bluuebunny/crossref_metadata_2025 huggingface dataset:
High rates of adverse effects and patient unawareness of withdrawn lipid‐lowering drug combination in a public hospital clinic
Authors: Schiff Gordon D. , Keehr Leah M. , Sai Theophilus T. , Bult Judilynn
Published: December 2002

Purpose

Examine use, patient awareness and outcomes of concurrent cerivastatin and gemfibrozil in a public hospital clinic system 2 weeks following cerivastatin withdrawal.

Methods

Electronic pharmacy records for cerivastatin prescriptions for 1 year preceding withdrawal were downloaded and linked to gemfibrozil prescriptions. Patients with concurrent prescriptions were surveyed for current use, awareness of withdrawal/warnings, adverse effects and creatine phosphokinase (CK) results.

Results

From August 2000 to August 2001, 29 377 prescriptions for cerivastatin were dispensed for 10 780 unique patients; 211 (2%) also received gemfibrozil. Prescription time frames for the two drugs overlapped for 67 patients. Interview of 47 patients revealed 35 actually taking both. 18/35 (51.4%) were still taking both drugs 2 weeks after market‐withdrawal of cerivastatin. Only 7/46 (21.2%) had ‘heard the news’ about withdrawal. 19/46 (41.3%) described muscle‐related symptoms; nine reported severe symptoms. Only 13 (28.3%) had CK monitoring. 5/8 symptomatic patients monitored had CK values >200 U/L. (>1000 U/L in two cases.)

Conclusions

Despite escalating labeled warnings, nearly 2% of patients prescribed cerivastatin received gemfibrozil prescriptions, 1/3 concurrently. Most were still taking this combination 2 weeks after cerivastatin withdrawal and unaware of publicized warnings. Nearly half experienced muscle‐related symptoms. More reliable methods for preventing prescription/dispensing of interacting medications and alerting patients about drug recalls are warranted. Copyright © 2002 John Wiley & Sons, Ltd.
Patterns and perceptions of complementary and alternative medicine (CAM) among leukaemia patients visiting haematology clinic of a north Indian tertiary care hospital
Authors: Gupta M. , Shafiq N. , Kumari S. , Pandhi P.
Published: December 2002

Purpose

The use of complementary and alternative medicine (CAM) in cancer treatments is widespread with substantial number of patients deserting conventional cancer therapies in favour of unproven methods. The present study aimed at discovering the prevalence of use of CAM cancer therapies in leukaemia patients visiting haematology clinic of a north Indian tertiary care hospital.

Methods

533 consecutive leukaemia patients were interviewed. Information was gathered about patients' demographics, types of CAM taken, sequence of seeking CAM and conventional medicine, sources of recommendation, reasons of opting for CAM, and areas of satisfaction and dissatisfaction associated with the use of CAM. Patients were also asked if they had informed their doctor about CAM use.

Results

Prevalence of CAM use in leukaemia patients was found to be 56.6%. Ayurveda was the most commonly used CAM (33%). Most of the patients sought conventional medicine first, followed by CAM therapies. Fifty‐two percent of the patients opted for CAM hoping for a miracle cure and 51% were dissatisfied with these therapies. Family members and neighbours constituted major source of recommendation of CAM therapy. Only 3.8% of the patients had informed their doctors about CAM use.

Conclusion

A sizeable percentage of patients receiving conventional treatment for leukaemia also use CAM therapies. Clinicians should not underestimate the value of hopeful attitude in their management of leukaemia patients and ought to be conversant with popular forms of CAM cancer therapies. Copyright © 2002 John Wiley & Sons, Ltd.
Seasonality and personality: a prospective investigation of Five Factor Model correlates of mood seasonality
Authors: Murray Greg , Allen Nicholas B. , Rawlings David , Trinder John
Published: December 2002

The aim of the present study was to explore winter pattern seasonality of mood by investigating its Five Factor Model (FFM) correlates. The study was an advance on existing research in that seasonality was measured not as a retrospective self‐description of mood variation, but as a prospective pattern of current mood states in winter and summer (across two years). Based on contemporary theorizing about the structure and function of mood, Positive Affect (PA) was the mood construct selected for measurement. A seasonality score was calculated for each participant as the difference between summer mood levels and winter mood levels. The NEO‐FFI was administered at all four waves. Three hundred and three respondents from a random community sample in Melbourne, Australia, provided complete data. Regression analyses found that the adaptive trait Openness to Experience (O) was specifically associated with the tendency towards lowered mood in winter relative to summer. The vulnerability trait Neuroticism (N) was not a directional predictor of winter pattern seasonality, but was the sole predictor of absolute seasonality score. Findings are discussed in terms of two affective processes that may be involved in mood variation across the seasonal time frame: adaptive environmental sensitivity and endogenous mood variability. Copyright © 2002 John Wiley & Sons, Ltd.
Permeation of a solvent mixture through an elastomeric membrane—The case of pervaporation
Authors: Barrière Benoît , Leibler Ludwik
Published: December 2002

This article presents a model for the permeation of solvent mixtures through an elastomer in the particular case of pervaporation. An analytical expression for each solvent permeation rate is derived, in the limited case of a membrane that undergoes small swelling, without making any assumptions on the solvent diffusion coefficients and their dependence on solvent concentrations. Applying this analytical expression to different situations, we fitted most of the curves previously published on pervaporation experiments. In particular, we correlated the synergy developed by a mixture of two solvents in the permeation process with the sign of their Flory–Huggins interaction parameter χAB. This explains why, in most cases (χAB > 0), a molecule permeating easily through a membrane is mixed with a molecule permeating much less easily; the latter can see its permeation flux increase by a factor 10 or 100 because the swelling of the polymer induced by the more permeable molecule “opens the meshes of the network” allowing the less permeable molecule to pass through more easily. Within our analysis, the efficiency of the pervaporation process, expressed through the separation factor, is derived very simply as a function of the interaction coefficients and the viscosities of solvents and exhibits an exponential dependence on the volume fraction of either component as seen in most experiments. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 183–193, 2003
Effect of crystallization and liquid–liquid phase separation on phase‐separation kinetics in poly(ethylene‐co‐vinyl alcohol)/glycerol solution
Authors: Shang Mengxian , Matsuyama Hideto , Maki Taisuke , Teramoto Masaaki , Lioyd Douglas R.
Published: December 2002

Liquid–liquid thermally induced phase separation of the polymer‐diluent system of poly(ethylene‐co‐vinyl alcohol) (EVOH)‐glycerol was examined under light scattering. For EVOH with an ethylene content of 38 mol % (EVOH38), maxima of the scattered light intensity were observed that indicated that phase separation occurred by the spinodal decomposition (SD). The growth of the structures formed by the general liquid–liquid phase separation obeyed a power‐law scaling relationship in SD. For EVOH with an ethylene content of 32 mol % (EVOH32), the liquid–liquid phase separation resulted from the polymer crystallization. In this case, the structure growth showed the characteristic behavior in which the crystalline particles were initially formed, and then the droplets formed by the liquid–liquid phase separation induced by the crystallization grew rapidly. Furthermore, the growth of the droplet by the phase separation was followed by an optical microscope measurement at a constant cooling rate. The phase‐separated structure formed after the crystallization can grow faster than that formed by the normal liquid–liquid phase separation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 194–201, 2003
Atomic force microscopy studies on the dewetting of perfluorinated ionomer thin films
Authors: Hill T. A. , Carroll D. L. , Czerw R. , Martin C. W. , Perahia D.
Published: December 2002

The surface structure and dewetting process of thin films of complex perfluorinated ion‐containing polymers have been studied with atomic force microscopy. These polymers, or ionomers, consist of hydrophilic, hydrophobic, and ionic groups, which are noncompatible with one another, and this results in the association of the polymers into supramolecular structures. These types of polymers have a broad range of technological uses, ranging from thin selective coatings to fuel cells in the form of polymer electrolyte membranes. As the technology calls for thinner films, the interfacial structure and dynamics (wetting/dewetting) of the films become critical in controlling the overall behavior of the polymers. The ionomer under consideration forms structured films consisting of bundles of micelles. These ultrathin films do not dewet above the glass‐transition temperatures of the polymers, contrary to what has been observed in thin diblock copolymers. Perturbing the system with a high‐ionic‐strength solution, however, results in a breakup of the primary aggregate and enhances the adhesion of the films and their stability. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 149–158, 2003
Depression in Men Receiving Androgen Deprivation Therapy for Prostate Cancer: A Pilot Study
Authors: Pirl William F. , Siegel Gabrielle I. , Goode Melissa J. , Smith Matthew R.
Published: December 2002

Purpose: Prostate cancer is the most common malignancy in men and one of the leading causes of cancer death in men internationally. Treatment for prostate cancer frequently includes androgen deprivation therapy (ADT). Reports of depressive symptoms arising during ADT are emerging. This study examines the prevalence rates and risk factors associated with major depression in this population. Method: 45 men with prostate cancer receiving ADT at the MGH Cancer Center were surveyed for depression with the SCID for Axis I disorders for DSM‐IV and the Beck Depression Inventory. Results: Major depressive disorder was prevalent in 12.8% of the men with prostate cancer receiving ADT, eight times the national rate of depression in men, 32 times the rate in men over 65 years old. Major depression was not associated with worsening disease, medical response to ADT, receiving chemotherapy, or the type of ADT. Past history of depression was associated with current depression in this population (p<0.000). No first onset cases of depression occurred on ADT in this sample. Conclusion: This data suggests a significant rate of major depression in men with prostate cancer receiving ADT and that men with past histories of depression may be at particular risk for recurrence of their depression while undergoing this treatment. Copyright © 2002 John Wiley & Sons, Ltd.
Which cancer patient completes a psychosocial intervention program?
Authors: Gilbar Ora , Neuman Ran
Published: December 2002

The present study explored the similarities and differences in patterns of psychological distress, coping strategies and social support of 41 cancer patients who dropped out of a psychosocial therapy program and 20 patients who completed the program as agreed. The findings indicated that only depression, out of nine brief symptom inventory subscales, predicted which patients would complete the program, i.e. patients with a high level of depression tended to complete the psychosocial intervention program. Copyright © 2002 John Wiley & Sons, Ltd.
Breast cancer survivors give voice: a qualitative analysis of spiritual factors in long‐term adjustment
Authors: Lynn Gall Terry , Cornblat Mark W.
Published: December 2002

As part of a cross‐sectional, quantitative study on adjustment factors in long‐term breast cancer survival, 52 women were asked to write in their own words how religious and spiritual factors played a part in their understanding of and coping with this illness. A subsample of 39 women responded to this question. The qualitative method of content analysis was used to define meaning units, descriptive categories and themes from the data. Interpretation of themes in the data focused on the role or function of spiritual/religious factors in long‐term adjustment to breast cancer. The majority of women discussed the positive role of various spiritual resources in their response to the experience of cancer, including relationship with God, religious coping activities (e.g. prayer), meaning and social support. A cognitive model of adjustment was proposed which shows how spiritual resources can help breast cancer survivors make meaning of and experience a sense of life affirmation and personal growth in relation to the cancer. Copyright © 2002 John Wiley & Sons, Ltd.
Cancer survivorship and psychological distress in later life
Authors: Deimling Gary T. , Kahana Boaz , Bowman Karen F. , Schaefer Michael L.
Published: December 2002

Recent research in psychosocial oncology has pointed to the traumatic nature of the stress experienced by cancer survivors. Most of this research has focused on children, young adults survivors and their families. This investigation proposes a conceptual model for understanding general psychological distress (anxiety, hostility and depression) and symptoms of posttraumatic stress (hyper‐arousal, avoidance and intrusiveness) that may be associated with cancer survivorship among older adults. Findings from a survey of 180 older adult, long‐term cancer survivors are used to illustrate the key features of this model. Results of multivariate analysis show that most older adult long‐term cancer survivors do not demonstrate clinical levels of posttraumatic stress disorder (PTSD), although over 25% evidence clinical levels of depression. However, many survivors display important symptoms of psychological distress that are related to the continuing effects of cancer and its treatment. Current cancer‐related symptoms are the strongest predictors of depression (beta=0.27, p=0.046) and the PTSD sub‐dimension of hyper‐arousal (beta=0.377, p=0.004). These effects persist even when the effects of other stressors and non‐cancer illness symptoms are statistically controlled. Additionally, it appears in this sample that symptoms of PTSD are significantly correlated with traditional measures of psychological distress. Copyright © 2002 John Wiley & Sons, Ltd.
Coping and distress among women under treatment for early stage breast cancer: comparing african americans, hispanics and non‐hispanic whites
Authors: Culver Jenifer L. , Arena Patricia L. , Antoni Michael H. , Carver Charles S.
Published: December 2002

This study examined coping and distress in African American (n=8), Hispanic (n=53), and non‐Hispanic White (n=70) women with early stage breast cancer. The participants were studied prospectively across a year beginning at the time of surgery. African American women reported the lowest levels of distress (particularly before surgery) and depression symptoms. Hispanic women reported the highest levels of self‐distraction as a coping response, non‐Hispanic Whites reported the highest use of humor. Hispanics reported the highest levels of venting, African Americans reported the lowest levels. African American and Hispanic women reported more religious coping than non‐Hispanic Whites. The data also provided evidence of a maladaptive spiral of distress and avoidant coping over time. Although some ethnic differences were identified, findings also point to a great many similarities across groups. Copyright © 2002 John Wiley & Sons, Ltd.
Treatment regimen, sexual attractiveness concerns and psychological adjustment among African American breast cancer patients
Authors: Taylor Kathryn L. , Lamdan Ruth M. , Siegel Jamie E. , Shelby Rebecca , Hrywna Mary , Moran‐Klimi Karen
Published: December 2002

Background:Among a sample of African American women recently diagnosed with breast cancer, we assessed the consequences of different treatment regimens on sexual attractiveness concerns, and the impact of sexual attractiveness concerns on current and subsequent psychological adjustment.Patients and Methods: The sample included 91 African American women with breast cancer; 90% had Stage I or II disease, 48% had chemotherapy, 47% had a lumpectomy, and 53% received a mastectomy. Feelings of sexual attractiveness and psychological adjustment were assessed an average of 3 months following surgery and again 4 months post‐baseline.Results: Regression analyses revealed that chemotherapy was associated with greater concerns about sexual attractiveness among lumpectomy patients (p<0.05), but not among mastectomy patients (p>0.20). The interaction also suggested that chemotherapy equalized the impact of types of surgery, as there was no difference on sexual attractiveness between surgery groups among women who had received chemotherapy (p>0.20). However, among women who had not received chemotherapy, mastectomy patients reported greater sexual attractiveness concerns (p<0.01). Finally, regression analyses revealed that feelings of sexual attractiveness were an important component of psychological well‐being, both cross‐sectionally (p<0.001) and longitudinally (p<0.001).Conclusion: Assessment of the combined impact of different treatment regimens on feelings of sexual attractiveness is particularly important given the current consensus that all breast cancer patients should receive chemotherapy, regardless of nodal status. Further, concerns about sexual attractiveness should be considered for inclusion as one component of psychosocial support programs for African American women with breast cancer, as our results suggested that they played a significant role in psychological adjustment. Copyright © 2002 John Wiley & Sons, Ltd.
Variation of pesticide sorption isotherm in soil at the catchment scale
Authors: Coquet Yves
Published: December 2002

The variation of the sorption isotherm of pesticides has seldom been explored at the catchment scale. Such a study was conducted at the scale of a 187‐ha agricultural catchment for three herbicides: atrazine, isoproturon and metamitron. Partition coefficient (Kd) values were measured in batch experiments on 51 topsoil samples, and showed moderate variability at the catchment scale (coefficient of variation CV ∼ 30%). Values of Kd ranged from 0.47 to 1.70 litre kg−1 for atrazine, 0.47 to 1.81 for isoproturon, and 0.55 to 2.21 for metamitron. A clustering method was used to reduce the number of samples on which to measure sorption isotherms to 14. Sorption isotherms agreed with the Freundlich rather than the linear model. Kf parameters had CV values similar to those for Kd, with values ranging from 0.78 to 2.13 mg litre kg−1 for atrazine, 0.61 to 1.82 for isoproturon, and 0.69 and 2.58 for metamitron. Nf exponents showed little variation (CV < 5%). Nf values were between 0.86 and 0.98 for atrazine, 0.85 and 0.90 for isoproturon, and 0.82 and 0.87 for metamitron. More than 97% of the Kf catchment‐scale variations could be explained by the variations of the soil organic carbon content.

© 2002 Society of Chemical Industry
Synthesis and insecticidal activity of benzoheterocyclic analogues of N′‐benzoyl‐N‐(tert‐butyl)benzohydrazide: Part 1. Design of benzoheterocyclic analogues
Authors: Sawada Yoshihiro , Yanai Toshiaki , Nakagawa Harumi , Tsukamoto Yoshihisa , Yokoi Shinji , Yanagi Mikio , Toya Tetsuya , Sugizaki Hiroyasu , Kato Yasuhito , Shirakura Hidetoshi , Watanabe Tetsuo , Yajima Yoshimi , Kodama Seiichirou , Masui Akio
Published: December 2002

The N′‐benzoyl group of N‐tert‐butyl‐N′‐benzoyl‐3,5‐dimethylbenzohydrazide (1) was converted to a series of benzoheterocyclecarbonyl groups in order to investigate the potential usefulness of superimposing a hydrazine insecticide on 20‐hydroxyecdysone. A series of analogues with benzodioxole, benzodioxane, benzodioxapine, indole, benzoxazole, benzoxazine or benzothiazole instead of the phenyl group of (1) were synthesized and tested for their insecticidal activity against the common cutworm (Spodoptera litura F). N‐tert‐Butyl‐N′‐(3,5‐dimethylbenzoyl)‐1,3‐benzodioxole‐5‐carbohydrazide and N‐tert‐butyl‐N′‐(3,5‐dimethylbenzoyl)‐2,3‐dihydro‐1,4‐benzodioxine‐6‐carbohydrazide showed high insecticidal activities, superior to that of (1) and equal to that of the commercial insecticide tebufenozide (RH‐5992).

© 2002 Society of Chemical Industry
Synthesis and insecticidal activity of benzoheterocyclic analogues of N′‐benzoyl‐N‐(tert‐butyl)benzohydrazide: Part 3. Modification of N‐tert‐butylhydrazine moiety
Authors: Sawada Yoshihiro , Yanai Toshiaki , Nakagawa Harumi , Tsukamoto Yoshihisa , Tamagawa Yasushi , Yokoi Shinji , Yanagi Mikio , Toya Tetsuya , Sugizaki Hiroyasu , Kato Yasuhito , Shirakura Hidetoshi , Watanabe Tetsuo , Yajima Yoshimi , Kodama Seiichirou , Masui Akio
Published: December 2002

Nineteen analogues were synthesized by modifying the tert‐butylhydrazine moieties of N′‐tert‐butyl‐N′‐(3,5‐dimethylbenzoyl)‐5‐methyl‐2,3‐dihydro‐1,4‐benzodioxine‐6‐carbohydrazide and N′‐tert‐butyl‐N′‐(3,5‐dimethylbenzoyl)‐5‐methylchromane‐6‐carbohydrazide (chromafenozide), and the synthesized analogues were evaluated for their insecticidal activity against Spodoptera litura F. While all of the synthesized analogues had insecticidal activity inferior to those of the lead compounds, several of the analogues nonetheless showed high insecticidal activity. Chromafenozide has shown very high selectivity toward lepidopteran species.

© 2002 Society of Chemical Industry
Movement of pendimethalin, ioxynil and soil particles to field drainage tiles
Authors: Petersen Carsten T , Holm Jesper , Koch Christian B , Jensen Henry E , Hansen Søren
Published: December 2002

Knowledge of the movement of herbicides and soil particles to sub‐surface tile drainage may help to predict chemical leaching to surface waters and deeper groundwater systems. The movement of pendimethalin (2 years), ioxynil (1 year) and soil particles (3 years) to two tile drains was investigated on a sandy loam soil under natural weather conditions. Herbicide and particle concentrations in the drain water showed a very dynamic pattern. The largest herbicide concentrations were detected during the first tile drain flow events after application. Very little herbicide was lost with drain water later than 2 months after application. The turbidity, reflecting concentrations of soil particles, correlated positively and strongly with the pendimethalin concentration and negatively with the rate of drain water discharge, whereas it was uncorrelated with the ioxynil concentration. Peak turbidity values occurred during or shortly after rainfall events, either in break of frost situations, or on unfrozen soil coinciding with the occurrence of peak moisture contents in the topsoil well (3–7%) above field capacity. On average, 0.0013% of the applied pendimethalin and 0.0015% of the applied ioxynil were lost with drain water. The results suggest that preferential flow promotes the movement of all three substances to the tile drains but indicate somewhat different transport mechanisms for the two herbicides.

© 2002 Society of Chemical Industry
Dissipation of the herbicide dithiopyr in soil and residues in wheat (Triticum aestivum L) grain under Indian tropical conditions
Authors: Saikia Nirmali , Kulshrestha Gita
Published: December 2002

Dissipation of dithiopyr in soil was monitored after application to wheat crop as pre‐ or post‐ emergence applications at two rates, viz 100 and 200 g AI ha−1. The level of dithiopyr in the soil was assessed by gas chromatography, and its disappearence was found to follow a first‐order decay curve irrespective of rate or method of application. The half‐life in soil ranged between 17.3 and 25.0 days and residues at harvest (150 days after application) ranged between 4.0 and 8.8% of amounts applied. Investigation of microbial degradation of dithiopyr was conducted in minimal salt and Czapek Dox media in which 80% of the compound degraded within 15 days. Residues were not detected in wheat grain at harvest.

© 2002 Society of Chemical Industry
Derivatization procedures for the detection of estrogenic chemicals by gas chromatography/mass spectrometry
Authors: Ding Wang‐Hsien , Chiang Cheng‐Che
Published: December 2002

This work evaluated derivatization procedures for detecting both natural and synthetic estrogenic chemicals by gas chromatography/mass spectrometry (GC/MS). Different silylating agents, mainly trimethylsilylating (TMS) agents, were compared, and the roles of various content of trimethylchlorosilane (TMCS, as a stimulator) were investigated. The difference in the abundances of the derivatives was caused by the steric hindrance of multiple hydroxyl groups and ethynyl groups in the structures of estrogenic chemicals. The use of TMCS produces an increase in the derivatization yield, especially for the compounds with multiple hydroxyl groups (i.e., 17β‐estradiol (E2) and estriol (E3)). Mass spectra of O‐TMS derivatives and tentative fragmentation profiles are proposed. Molecular ions were the base peaks for all the derivatives, and were used as the quantitation ions to obtain maximum detection sensitivity and specificity. Sample enrichment was achieved by Oasis® HLB solid‐phase extraction cartridges. The quantitation limits of these compounds ranged from 5 to 10 ng/L in 1000‐mL water samples. Recovery of the estrogenic chemicals in spiked various water samples ranged from 78 to 102% while relative standard deviation (RSD) ranged from 1 to 15%. Copyright © 2002 John Wiley & Sons, Ltd.
Evaluation of protocols for reproducible electrospray in‐source collisionally induced dissociation on various liquid chromatography/mass spectrometry instruments and the development of spectral libraries
Authors: Bristow Anthony W. T. , Nichols William F. , Webb Kenneth S. , Conway Brian
Published: December 2002

Mass spectral libraries provide a tool for identifying unknown compounds using both molecular weight and fragmentation information. Mass spectrometers with electrospray ionisation (ESI) and atmospheric chemical ionisation (ApCI) sources have the capability to produce data of this type using in‐source collisionally induced dissociation (CID), and in‐source CID libraries can be created. Due to the variation in electrospray source design from different instrument manufacturers, the production of reproducible in‐source CID spectra that can be used in libraries for all instrument types is not a trivial task. To date, the evaluation of the production of in‐source CID libraries has tended to focus on similar instruments from one manufacturer. The studies have also tended to focus on specific compound classes, with a limited molecular weight range.

This report describes the findings from the investigation of protocols for the creation of mass spectral libraries using ESI in‐source CID on six instruments from four different manufacturers. The overall goal was to create a spectral library for the identification of unknowns. The library could then be applied across all manufacturers' electrospray instruments.

Two different experimental protocols were attempted. The first used a tuning compound to establish standard ESI source conditions, with fixed fragmentation potentials. The second involved the attenuation of the [M + H]+ ion to a known degree. A diverse range of compounds (pharmaceutical, photographic, pesticides) was tested to establish the reproducibility of the spectra on the six instruments. Both protocols produced spectra on the various instruments that in many cases were very similar. In other examples, the spectra differed not only in their relative ion abundances, but also in terms of the spectral content. Important observations regarding the effect of ion source design are also reported.

The degree of spectral reproducibility was calculated off‐line by comparing the five most abundant ions (20% for each ion that matches) from each spectrum on each instrument. This approach was adopted, as we do not possess a software package that met our requirements for spectral comparison. Match factors (% fit) were calculated by comparing each spectrum against the spectra recorded for the same compound and then for all other compounds, on each instrument. The % fit values derived by the off‐line approach gave a clear view of the spectral reproducibility from instrument to instrument and also discriminated the spectra of the various compounds from each other. The applicability of this approach was tested using a blind trial in which several compounds were presented as unknowns, their in‐source CID spectra recorded and the five‐ion approach used for identification. Copyright © 2002 John Wiley & Sons, Ltd.
Different electrospray tandem mass spectrometric approaches for rapid characterization of phospholipid classes of Curosurf®, a natural pulmonary surfactant
Authors: Pelizzi Nicola , Catinella Silvia , Barboso Silvia , Zanol Margherita
Published: December 2002

Curosurf® is a pulmonary surfactant used in the treatment or prophylaxis of neonatal respiratory distress syndrome. It contains low molecular weight hydrophobic apoproteins and a series of lipids including phosphatidylcholines, lisophosphatidylcholines, phosphatidylethanolamines, sphingomyelins, phosphatidylinositols, phosphatidylglycerols and phosphatidylserines. In the present work, a rapid method to qualitatively map the Curosurf® phospholipid classes without prior derivatization or chromatographic separations is described. In particular, a series of specific electrospray tandem mass spectrometric (ES‐MS/MS) experiments, i.e. product ion, precursor ion and neutral loss scans, were chosen on the basis of the chemical nature of each phospholipid class and then used to identify single components of the commercial suspension, directly infused into the ion source of the mass spectrometer. Copyright © 2002 John Wiley & Sons, Ltd.
Determination of non‐steroidal estrogens in breast milk, plasma, urine and hair by gas chromatography/mass spectrometry
Authors: Choi Man Ho , Kim Kyoung‐Rae , Hong Jong Ki , Park Song Ja , Chung Bong Chul
Published: December 2002

It is suspected that all the natural estrogens occurring in the human body, as well as dietary and synthetic estrogens, diversely affect the endocrine system depending on their exposure patterns. More rapid, reliable and accurate measurements of these compounds in various biological matrices are thus becoming an important task. After solid‐phase extraction using an Oasis HLB extraction cartridge, the estrogen concentrates were derivatized with a mixture of N‐methyl‐N‐trifluorotrimethylsilylacetamide/ammonium iodide/dithioerythritol (1000:4:5, v/w/w) for analysis by gas chromatography/mass spectrometry in the selected ion‐monitoring (SIM) mode. The qualitative identification of estrogens detected in SIM mode was further confirmed by tandem mass spectrometry using low‐energy collision‐induced dissociation (CID) mode. The method for the assay of the 20 estrogens was linear over the ranges of 1–1000 µg/L for biological fluids and 1–200 µg/kg for hair with high correlation coefficient (>0.99). The limits of quantitation (LOQ) ranged from 1.0–10 µg/L (or µg/kg) and the limit of detection ranged from 0.2–3 µg/L (or µg/kg). The average precision (% CV) and accuracy (% bias) of the method determined at the LOQ, low, and medium concentrations were in the ranges 2.6–9.2 and −4.1–7.7, respectively. The average extraction recovery of the estrogens from plasma and hair at the three concentration levels varied in the ranges 77–103% (1.9–14.3% CV) and 73–104% (3.1–14%), respectively. The distribution patterns of the estrogens were characteristic of each biosample. Five estrogens in the range 1.5–44.9 µg/L were measured in breast milk, 8 estrogens in the range 3.5–322 µg/L in plasma, 12 estrogens at 1.2–442 µg/L in urine, and biochanin‐A at 13.2–39.1 µg/kg in hair. Because of its high sensitivity, good precision and specificity, the present method was found suitable for the trace analysis of dietary and synthetic estrogens in complex biosamples such as breast milk, plasma, urine and hair. Copyright © 2002 John Wiley & Sons, Ltd.
Electron capture dissociation of weakly bound polypeptide polycationic complexes
Authors: Haselmann Kim F. , Jørgensen Thomas J. D. , Budnik Bogdan A. , Jensen Frank , Zubarev Roman A.
Published: December 2002

We have previously reported that, in electron capture dissociation (ECD), rupture of strong intramolecular bonds in weakly bound supramolecular aggregates can proceed without dissociation of weak intermolecular bonds. This is now illustrated on a series of non‐specific peptide‐peptide dimers as well as specific complexes of modified glycopeptide antibiotics with their target peptide. The weak nature of bonding is substantiated by blackbody infrared dissociation, low‐energy collisional excitation and force‐field simulations. The results are consistent with a non‐ergodic ECD cleavage mechanism. Copyright © 2002 John Wiley & Sons, Ltd.
Electrospray ionization mass spectra of monoimidazole/polyamine conjugates
Authors: Zhu Changjin , Jiang Yanfeng , Yang Xiaoli , Zhao Yufen
Published: December 2002

Imidazole/polyamine amides are biologically important molecules due to their specific DNA binding activity, and much attention has been attracted to the synthesis of their derivatives or analogues. In the present studies, the fragmentation of a series of synthetic monoimidazole/polyamine amides was investigated using electrospray ionization mass spectrometry (ESI‐MS) combined with tandem mass spectrometry (ESI‐MS/MS). All of the monoimidazole/polyamine amides produced the fragment ion m/z 183 except for the monoimidazole/ethyldiamine amide. The diamine amides produced this ion after the elimination of an alkene, the triamine amides produced it via their corresponding diamine amide fragments, and the tetraamine amide via its triamine and then diamine amide fragments. The characterization of the mass spectra for the different polyamine amides allowed identification of a specific product from the N‐acylation of spermidine, and should assist further study of the polyamine amides in DNA binding action. Copyright © 2002 John Wiley & Sons, Ltd.
Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry of lipids: ionization and prompt fragmentation patterns
Authors: Al‐Saad Khalid A. , Zabrouskov Vladimir , Siems William F. , Knowles N. Richard , Hannan Richard M. , Hill Herbert H.
Published: December 2002

Ionization and prompt fragmentation patterns of triacylglycerols, phospholipids (PLs) and galactolipids were investigated using matrix‐assisted laser desorption/ionization (MALDI). Positive ions of non‐nitrogen‐containing lipids appeared only in the sodiated form, while nitrogen‐containing lipids were detected as both sodiated and protonated adducts. Lipids containing acidic hydroxyls were detected as multiple sodium adducts or deprotonated ions in the positive and negative modes, respectively, with the exception of phosphatidylcholines. The positive MALDI spectra of triacylglycerols contained prompt fragments equivalent to the loss of RCOO− from the neutral molecules. Prompt fragment ions [PL–polar head]+ were observed in the positive MALDI spectra of all phospholipids except phosphatidylcholines. The phosphatidylcholines produced only a minor positive fragment corresponding to the head group itself (m/z 184). Galactolipids did not undergo prompt fragmentation. Post‐source decay (PSD) was used to examine the source of prompt fragments. PSD fragment patterns indicated that the lipid prompt fragment ions did not originate from the observed molecular ions (sodiated or protonated), and suggested that the prompt fragmentation followed the formation of highly unstable, probably protonated, precursor ions. Pathways leading to the formation of prompt fragment ions are proposed. Copyright © 2002 John Wiley & Sons, Ltd.
Mammalian reovirus core protein µ2 initiates at the first start codon and is acetylated
Authors: Swanson Magdalena I. , She Yi‐Min , Ens Werner , Brown Earl G. , Coombs Kevin M.
Published: December 2002

Mammalian reovirus is an enteric virus that contains a double‐stranded RNA genome. The genome consists of ten RNA segments that encode eight structural and three non‐structural proteins. The structural proteins form a double‐layered structure. The innermost layer, called the core, consists of five proteins (λ1, λ2, λ3, µ2, and σ2). Protein λ3 is the RNA‐dependent RNA polymerase (RdRp) and µ2 is thought to be an RdRp cofactor. Translation of most reovirus proteins is known to commence at the first start codon. However, the translation initiation site of the viral core protein µ2, encoded by the M1 RNA segment, has been in dispute. Although the theoretical molecular weight of µ2 is 83 267 Da the actual molecular weight is unknown because µ2 runs aberrantly in SDS‐PAGE and has resisted characterization by Edman degradation, indicating that the amino terminus is post‐translationally modified. In this study, we used proteolysis coupled with MALDI‐Qq‐TOFMS to determine that translation of µ2 initiates at the first AUG codon, that its actual molecular weight approximates the theoretical value of 83 kDa, that the amino terminal methionine residue is removed, and that the next amino acid (alanine) is post‐translationally acetylated. Copyright © 2002 John Wiley & Sons, Ltd.
Solid‐phase microextraction liquid chromatography/tandem mass spectrometry for the analysis of chlorophenols in environmental samples
Authors: Sarrión M. N. , Santos F. J. , Moyano E. , Galceran M. T.
Published: December 2002

Liquid chromatography with atmospheric pressure chemical ionisation mass spectrometry (LC/APCI‐MS), using negative ion detection in a triple quadrupole instrument, was used for the determination of chlorophenols (CPs) in environmental samples. In‐source collision‐induced dissociation (CID) was compared with MS/MS fragmentation. In general, less fragmentation was observed in MS/MS as compared with in‐source CID, with the latter providing more intense fragment ions due to chemical ionisation. Under MS/MS conditions [M − H − HCl]− was the main fragment ion observed for all compounds except for pentachlorophenol, which showed no fragmentation. For multiple reaction monitoring (MRM) acquisition mode, the transition from [M − H]− to [M − H − HCl]− was selected, leading to detection limits down to 0.3 ng injected. Direct and headspace‐solid‐phase microextraction (HS‐SPME) were used as preconcentration procedures for the analysis of CPs in wood and in industrially contaminated soils. CPs were quantified by standard addition, which led to good reproducibility (RSD between 4 and 11%) in both SIM and MRM modes, and detection limits down to ng/g. The combination of MS/MS and in‐source CID allowed confirmation of the presence of CPs in environmental samples. Copyright © 2002 John Wiley & Sons, Ltd.
Structural characterization of chromone C‐glucosides in a toxic herbal remedy
Authors: Wang Wu , Cuyckens Filip , Van den Heuvel Hilde , Apers Sandra , Pieters Luc , Steenkamp Vanessa , Stewart Michael J. , Luyckx Valerie A. , Claeys Magda
Published: December 2002

Two novel compounds, 8‐C‐D‐glucopyranosyl‐7‐hydroxy‐5‐methylchromone‐2‐carboxylic acid and a 2‐O′‐p‐coumaroyl derivative thereof, were identified in a herbal tea that caused severe vomiting in a South African patient who had taken the traditional remedy to clean his stomach. For structural characterization, electrospray (ES) ionization in combination with collision‐induced dissociation (CID) and tandem mass spectrometry (MS/MS) were used, as well as UV and nuclear magnetic resonance (NMR) spectroscopy. Specific ions or neutral losses generated under conditions of ES‐MS/CID/MS permitted the establishment of structural features such as the free carboxyl group, the C‐hexosidic part and the p‐coumaroyl group. NMR spectroscopy was necessary to support the structure of the chromone‐type aglycone and the glucosidic parts. Since the compounds are structurally related to aloesin and aloeresin A, which are chemotaxonomic markers of Aloe species, and have not been previously reported, we propose that they were formed by oxidative degradation during preparation of the herbal tea from an Aloe species or during its storage. Copyright © 2002 John Wiley & Sons, Ltd.
Investigation of matrix effects in bioanalytical high‐performance liquid chromatography/tandem mass spectrometric assays: application to drug discovery
Authors: Mei Hong , Hsieh Yunsheng , Nardo Cymbylene , Xu Xiaoying , Wang Shiyong , Ng Kwokei , Korfmacher Walter A.
Published: December 2002

A series of studies was performed to investigate some of the causes for matrix effects (‘ion suppression’ or ‘ion enhancement’) in bioanalytical high‐performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) assays. Previous studies have reported that matrix effects are mainly due to endogenous components in biological fluids and are a greater concern for electrospray ionization (ESI) than for atmospheric pressure chemical ionization (APCI). In this report we demonstrate that: (1) matrix effects can also be caused by exogenous materials, such as polymers contained in different brands of plastic tubes, or Li‐heparin, a commonly used anticoagulant; (2) matrix effects are not only ionization mode (APCI or ESI) dependent, but also source design (Sciex, Finnigan, Micromass) dependent; and (3) for at least one vendor's design, we found the APCI mode to be more sensitive to matrix effects than the ESI mode. Based on these findings, we have proposed the following simple strategies to avoid matrix effects: (1) select the same brand of plastic tubes for processing and storing plasma samples and spiked plasma standards; (2) avoid using Li‐heparin as the anticoagulant; and (3) try switching the ionization mode or switching to different mass spectrometers when matrix effects are encountered. These three strategies have allowed us to use protein precipitation and generic fast LC techniques to generate reliable LC/MS/MS data for the support of pharmacokinetic studies at the early drug discovery stage. Copyright © 2002 John Wiley & Sons, Ltd.
The unanticipated loss of SO2 from sulfonamides in collision‐induced dissociation
Authors: Wang Zhen , Hop Cornelis E. C. A. , Kim Mi‐Sook , Huskey Su‐E. W. , Baillie Thomas A. , Guan Ziqiang
Published: December 2002

A potent and selective sulfonamide β3 agonist with an excellent pharmacokinetic profile has recently been synthesized. During the analysis by liquid chromatography/tandem mass spectrometry (LC/MS/MS) of metabolites of the sulfonamide N‐{4‐[2‐(2‐hydroxy‐2‐pyridin‐3‐ylethylamino)ethyl]phenyl}‐4‐[4‐(4‐trifluoromethylphenyl)thiazol‐2‐yl]benzulfonamide (compound A), we observed loss of 64 Da for a few of the metabolites in the negative ion mode. Accurate mass measurements performed with Fourier transform ion cyclotron resonance (FTICR) mass spectrometry and quadrupole time‐of‐flight (Q‐TOF) mass spectrometry suggested that the loss of 64 Da corresponded to the loss of SO2. The same phenomenon was observed for a group of structurally related and commercially available compounds that also contain a sulfonamide moiety. MS/MS analysis of the fragment ions that had lost SO2 in the ion source suggested that these ions were covalently bound rather than ion‐molecule complexes. The neutral loss involving the cleavage of two bonds was unanticipated and suggested a complex rearrangement process. A mechanism for the loss of SO2 has been proposed. Copyright © 2002 John Wiley & Sons, Ltd.
An Adaptive Controller for Two Cooperating Flexible Manipulators
Authors: Damaren Christopher J.
Published: December 2002

The control problem for two serial flexible multilink robots which carry
a common rigid payload is considered. An adaptive controller with feedback
and feedforward elements is presented which can track a prescribed trajectory
for the payload with simultaneous vibration suppression when the manipulated
payload is sufficiently large. A free load‐sharing parameter appears in the
passivity‐based control law which allows the torque requirement to be shared
between the two arms in a largely arbitrary fashion. Simulation results using
a complex model are given which demonstrate excellent tracking performance
in the face of complete payload uncertainty. © 2003 Wiley Periodicals,
Inc.
Progression of the stacked Golgi compartments in the yeast Saccharomyces cerevisiae by overproduction of GDP–mannose transporter
Authors: Hashimoto Hitoshi , Abe Masato , Hirata Aiko , Noda Yoichi , Adachi Hiroyuki , Yoda Koji
Published: December 2002

The Golgi compartments of the yeast Saccharomyces cerevisiaeare dispersed within the cytoplasm, in contrast to the stacked cisternae in the mammalian cell, and consequently are observed as a punctate pattern by immunofluorescent staining of Golgi‐marker proteins. The VIG4/VRG4 gene encodes the essential yeast GDP–mannose transporter, which is a polytopic membrane protein in the early and medial Golgi compartments. Upon overexpression of this gene by the aid of a strong promoter and multicopy vector, we found that stacked multivesicular structures, which resembled the cisternae of mammalian Golgi apparatus, had developed in S. cerevisiae. Immuno‐electron microscopy showed that the GDP–mannose transporter was located on the stacked cisternae. Immuno‐isolation and immunoblotting analyses of the vesicles showed that the overproduced GDP–mannose transporter also co‐localized with the Golgi glycosyltransferases, but not with the ER‐ or late Golgi‐marker proteins as in the control cell. We propose that the localization mechanism of the GDP–mannose transporter in the Golgi compartment would be efficient and hardly saturable, and therefore the overproduced protein induced a progression of Golgi‐like compartments rather than being mislocalized in other compartments, such as the ER or a vacuole. Copyright © 2002 John Wiley & Sons, Ltd.
Cloning, sequencing and characterization of a gene encoding dihydroxyacetone kinase from Zygosaccharomyces rouxii NRRL2547
Authors: Wang Zheng‐Xiang , Kayingo Gerald , Blomberg Anders , Prior Bernard A.
Published: December 2002

The dihydroxyacetone pathway, an alternative pathway for the dissimilation of glycerol via reduction by glycerol dehydrogenase and subsequent phosphorylation by dihydroxyacetone (DHA) kinase, is activated in the yeasts Saccharomyces cerevisiae and Zygosaccharomyces rouxii during osmotic stress. In experiments aimed at investigating the physiological function of the DHA pathway in Z. rouxii, a typical osmotolerant yeast, we cloned and characterized a DAK gene encoding dihydroxyacetone kinase from Z. rouxii NRRL 2547. Sequence analysis revealed a 1761 bp open reading frame, encoding a peptide composed of 587 deduced amino acids with the predicted molecular weight of 61 664 Da. As the amino acid sequence was most closely homologous (68% identity) to the S. cerevisiae Dak1p, we named the gene and protein ZrDAK1 and ZrDak1p, respectively. A putative ATP binding site was also found but no consensus element associated with osmoregulation was found in the upstream region of the ZrDAK1 gene. The ZrDAK1 gene complemented a S. cerevisiae W303‐1A dak1Δdak2Δ strain by improving the growth of the mutant on 50 mmol/l dihydroxyacetone and by increasing the tolerance to dihydroxyacetone in a medium containing 5% sodium chloride, suggesting that it is a functional homologue of the S. cerevisiae DAK1. However, expression of the ZrDAK1 gene in the S. cerevisiae dak1Δdak2Δ strain had no significant effect on glycerol levels during osmotic stress. The ZrDAK1 sequence has been deposited in the public data bases under Accession No. AJ294719; regions upstream and downstream of ZrDAK1are deposited as Accession Nos AJ294739 and AJ294720, respectively. Copyright © 2002 John Wiley & Sons, Ltd.
Editorial Foreword
Authors: Trautmann Thomas R.
Published: December 2002

RACE AND SOCIAL MOBILITY Racial discrimination is an impediment to upward social mobility, but it is not always easy to measure its effects in relation to competing factors. The first essay argues for the importance of history in making this determination.