 of 394 (95%) injuries were captured by the classification. Setting out and hauling in the gear and nets were the processes with the most injuries and accounted for 58.9% of all injuries. A relatively large number of injuries occurred when embarking and disembarking. Specific risks were identified in a number of other working processes.

Conclusion

Specific areas for risk prevention in fishery may be identified by using a detailed classification system that takes both the specific method of fishing and the working processes into consideration. Am. J. Ind. Med. 44:424–430, 2003. © 2003 Wiley‐Liss, Inc.
Kombinatorische Flüssigphasensynthese von Bibliotheken: auf der Suche nach Modulatoren für Protein‐Protein‐ und Protein‐DNA‐Wechselwirkungen in der zellulären Signaltransduktion
Authors: Boger Dale L. , Desharnais Joel , Capps Kevin
Published: September 2003

Hochdurchsatzsynthese und ‐screening von Verbindungsbibliotheken haben große Erwartungen für die Wirkstoffsuche geweckt. Für die Herstellung solcher Bibliotheken an der Festphase und in Lösung sind leistungsfähige Methoden entwickelt worden. Die Synthesestrategie wird schon lange nicht mehr nach allgemeinen Erwägungen ausgewählt, sondern mit Blick auf die spezielle Fragestellung. In diesem Aufsatz beschreiben wir Unterschiede zwischen den beiden Methoden, die bei der Entwicklung neuer Programme helfen sollen. Als Beispiel beschreiben wir unsere Versuche, mithilfe von Lösungstechniken Modulatoren für zelluläre Signale durch Beeinflussung von Protein‐Protein‐ oder Protein‐DNA‐Wechselwirkungen zu identifizieren. Das Vorurteil, niedermolekulare Substanzen seien für therapeutische Intervention an solchen Zielstrukturen ungeeignet, konnten wir beim Screening unserer Bibliotheken gegen eine repräsentative Auswahl extrazellulärer und intrazellulärer Targets widerlegen: Mithilfe zahlreicher Testmethoden identifizierten wir die ersten niedermolekularen Modulatoren für Protein‐Protein‐Wechselwirkungen und erarbeiteten ein allgemeines Verfahren für derartige Untersuchungen.
Neuere Entwicklungen in der katalytischen asymmetrischen Synthese von α‐ und β‐Aminosäuren
Authors: Ma Jun‐An
Published: September 2003

Zur stereoselektiven Synthese von Aminosäuren, die von zentraler Bedeutung für den Aufbau chiraler Naturstoffe und Pharmazeutika ist, wird neben Enzymen ein breites Sortiment von chiralen Reagentien, Auxiliaren und Katalysatoren eingesetzt. Effiziente Methoden zur Synthese von chiralen proteinogenen und nichtproteinogenen Aminosäuren beruhen häufig auf asymmetrischen Reaktionen unter Verwendung katalytischer Mengen chiraler Verbindungen. Dieser Kurzaufsatz fasst neuere Entwicklungen zur katalytischen Synthese von α‐ und β‐Aminosäuren zusammen.
Titelbild: Single‐Wall Carbon Nanotube–Ferrocene Nanohybrids: Observing Intramolecular Electron Transfer in Functionalized SWNTs (Angew. Chem. 35/2003)
Authors: Guldi Dirk M. , Marcaccio Massimo , Paolucci Demis , Paolucci Francesco , Tagmatarchis Nikos , Tasis Dimitrios , Vázquez Ester , Prato Maurizio
Published: September 2003

Kohlenstoffnanoröhren sind ein zentrales Forschungsgebiet der modernen Materialwissenschaften. D. M. Guldi, F. Paolucci, M. Prato et al. beschreiben in ihrer Zuschrift auf S. 4338 ff. die Präparation einer Nanohybridverbindung aus einer einwandigen Nanoröhre und Ferrocen (SWNT‐Fc), die durch photoinduzierten Elektronentransfer in einen langlebigen ladungsgetrennten Zustand (SWNT.−‐Fc.+) überführt werden kann. Die radikalanionische Form der Nanoröhre wurde mit Laser‐Blitzphotolyse detektiert.
Solution‐Phase Combinatorial Libraries: Modulating Cellular Signaling by Targeting Protein–Protein or Protein–DNA Interactions
Authors: Boger Dale L. , Desharnais Joel , Capps Kevin
Published: September 2003

The high‐throughput synthesis and screening of compound libraries hold tremendous promise for drug discovery and powerful methods for both solid‐phase and solution‐phase library preparation have been introduced. The question of which approach (solution‐phase versus solid‐phase) is best for the preparation of chemical libraries has been replaced by which approach is most appropriate for a particular target or screen. Herein we highlight distinctions in the two approaches that might serve as useful considerations at the onset of new programs. This is followed by a more personal account of our own focus on solution‐phase techniques for the preparation of libraries designed to modulate cellular signaling by targeting protein–protein or protein–DNA interactions. The screening of our libraries against a prototypical set of extracellular and intracellular targets, using a wide range of assay formats, provided the first small‐molecule modulators of the protein–protein interactions studied, and a generalized approach for conducting such studies.
Cover Picture: Transformation of a Spherical Supramolecular Dendrimer into a Pyramidal Columnar Supramolecular Dendrimer Mediated by the Fluorophobic Effect (Angew. Chem. Int. Ed. 36/2003)
Authors: Percec Virgil , Glodde Martin , Johansson Gary , Balagurusamy Venkatachalapathy S. K. , Heiney Paul A.
Published: September 2003

The mode of the self‐assembly of (3,4,5)2G2‐CO2Me monodendrons changes from a spherical to a pyramidal supramolecular dendrimer upon replacement of the aliphatic chains by partially fluorinated chains. This metamorphosis was verified with a combination of small‐ and wide‐angle X‐ray diffraction, electron density calculations, and molecular modeling studies. For more information on this process, see the Communication by V. Percec et al. on page 4338 ff.
Enhanced Li+ Binding Energies in Alkylbenzene Derivatives: The Scorpion Effect
Authors: Mó Otilia , Yáñez Manuel , Gal Jean‐François , Maria Pierre‐Charles , Decouzon Michèle
Published: September 2003

The gas‐phase lithium cation basicities (LCBs; Gibbs free energy of binding) of ethyl‐, n‐butyl‐, and n‐heptylbenzene have been measured by Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry. The structures of the corresponding complexes and their relative stabilities were investigated through the use of B3LYP/6‐311G+(3df,2p)//B3LYP/6‐31G(d) density functional theory calculations. For n‐butylbenzene and n‐heptylbenzene, the most stable adducts correspond to π complexes in which the alkyl chain coils toward the aromatic ring to favor its interaction with the metal cation. The extra stabilization provided by the flexible alkyl chain polarized by the charge on Li+ is named the “scorpion effect”. Conversely, these coiled conformations are among the least stable in the neutral system; they are not all stationary points on the potential‐energy surface. The formation of complexes with a coiled alkyl chain leads to a significant enhancement of the Li+ bonding energies (LBEs), which are approximately 20–30 kJ mol−1 higher than those calculated for alkylbenzene π complexes in which an uncoiled chain remains distant from the cation and thus minimizes the scorpion effect. This enhancement is less significant when LCBs are concerned, because the scorpion effect is entropically disfavored. There is very good agreement between the experimental Li+ gas‐phase basicities and the calculated values, provided that the statistical distribution of the conformers present in the gas phase is taken into account in this calculation.
Scalar Coupling between the 15N Centres in Methylated 1,8‐Diaminonaphthalenes and 1,6‐Diazacyclodecane: To What Extent is 2HJNN a Reliable Indicator of NN Distance?
Authors: Lloyd‐Jones Guy C. , Harvey Jeremy N. , Hodgson Paul , Murray Martin , Woodward Robert L.
Published: September 2003

The scalar couplings between hydrogen bonded nitrogen centres (2HJNN) in the free‐base and protonated forms of the complete series of [15N2]‐N‐methylated 1,8‐diamino naphthalenes in [D7]DMF solution have been determined, either directly (15N{1H} NMR), or, indirectly (13C{1H} NMR and simulation of the X part of the ABX spectrum (X=13C, A,B=15N)). Additionally, the 2HJNN value in the HBF4 salt of [15N2]‐1,6‐dimethyl‐1,6‐diazacyclodecane was determined, indirectly by 13C{1H} NMR spectroscopy. As confirmed by DFT calculations and by reference to CSD, the rigid nature of the naphthalene scaffold results in rather low deviations in N,N distance or H‐N,N angle within each series, apart from the free base of the permethylated compound (proton sponge) where the naphthalene ring is severely distorted to relieve strain. Despite such restrictions, the 2HJNN values increase smoothly from 1.5 to 8.5 Hz in the protonated series as the degree of methylation increases. The effect in the free‐base forms is much less pronounced (2.9 to 3.7 Hz) with no scalar N,N coupling detected in the permethylated compound (proton sponge) due to the lack of hydrogen bond between the N,N centres. Neither the pKa nor the NN distance in the protonated forms correlates with 2HJNN. However, the sum of the 13C NMR shifts of the naphthalene ring C(1,8) carbons which are attached directly to the nitrogen centres correlates linearly with 2HJNN and with the degree of methylation. The gas‐phase computed 2HJNN is almost constant throughout the homologous series, and close to the experimental value for the tetramethylated ion. However, the computed coupling constant is attenuated in structures involving microsolvation of each N‐H unit, and the trend then matches experiment. These experimental and computational observations suggest that Fermi contact between the two N centres is decreased upon formation of strong charge‐dispersing intermolecular hydrogen bonds of the free N‐H groups with the solvent.
Car–Parrinello Molecular Dynamics Study of the Rearrangement of the Valeramide Radical Cation
Authors: Semialjac Marija , Schröder Detlef , Schwarz Helmut
Published: September 2003

Car–Parrinello molecular dynamics (CPMD) studies of neutral (1) and ionized (1+.) valeramide are performed with the aim of providing a rationalization for the unusual temperature effect on the dissociation pattern of 1+. observed in mass spectrometric experiments. According to CPMD simulations of neutral valeramide 1 performed at approximately 500 K, the conformation with the fully relaxed carbon backbone predominates (96 %). Conformational changes involving folding of the carbon backbone into conformers that would allow intramolecular H transfers are predicted not to take place spontaneously at this temperature because of the barrier heights associated with these transitions (3.5 and 6.9 kcal mol−1), which cannot be overcome by thermal motion alone. For 1+., CPMD simulations performed at ≈300 K reveal a substantial stability of a conformation in which the carbon backbone is fully relaxed; no reaction is observed even after 7 ps. However, when conformers with already folded carbon‐backbones are used as initial geometries in the CPMD simulations, the γ‐hydrogen migration (McLafferty rearrangement resulting in C3H6) is already completed within 2 ps. For this important process, the free activation energy associated with both a required conformational change and the subsequent H transfer equals 4.5 kcal mol−1, while for the formally related δ‐H shift (which eventually gives rise to the elimination of C2H4/C2H5.) it amounts to 7.0 kcal mol−1. Since the barriers associated with conformational changes are energetically more demanding than those of the corresponding hydrogen transfers, 1+. is essentially trapped by conformational barriers and long‐lived at ≈300 K. At elevated temperatures (500 K), the preferred reaction (within 7.3 ps) in the CPMD simulation corresponds to the McLafferty rearrangement. The estimated free activation energy associated with this process amounts to 2.5 kcal mol−1, while the free activation energy for the δ‐H transfer equals 4.4 kcal mol−1. This relatively small free activation energy for the McLafferty rearrangement might cause dissociation of a substantial fraction of 1+. prior to the time‐delayed mass selection, which would reduce the C3/C2 ratio in the experiments conducted with metastable ions that have a lifetime in the order of some μs at a source temperature of 500 K.
Structure defects and optical damage resistance in doubly doped In:Nd:LiNbO3 crystal waveguide substrates
Authors: Zhen X. H. , Zhao L. C. , Xu Y. H.
Published: September 2003

A series of In:Nd:LiNbO3 crystals were grown by Czochralski technique and were made into waveguide substrates. The optical damage resistance of the In:Nd:LiNbO3 waveguide substrates was characterized by measurement of the holographic method. The optical damage resistance of In (3.0 mol%):Nd:LiNbO3 was much higher than that of other In:Nd:LiNbO3. The ultraviolet‐visible (UV‐Vis) absorption spectra the In:Nd:LiNbO3 crystals were measured and investigated. The structure defects were discussed in this paper to explain the enhance of the optical damage resistance in the In:Nd:LiNbO3 crystals. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Influence of the Crystallization Solvent on Molecular and Supramolecular Structures of Silver(I) Tris(3‐Phenylpyrazolyl)methane Complexes
Authors: Reger Daniel L. , Semeniuc Radu F. , Smith Mark D.
Published: September 2003

The compound [{HC(3‐Phpz)3}Ag](BF4) (pz = pyrazolyl ring) has been prepared and shown to crystallize in four different forms depending on the solvent. Vapor‐phase diffusion of diethyl ether into nitromethane solutions of the complex produces two polymorphs, an orthorhombic form (1) and triclinic form (2). Both polymorphs are coordination polymers constructed by a κ2−κ1 coordination of the tris(3‐Phpz)methane units and have similar, but different, supramolecular structures. In 1 there are two independent chains linked by C−H···π interactions. In 2 only one type of chain is present, with a different internal structure than in 1. Non‐covalent forces, mainly C−H···π interactions, organize the chains into sheets and the sheets into a final 3‐D supramolecular structure in the case of 1, while in the case of 2 only a 2‐D supramolecular structure forms. In contrast, vapor‐phase diffusion of diethyl ether into acetonitrile or acetone solutions produces [{HC(3‐Ph‐pz)3}Ag{(CH3)2CO}](BF4) (3) and [{HC(3‐Phpz)3}Ag{CH3CN}](BF4) (4). In these compounds, the ligand shows tripodal coordination to a single silver center and coordination of one solvent molecule to the metallic center. Both compounds form 3‐D supramolecular structures organized by both C−H···π interactions and weak C−H···F hydrogen bonds and in the case of 4 π−π stacking. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Organocalcium Compounds with Catalytic Activity for the Ring‐Opening Polymerization of Lactones
Authors: Westerhausen Matthias , Schneiderbauer Stefan , Kneifel Alexander N. , Söltl Yvonne , Mayer Peter , Nöth Heinrich , Zhong Zhiyuan , Dijkstra Pieter J. , Feijen Jan
Published: September 2003

The equimolar reaction of calcium bis[bis(trimethylsilyl)amide] with 2,2,6,6‐tetramethylheptane‐3,5‐dione (Htmhd) in THF yields liquid mononuclear [Ca(tmhd){N(SiMe3)2}(THF)3] (1). A similar reaction in toluene with a stoichiometric ratio of 2:3 gives the dinuclear complex [{(THF)Ca}2(tmhd)2(µ‐tmhd){µ‐N(SiMe3)2}] (2). The calcium atoms of these complexes are in a distorted octahedral environment. In 2 the complex consists of two octahedra connected by a common face of one nitrogen base and two oxygen atoms; the bridging Ca−N bond lengths are extremely large. The metalation of the tetradentate Jacobsen reagent with calcium bis[bis(trimethylsilyl)amide] in 1,2‐dimethoxyethane (DME) gives the corresponding calcium complex 3, nearly quantitatively, as its DME adduct. The calcium atom is in an unusual trigonal prismatic coordination sphere. The metathesis reaction of 3 with tin(II) chloride yields the corresponding yellow tin(II) complex with the metal atom in a distorted square‐pyramidal environment. Complexes 2 and 3 show catalytic reactivity in the ring‐opening polymerization of cyclic esters such as lactones and lactides. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Syntheses and Crystal Structures of Highly Diastereomerically Enriched Lithiated Benzylsilanes in the Presence of External Donor Molecules: Experiment and Theory
Authors: Strohmann Carsten , Buchold Daniel H. M. , Seibel Timo , Wild Kerstin , Schildbach Daniel
Published: September 2003

The solid‐state structures of the lithiated (aminomethyl)benzylsilanes Me2Si[(R)‐(CHPhLi·0.5TMEDA)](CH2SMP) [{(R,S)‐2}2·TMEDA] and Me2Si[(R)‐(CHPhLi·DABCO)](CH2SMP) [(R,S)‐2·DABCO] [CH2SMP = (S)‐2‐(methoxymethyl)pyrrolidinomethyl] and the absolute configurations at the stereogenic metallated carbon centres of these compounds were determined by single‐crystal X‐ray diffraction methods. The crystal structures of the TMEDA‐bridged dimer [(R,S)‐2]2·TMEDA and monomeric (R,S)‐2·DABCO were compared to that of the parent compound (R,S)‐2, a coordination polymer. By computational methods [B3LYP/6−31+G(d)], the mechanism of the deprotonation of the starting compound, (aminomethyl)benzylsilane [(S)‐1], as well as the stability of configuration of the lithiated derivatives of (R,S)‐2, were examined. For the highly diastereoselective substitution reactions of the derivatives of (R,S)‐2 with iodomethane, inversion of the configuration at the metallated carbon centre was observed and correlated with the results of the quantum‐chemical studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Solvent‐Free and TMEDA‐Solvated Mixed Alkali Metal‐Magnesium Tris‐diisopropylamides
Authors: Hevia Eva , Kenley Fiona R. , Kennedy Alan R. , Mulvey Robert E. , Rowlings René B.
Published: September 2003

A trio of heterobimetallic tris‐diisopropylamides, the solvent‐free potassium‐magnesium amide [{KMg(NiPr2)3}∞], its TMEDA solvate [KMg(NiPr2)3·TMEDA] and the sodium congener [NaMg(NiPr2)3·TMEDA] has been synthesised by mixing the appropriate metal alkyl reagents with three molar equivalents of diisopropylamine in a hydrocarbon medium, to which, in the last two cases, TMEDA is added. All three amides have been successfully crystallographically characterised by X‐ray diffraction studies. Representing the first pure s‐block mixed‐metal diisopropylamide free of solvent molecules or other stabilising anionic co‐ligands, the first compound adopts an infinite spiral chain of ···K‐(μ‐N)2‐Mg‐N··· links, the metal‐N framework of which is supported by agostic K···C intra‐dinuclear and inter‐dinuclear contacts. The dinuclear tris‐amido motif is maintained in both TMEDA complexes, the metal‐N cores of which are essentially isostructural, but the presence of the chelating diamine blocks the propagating terminal site on the alkali metal and so gives rise to discrete molecular structures. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Homo‐ and Heteroleptic Hypersilylcuprates — Valuable Reagents for the Synthesis of Molecular Compounds with a Cu−Si Bond
Authors: Klinkhammer Karl W. , Klett Jan , Xiong Yun , Yao Shenglai
Published: September 2003

Unsolvated hypersilanides MHyp [Hyp = Si(SiMe3)3] of the heavier alkali metals (MI = Na, K, Cs) react with copper tert‐butoxide in toluene to yield crystalline heteroleptic cuprates [MI(toluene)][tBuOCuHyp]. These cuprates proved to be valuable sources for pure hypersilylcopper and other cuprates bearing hypersilyl ligands such as the di(hypersilyl)‐ cuprates MI[CuHyp2]. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)