bluuebunny/crossref_metadata_2025 huggingface dataset:
A comparison of face-to-face and videoconference administration of the Hamilton Depression Rating Scale
Authors: Kobak Kenneth A
Published: July 2004

To determine whether the mode of administration affected the psychometric properties of the Hamilton Depression Rating Scale (HAMD), 21 subjects with an affective disorder were administered two HAMD interviews on the same day, once via videoconference (at 384 kbit/s) and once face-to-face, by two independent interviewers. The interviewers were blind to the results of the other interview. The mean HAMD scores were almost identical (18.4 for videoconferencing and 18.2 for face to face). The intra-class correlation between the two sets of scores was 0.88. When another group of 21 subjects had the HAMD administered in two face-to-face interviews on the same day, the inter-rater reliability was not significantly different from that for the videoconference cohort. Most patients (91%) thought videoconferencing was a useful way to receive a psychological evaluation when other means were unavailable or limited. The study shows the psychometric equivalence of remote and face-to-face HAMD administration.
Health professionals' responses to the introduction of a home telehealth service
Authors: Hibbert Derek , Mair Frances S , May Carl R , Boland Angela , O'Connor Jane , Capewell Simon , Angus Robert M
Published: July 2004

An ethnographic (participant observation) study was undertaken of the socio-technical processes involved in the implementation, within a randomized controlled trial, of a home telehealth nursing service for patients with chronic obstructive pulmonary disease (COPD). Ethnographic field notes were taken about technology-related tasks and the interplay between the research team and the 12 nurses who were to use the telehealth equipment. Views of the technology were linked to views of professional self-image and status. The technology was sometimes seen as unhelpful in establishing effective relationships with patients. Considerable work by all participants, over a period of months, was required to develop the technology in ways that minimized the risk to the stability of the specialist service and existing nurse–patient relationships. Our work highlights the complex problems that health professionals encounter when they try to integrate new technologies into routine service delivery. The concerns arising from the interplay of new technology with existing professional practices and relationships go beyond simple issues of training.
Comparison of an auto-stereoscopic display and polarized stereoscopic projection for macroscopic pathology
Authors: Hutarew Georg , Moser Karin , Dietze Otto
Published: July 2004

We investigated stereoscopic imaging for gross examination in telepathology. A conventional macroscopic station was equipped with two cameras mounted 6.5 cm apart and images were produced of 30 different routine pathology specimens. Still images were displayed on a three-dimensional auto-stereoscopic display with a lenticular plate (which did not require the viewer to wear special glasses) and as a three-dimensional projection that required the viewer to wear glasses with polarized lenses. Nine observers (pathologists, laboratory technicians and engineers) viewed the three-dimensional images first on the auto-stereoscopic display and then with polarized projection. The observers scored the images for spatial reproduction, surface structure, proportions, colour and sharpness (10 indices in total, each rated on a five-point Likert scale of 1–5, with lower scores indicating better quality). Results were compared with those from five observers who had previously viewed the corresponding two-dimensional images on a conventional (two-dimensional) display. The mean scores across each of the 10 indices were 2.9 (two-dimensional display), 2.1 (auto-stereoscopic display) and 1.6 (polarized projection). All observers stated that the polarized projection had superior image quality with regard to resolution, colour and surface structures. The results obtained in the present study with still images have encouraged us to integrate stereoscopy into a dynamic telepathology system.
A study of a rural telemedicine system in the Amazon region of Peru
Authors: Martínez Andrés , Villarroel Valentín , Seoane Joaquín , del Pozo Francisco
Published: July 2004

Voice and data communication facilities (email via VHF radio) were installed in 39 previously isolated health facilities in the province of Alto Amazonas in Peru. A baseline study was carried out in January 2001 and a follow-up evaluation in May 2002, after nine months of operation. We measured the reliability of the technology and the effect the system had on staff access to medical training and information. We also measured the indirect effects on the general population of access to better health-care. The experimental data were collected from 35 of the 39 sites in face-to-face questionnaire interviews. Before installation of the system, the mean consultation rate was 3 per month per facility (95% CI 1.5 to 4.5). At the end of the study, the mean consultation rate was 23 per month per facility (95% CI 14.7 to 31.5). There were 205 emergency transfers from the 39 health facilities. The system was employed in all these cases to alert the referral centre. The mean time required for evacuation was reduced from 8.6 h to 5.2 h. Health-care personnel reported that in 58 of the emergency cases (28%) the use of the system saved the life of the patient. The study shows that the use of communication technologies appropriate to local needs solves many problems in rural primary care, and that voice and email communication via VHF radio are feasible and useful for rural telemedicine.
Videoconferencing in child and adolescent telepsychiatry: a systematic review of the literature
Authors: Pesämaa Lilli , Ebeling Hanna , Kuusimäki Marja-Leena , Winblad Ilkka , Isohanni Matti , Moilanen Irma
Published: July 2004

A systematic review of child and adolescent telepsychiatry was conducted. It was based on a search of the electronic databases MEDLINE and PsycINFO covering the period 1966 to June 2003. Studies were selected for review if they concerned videoconferencing for patient care or consultation, evaluated a clinical service or education, or assessed satisfaction with videoconferences. Twenty-seven articles were identified that fulfilled the selection criteria. These comprised two reports of randomized controlled experiments, 10 of descriptive questionnaire studies or observational surveys, seven case studies and eight other reports. Only three of the studies presented some calculations of cost-effectiveness. When classified by 'Quality of Evidence' criteria, only two studies were in category I (the highest), one was in II-2 and the rest fell into category III (the lowest). Most studies of child and adolescent telepsychiatry examined satisfaction with videoconferencing or described programmes or care regimens. Videoconferencing seemed to improve the accessibility of services and served an educational function. Some papers also mentioned savings in time, costs and travel. Problems with non-verbal communication and the audiovisual quality of the videoconference were mentioned as drawbacks. Telepsychiatry therefore seems to offer several benefits, at least in sparsely populated regions. Well designed and properly controlled trials are required to evaluate the clinical value of this promising method in child psychiatry, where there is a constantly increasing need for services.
EXPLAINING MENTAL ILLNESS
Authors: GOLDMAN E.
Published: July 2004

Like late-eighteenth- and early-nineteenth-century doctors such as Benjamin Rush and Amariah Brigham, Nathaniel Hawthorne recognized the pathogenic potential of excessive religious zeal. In much of his short fiction Hawthorne offers a medical perspective of characters who obsessively find sin either in themselves or others. Yet he was skeptical about a new medical perspective of the human mind that potentially obscured the moral symbolism, or what he referred to as the “moral signification,” of apparent mental illness. In his short fiction Hawthorne thus tries to resolve an implicit dialogue between medical and theological views of the mind by fusing the Puritan sensitivity to symbol and moral signification with a keen medical awareness of the dangers of religious enthusiasm and unhealthy obsession with discovering moral signification. His mode of narration “saneitizes” the insane search for moral signification exemplified by characters such as Ethan Brand, Roderick Elliston, and the Minister Hooper.
READING THE RINSINGS OF THE CUP
Authors: MACHOR J. L.
Published: July 2004

Although a widely shared critical perception is that Herman Melville's first two books, Typee (1846) and Omoo (1847), received comparable responses from reviewers in the late 1840s, the antebellum reception of the second novel was anything but a mirror of the response to the first. Not only did Omoo sell fewer copies and receive fifty fewer reviews than Typee, but reviewers also read Omoo through an altered set of interpretive assumptions that turned it, in their view, into a problematic and ultimately disappointing sequel. Part of this shift involved a marked increase in objections to Melville's critique in Omoo of Christian missionaries. A major factor in this response was that reviewers, after having struggled with the question of Typee's authenticity, were inclined to take Omoo as a prima facie work of fiction. Such an assumption meant that, in the logic of antebellum reading formations, Omoo's credibility as social critique was suspect by virtue of its fictional status. This impugning of the novel's authority, in turn, helped pave the way for reviewer responses that questioned the author's own morality. Adding to the problem was the fact that several key reviewers found Omoo to be disappointing because it failed to mark an advance on Typee. Such turns in audience response were significant in repositioning Melville in the antebellum literary marketplace, not only in terms of the public perception of his writings but also in the way in which he conceived his relation to his audience with his next novel, Mardi (1849).
ARTFUL TALES OF ORIGINATION IN OLIVE SCHREINER'S THE STORY OF AN AFRICAN FARM
Authors: SHAPPLE D. L.
Published: July 2004

Olive Schreiner's The Story of an African Farm (1883) has long been considered an anticolonial novel that nevertheless, because of its author's affiliation with a European colonial culture, neglects to investigate the problem of disenfranchised African labor in significant detail. In this essay I reassess Schreiner's anticolonialism by placing it in the context of her growing postcolonial aspirations. This rather paradoxical position of the colonist becoming a postcolonial manifests itself in the novel's central artist figure, Waldo, who, while descended from European colonists, manages to make himself at home in his South African environment. Employing nineteenth-century ethnological and aesthetic discourses in the construction of this curious figure (which I refer to as the colonial indigene), Schreiner establishes a connection among the novel, colonial art, and an indigenous South African culture. The novel's narrative present is set during a period of intense border struggle, and while indigenous artists like the San known to the colonists as the Bushmen) have disappeared from the novel's narrative present, Schreiner's colonial indigene takes their place. This imaginative displacement thus corresponds with a demographic one, while also manifesting itself in The Story of an African Farm through a fetishistic aesthetic and the uncanny return of a frequently overlooked African laborer.
A Reply to Francis & Robbins
Authors: Davie Grace
Published: July 2004

I am grateful for the chance to reply to this article, which raises important issues concerning the relationships between religious belief, belonging and practice. My reactions are two-fold: first, that I agree with its conclusions, and secondly, that these are entirely consonant with the aims that I set myself when I wrote Religion in Britain since 1945—complete with its now famous (or infamous) subtitle ‘believing without belonging’.
Occurrence, Size, and Tag Retention of Sneaker Male Hatchery Rainbow Trout
Authors: Isely J Jeffery , Grabowski Timothy B
Published: July 2004

One alternative reproductive tactic involving early-maturing, cryptic males is referred to as “sneaking.” Although sneakers tend to be easily detectable upon close inspection, little is known about the proportion of a fish population consisting of sneakers. We examined 15,400 age-1 rainbow trout Oncorhynchus mykiss in a hatchery. Total length (mm), wet weight (g), and sex (sneaker male or unknown) were recorded for each fish. We also individually tagged each sneaker male with soft visual implant alphanumeric (VIalpha) tags that were sequentially numbered and held the fish for 25 d before inspection. Sneakers constituted 2.8% of the hatchery rainbow trout population and were smaller in total length and weight than typical rainbow trout of the same age. Retention of the VIalpha tags in sneakers was 58.9%, significantly lower than has been reported under similar circumstances. We found that sneaker males may contribute substantially to hatchery populations. Reduced tag retention in sneakers may bias studies evaluating the effect of hatchery fish on wild populations. We believe that hatchery-produced sneaker males have the potential to contribute importantly to the genetic composition of wild populations.
Relationship of Lipid Content to Size and Condition in Walleye Fingerlings from Natural and Aquacultural Environments
Authors: Copeland Timothy , Carline Robert F
Published: July 2004

Condition indices are widely used in the evaluation of fish populations, but most research on the relationship of condition indices to body composition has taken place in laboratory environments. Our objectives were to assess the relative ability of measures of size and three versions of condition index to predict the lipid content of fingerling walleyes Sander vitreus from aquacultural or natural environments. Fingerlings were either intensively cultured through the fall of 1994, were stocked and spent 3–4 months at large in four lakes, or were intensively cultured and maintained overwinter in hatchery ponds. Variation in condition indices accounted for less than 35% of the variation in lipid. No index performed substantially better than the others. The relationship of condition to lipid content was not consistent between environments or seasons (ANCOVA: F = 403.4, P < 0.0005). Relationships were also different among the four lake populations (ANCOVA: F = 33.9, P < 0.0005). Inconsistencies seem to be the result of differences in seasonal and environmental stress. The utility of condition indices as surrogates for body composition should be verified with each use. Furthermore, comparisons of fingerlings from aquacultural environments with fingerlings from natural environments are unlikely to be physiologically meaningful.
Overwintering Yellow Perch Fry in Alabama
Authors: Saoud I Patrick , Rodgers Leonard , Chappell Jesse , Davis D Allen
Published: July 2004

Wild harvests of yellow perch Perca flavescens have failed to keep up with the strong market demand for the fish. Moreover, yellow perch has many attributes that make it attractive for commercial aquaculture in the USA. One drawback to yellow perch culture in the north-central region of the United States is that low winter water temperatures inhibit somatic growth. In this study, yellow perch juveniles were stocked at three densities (30, 60, and 90 per tank) in 600-L tanks in Auburn, Alabama, in early January and maintained throughout the winter until mid-April. Water in the tanks was circulated through an earthen pond and returned to the research system by means of a water pump. Tanks were aerated by means of submersible air diffusers and a regenerative air blower. Fish were offered a commercial, slow-sinking feed at 5% of body weight, and temperature was measured hourly by a remote data logger. Survival was greater than 99% in all treatments. When water temperature was below 20°C, absolute growth was 0.06, 0.05, and 0.04 g/d for the low-, medium-, and high-stocking density treatments, respectively. When water temperature was above 20°C, absolute growth was 0.58, 0.48, and 0.46 g/d for the low-, medium-, and high-stocking density treatments, respectively. Yellow perch juveniles survived well and grew well in Alabama during fall and spring seasons when temperatures were above 20°C.
Increasing Production of Copepod Nauplii in a Brown-Water Zooplankton Culture with Supplemental Feeding and Increased Harvest Levels
Authors: Lemus Jason T , Ogle John T , Lotz Jeffrey M
Published: July 2004

Two experiments were performed to investigate increasing the number of copepod nauplii obtained from a brown-water zooplankton culture for feeding to larval red snapper Lutjanus campechanus. Brown-water zooplankton cultures rely on the regular exchange of (brown) estuarine water to nourish and harvest the copepods. The majority of copepods in both experiments were Acartia tonsa. The goal of the first experiment was to determine whether adding rice bran to a brown-water zooplankton culture would increase copepod density. Brown-water zooplankton cultures supplemented with rice bran had significantly higher naupliar densities than either brown-water zooplankton cultures without rice bran or zooplankton cultures supplemented with rice bran but without brown-water exchanges. Both the rice-bran-supplemented brown-water zooplankton culture and the rice bran zooplankton culture had higher copepodid densities than the brown-water zooplankton culture, but they were not different from each other. The goal of the second experiment was to determine the harvest rate (25, 50, and 75% of the water volume every other day) that would produce the most copepods. Copepod densities increased with a decrease in harvest rate; however, naupliar yields increased with increasing harvest rate. Copepod populations subjected to the various harvest rates appeared to undergo similar dynamics and were thus equally sustainable. There were significantly more nauplii harvested with the 75% harvest rate than with the other rates, but there was no difference in the number of harvested copepodids resulting from the different harvest rates. Naupliar yields of brown-water zooplankton cultures may be increased by rice bran supplementation and harvesting 75% of the culture volume every other day.
Prevalence of Furunculosis in Chinook Salmon Depends on Density of the Host Exposed by Cohabitation
Authors: Ogut Hamdi , Reno Paul
Published: July 2004

Chinook salmon Oncorhynchus tshawytscha were experimentally infected with Aeromonas salmonicida to determine the dependence of initiation and spread of a furunculosis epizootic on host density. Groups of 30 and 60 recipient Chinook salmon (1.7 ± 0.14 g) were held in various volumes of water at a wide range of densities (15.52, 7.76, 1.23, 0.61, 0.32, 0.15, and 0.047 g fish/L) for 23–33 d, and each were exposed to a single infectious individual by cohabitation. Significant relationships (r  2 = 0.55) were found between host density (g fish/L) and survival from furunculosis. No pathogen transmission occurred at the lowest density. Acute and chronic patterns of furunculosis were obtained by adjusting densities. It took longer to observe disease-specific mortality among recipient fish at lower densities compared with higher densities even when donors were similarly infectious. The results have important implications for stocking salmonids regarding natural route of transmission and in understanding the pattern of the density effect on furunculosis epizootics in Chinook salmon.
Effects of Dietary Protein Concentration on Production Characteristics of Pond-Raised Channel Catfish Fed Once Daily or Once Every other Day to Satiation
Authors: Li Menghe H , Manning Bruce B , Robinson Edwin H , Bosworth Brian G
Published: July 2004

We evaluated the effects of dietary protein and feeding regime on the production characteristics, processing yield, and body composition of channel catfish Ictalurus punctatus. Stocker-size fish with an average weight of 93 g/fish were stocked into twenty-four 0.4-ha ponds at a rate of 11,115 fish/ha. Fish were fed once daily or every other day (EOD) to apparent satiation with three commercial diets containing 28, 32, or 35% protein in a 2 × 3 factorial arrangement for 110 d. Compared with daily feeding, EOD feeding resulted in lower average net production, feed consumption, weight gain per fish, and feed conversion ratio and produced fewer marketable fish. The EOD ponds required less aeration than ponds with fish fed daily. Fish fed EOD had lower visceral fat and fillet fat, carcass yield, and fillet yield compared with fish fed daily. Dietary protein levels had no effect on net production, aeration time, processing yield, fillet composition, and feed consumption and weight gain per fish. However, the feed conversion ratio was higher for fish fed the 28% protein diet than for fish fed the other two diets, which was unexpected because we have not observed this in other studies. Neither dietary protein nor feeding regime had an effect on pond water total ammonia nitrogen, un-ionized ammonia, or nitrite-nitrogen concentrations; these nitrogenous compounds were highly variable among ponds and time. The results from the present study demonstrated that dietary protein levels in the range of 28% to 35% had no effect on channel catfish growth or production whether the fish were fed once daily or once EOD to satiation. Feeding EOD may improve feed efficiency and reduce feed cost and aeration time but will also reduce production and processing yield and extend the production cycle compared with feeding daily.
Isolation of Edwardsiella ictaluri from Tadpole Madtom in a Southwestern New Jersey River
Authors: Klesius Phillip , Lovy Jan , Evans Joyce , Washuta Edmund , Arias Cova
Published: July 2004

In 2002, New Jersey Division of Fish and Wildlife biologists conducted an aquatic assessment in a section of the Cohansey River in Cumberland County. Three of seven tadpole madtoms Noturus gyrinus collected were observed to have an ulcerative lesion on the head between the eyes. Gram-negative, oxidase-negative rods were isolated from the head kidneys of two of the madtoms and from the cranial ulcer of the third madtom. Four different identification methods— API-20E, whole-cell fatty acid methyl esters (FAME), BIOLOG, and enterobacterial repetitive intergenic consensus (ERIC) sequences—ascribed the isolates to the species Edwardsiella ictaluri. A phenotypic comparison using FAME and BIOLOG data revealed that E. ictaluri isolates from wild madtoms shared a high degree of similarity to E. ictaluri isolates from cultured channel catfish with enteric septicemia of catfish (ESC) from southeastern states. However, fingerprinting by amplified fragment length polymorphisms (AFLP) demonstrated that the three madtom isolates were genetically different from the other E. ictaluri isolates. Koch's postulates were fulfilled by using the tadpole madtom E. ictaluri isolate in juvenile channel catfish. Sixty percent mortality was achieved in intraperitoneal injection of catfish with the isolate (1 × 104 colony-forming units/ fish), produced 60% mortality. The results indicate that the ictalurid tadpole madtom is susceptible to ESC by natural infection. This is the first report of a bacterial disease affecting tadpole madtoms.
Severe Acute Respiratory Syndrome (SARS): The Pharmacist's Role
Authors: Chin Thomas W. F. , Chant Clarence , Tanzini Rosemary , Wells Janice
Published: July 2004

Objectives. After two outbreaks of severe acute respiratory syndrome (SARS) occurred in Toronto, Ontario, Canada, from March–June 2003, we reviewed the unexpected role and responsibilities of pharmacists during these two crises, and present strategies for better crisis preparedness.

Methods and Results. Pharmacists were actively involved in battling the SARS crises. After conducting extensive literature searches and evaluations, pharmacists prepared administration and dosing guidelines for the two investigational drugs, ribavirin and interferon alfacon‐1, that were being used to treat the syndrome. They provided direct patient care under modified conditions. They revised drug distribution procedures and developed new ones to meet more stringent infection‐control standards. Collaborative teamwork with key stakeholders was important in accomplishing tasks in an efficient and timely manner. Regular communication with health care staff took place internally and externally. Education and updated information for pharmacists was crucial.

Conclusion. Pharmacists can play a vital role during crises in the areas of drug distribution, drug information, and direct patient care. Collaborative teamwork and close communication are keys to success. Pharmacists must be proactive and take a leadership role in assuming pharmacy‐related responsibilities. By evaluating what worked and what didn't, pharmacists can develop procedures for future crises requiring pharmacy support.
The Utility of Insulin Glargine in the Treatment of Diabetes Mellitus
Authors: Stroup Jeffrey , Kane Michael P. , Busch Robert S. , Bakst Gary , Hamilton Robert A.
Published: July 2004

Study Objectives. To compare hemoglobin A1c (A1C) values at baseline with those after 1 year of insulin glargine therapy and, secondarily, to compare insulin dosage and patients' body weight at baseline and at 1 year.

Design. Retrospective study.

Setting. Private endocrinology practice.

Patients. One hundred ninety‐seven patients with diabetes mellitus who were first prescribed insulin glargine from May 2001–April 2002 and were evaluable after 1 year of therapy.

Intervention. Patients received insulin glargine instead of NPH insulin or in addition to their oral drug therapy.

Measurements and Main Results. Patients with diabetes type 1 (receiving insulin therapy) or type 2 (receiving oral drug therapy only, a combination of oral drug therapy and insulin, or insulin only) who had been treated with insulin glargine for 1 year were evaluated. Overall, A1C values decreased significantly (p<0.001) by 0.53 ± 1.4% from a baseline mean of 8.1 ± 1.7%. In 129 patients with type 2 diabetes previously treated with NPH insulin, A1C decreased significantly (p<0.001) 0.57 ± 1.5% from baseline. The A1C decreased by 0.71 ± 1.3% (p=0.0043) from baseline in 33 patients with type 2 diabetes who previously received oral agents only. Thirty‐five patients with type 1 diabetes demonstrated no significant change in A1C (‐0.22 ± 1.0%, p=0.217) from baseline. In patients receiving insulin at baseline, the number of daily injections increased significantly (p<0.0001) from a median of two at baseline to three at 1 year. Overall, no significant change was noted in total daily insulin requirement or in body weight in any of the patient groups over the 1‐year period.

Conclusion. Compared with baseline, insulin glargine therapy at 1 year was associated with an overall significant reduction in A1C of 0.53 ± 1.4%.
Alendronate‐Induced Auditory Hallucinations and Visual Disturbances
Authors: Coleman Craig I. , Perkerson Kristen A. , Lewis Anne
Published: July 2004

A 79‐year‐old Caucasian woman who had been taking alendronate 10 mg/day for over 2 years to prevent osteoporosis reported hearing “voices in her head” along with red‐colored visual disturbances. These auditory hallucinations and visual disturbances began shortly after her regimen was changed from alendronate 10 mg/day to 70 mg once/week. Assessment of causality using the Naranjo and Jones algorithms revealed a “probable” and “highly probable” relationship, respectively, between this adverse drug event and the switch from daily to weekly alendronate therapy. Other bisphosphonates, such as etidronate and pamidronate, have caused both reversible and irreversible auditory, visual, and olfactory hallucinations beginning 2 hours–1 week after drug administration. The mechanism behind these adverse effects is unknown but is thought to be independent of calcium homeostasis. Clinicians should be aware of central nervous system toxicity as a rare but potential adverse effect associated with bisphosphonates.
Meropenem Administered as a Prolonged Infusion to Treat Serious Gram‐Negative Central Nervous System Infections
Authors: Capitano Blair , Nicolau David P. , Potoski Brian A. , Byers Karin E. , Horowitz Michael , Venkataramanan Raman , Paterson David L.
Published: July 2004

The treatment of gram‐negative infection of the central nervous system (CNS) presents a clinical challenge due to antibiotic resistance and difficulties with penetration into the cerebrospinal fluid (CSF). Two patients with gram‐negative CNS infections were treated successfully with high‐dose, prolonged infusions of meropenem. The CSF meropenem concentrations exceeded the minimum inhibitory concentration of the pathogen for virtually the entire dosing interval in both cases. Our experience demonstrates that dosage modification to maximize pharmacodynamic targets and bactericidal activity may be practically applied to optimize antibiotic treatment for difficult‐to‐treat CNS infections.
Cephalexin‐Induced Acute Tubular Necrosis
Authors: Longstreth Kristen L. , Robbins Steven D. , Smavatkul Chanigan , Doe Nathaniel S.
Published: July 2004

A 24‐year‐old woman with a history of penicillin allergy developed reversible acute renal failure after receiving cephalexin for 4 days. The patient experienced nausea, vomiting, diarrhea, pruritus, cough, and an elevated creatinine level of 2.2 mg/dl. The patient's creatinine level continued to rise, peaking at 5.3 mg/dl on hospital day 3. Nephrotoxic acute tubular necrosis was confirmed by electron microscopy. Within 1 month of discharge from the hospital, the patient's creatinine level decreased to 0.6 mg/dl. Although the renal injury most commonly associated with the cephalosporin class of antibiotics is allergic interstitial nephritis, currently available cephalosporins infrequently can cause direct tubular toxicity.
Synthesis, Properties and Applications of BICAP: a New Family of Carbazole‐Based Diphosphine Ligands
Authors: Botman Peter N. M. , Fraanje Jan , Goubitz Kees , Peschar René , Verhoeven Jan W. , van Maarseveen Jan H. , Hiemstra Henk
Published: July 2004

A new family of bidentate phosphine ligands based on the biscarbazole backbone has been synthesized and applied in the ruthenium‐ and rhodium‐catalyzed asymmetric hydrogenations of methyl acetoacetate and dimethyl itaconate. The nitrogen atoms in these BICAP ligands allow facile introduction of substituents providing structurally similar, but electronically different ligands, which were used to fine‐tune these reactions to 98% and 55% ee, respectively.
Fluoride Ion‐Promoted α‐Ketol Rearrangement during Unmasking of Silyl‐Protected Medium‐Ring Dihydroxy Ketones
Authors: Hartung Ryan E. , Hilmey David G. , Paquette Leo A.
Published: July 2004

A new strategy for implementing α‐ketol rearrangements under mild conditions is presented. The reactants are mono‐ and disilylated stereoisomers of α,α′‐ and α,β‐dihydroxycycloheptanones and ‐cyclooctanones. Compounds of this class experience ready deprotection upon treatment with tetrabutylammonium fluoride. In certain examples, this process is accompanied by structural isomerization. Since the product diols are stable to the reaction conditions, these chemical changes have been attributed to kinetically controlled events following transient alkoxide generation resulting from cleavage of the OSi bond proximal to the carbonyl group. The experimental findings are evaluated against a backdrop of calculated (MM3) steric energies of the silicon‐free products and their response to equilibration under strongly basic conditions.
Synthesis of the 8‐Hydroxy Acid of Jasplakinolide
Authors: Wattanasereekul Saengchai , Maier Martin E.
Published: July 2004

The protected ω‐hydroxy acid 4b contained in the depsipeptide jasplakinolide (1) was prepared in a sequence of 13 steps from the silylated 3‐hydroxy ester 6. By chain extension 6 was converted to the allyl alcohol 10. A subsequent asymmetric cyclopropanation of the allylic alcohol 10 using the Charette method provided the hydroxymethylcyclopropane 12 with excellent diastereoselectivity. This cyclopropanation was used to establish the methyl‐bearing stereocenter at C‐6 of the hydroxy acid 4 by reductive ring cleavage of the (iodomethyl)cyclopropane 14. The alkene 15 was used for a cross alkene metathesis reaction with 2‐methylacrylate 20 providing the enoate 19. The derived allylic iodide 24 served as an electrophile in the final Evans alkylation step to give the ω‐hydroxy acid derivative 26.
Highly Selective Copper‐Catalyzed Monoarylation of Aniline
Authors: Haider Joachim , Kunz Klaus , Scholz Ulrich
Published: July 2004

A series of mono‐, bi‐ and tridendate ligands was investigated in the copper‐catalyzed monoarylation of aniline with p‐chloronitrobenzene. Excellent selectivities at high conversions were observed when bridged bisimidazolidenes as well as biphenyl‐bisalkylphosphines were employed. The X‐ray crystal structure of bis(tert‐butyl)biphenylphosphine‐copper complex indicates a significant binding of the metal center to the aryl moiety and, thus, an almost bidendate coordination mode. Chelating bisphosphines, glycol, phenanthroline or other mono‐ to tridendate ligands led to less selective or productive catalysts.
Transition Metal‐Catalyzed Synthesis of Novel Biologically Relevant Tryptophan Analogues
Authors: van Esseveldt Bart C. J. , van Delft Floris L. , Smits Jan M. M. , de Gelder René , Schoemaker Hans E. , Rutjes Floris P. J. T.
Published: July 2004

A synthetic approach to the synthesis of novel tryptophan derivatives and benzofuran‐containing amino acids is detailed. The sequence starts from enzymatically resolved enantiopure acetylene‐containing amino acids, of which the acetylene function can be efficiently transformed into the targeted 2‐substited indole and benzofuran moieties via Sonogashira‐type coupling and metal‐catalyzed cyclization.
Dendrimer–Palladium Complex Catalyzed Oxidation of Terminal Alkenes to Methyl Ketones
Authors: Zweni Pumza P. , Alper Howard
Published: July 2004

Silica‐supported polyamidoamine (PAMAM) dendrimers with different spacer lengths were prepared. After the introduction of diphenylphosphino groups, complexation to dibenzylidenepalladium(0) gave the desired silica‐supported dendrimer–palladium catalyst complexes G0 to G4‐C2‐Pd. These catalysts showed activity towards the oxidation of terminal alkenes to methyl ketones. A dependence of catalytic activity on the spacer length of the diamine in PAMAM was observed.
Double Elimination Protocol for Convenient Synthesis of Dihalodiphenylacetylenes: Versatile Building Blocks for Tailor‐Made Phenylene‐Ethynylenes
Authors: Orita Akihiro , Miyamoto Kazuhiko , Nakashima Mikio , Ye Fangguo , Otera Junzo
Published: July 2004

Dihalodiphenylacetylenes are conveniently synthesized by a double elimination reaction of β‐substituted sulfones which are readily obtained from halogen‐substituted benzyl sulfone and benzaldehyde derivatives. Halogens can be incorporated at any desired positions in the diphenylacetylene skeleton simply by choosing the substitution position of the halogen on the aromatic rings of the starting compounds. The diphenylacetylenes with different halogen substituents thus obtained undergo sequential carbon‐carbon bond formations due to the different reactivities of the halogens. Thus, various moieties can be incorporated on the diphenylacetylene skeleton at whichever positions so that a variety of tailor‐made phenylene‐ethynylenes with regulated structure and composition could be designed.
Utilization of 2‐(4‐Nitrophenylsulfonyl)ethoxycarbonyl (Nsc) as a Substitute for 9H‐Fluoren‐9‐ylmethoxycarbonyl (Fmoc) in Liquid Phase Chemistry
Authors: Maier Thomas C. , Podlech Joachim
Published: July 2004

2‐(4‐Nitrophenylsulfonyl)ethoxycarbonyl (Nsc) is a useful substitute for the Fmoc group. It is easily removed not only with secondary amines but with tris(aminoethyl)amine (TAEA) and with resin‐bound TAEA, thus allowing for a simplified work‐up: the side products of the deprotection are removed either by extraction with phosphate buffer or by filtration.
Titanium‐Catalyzed Tandem Sulfoxidation‐Kinetic Resolution Process: A Convenient Method for Higher Enantioselectivities and Yields of Chiral Sulfoxide
Authors: Jia Xian , Li Xingshu , Xu Lijin , Li Yueming , Shi Qian , Au‐Yeung Terry T.‐L. , Yip C. W. , Yao Xinsheng , Chan Albert S. C.
Published: July 2004

A one‐pot, titanium‐catalyzed tandem sulfoxidation‐kinetic resolution process, which combines asymmetric oxidation (at lower temperature) and kinetic resolution (at room temperature), has been developed. Excellent ees (up to>99.9%) and higher chemical yields of sulfoxides were obtained and the results compared favorable with those from either oxidation or kinetic resolution.
Predetermined Helical Chirality in Octahedral Complexes with a Novel Pentadentate C2‐Symmetrical Chiral Bis(oxazoline) Ligand
Authors: Seitz Michael , Kaiser Anja , Powell Douglas R. , Borovik Andrew S. , Reiser Oliver
Published: July 2004

The first example of the pentadentate bis(oxazolines) has been synthesized using a modular approach that readily provides access to this ligand class. This ligand allows the controlled transfer of carbon‐centered to octahedral, metal‐centered chirality, as demonstrated both in the solid state as well as in solution. The characteristic CD band has been identified for dicationic, octahedral transition metal complexes with the Δ2‐configuration.
Involvement of an Oxidation‐Reduction Equilibrium in Chromium‐Mediated Enantioselective Nozaki–Hiyama Reactions
Authors: Schrekker Henri S. , Micskei Károly , Hajdu Csongor , Patonay Tamás , de Bolster Martin W. G. , Wessjohann Ludger A.
Published: July 2004

Ligand induced enantioselective versions of the chromium(II)‐mediated Nozaki–Hiyama reaction to homoallyl alcohols proved to be very difficult to achieve, especially if any other nucleophile than the parent allylchromium(III) species was applied. Also, the reaction is frequently accompanied by the formation of oxidation side products, predominantly allyl ketones. This can be explained by an Oppenauer–(Meerwein–PonndorfVerley) type mechanism (OMPV reaction). The addition of an enantiopure ligand to racemic chromium homoallyl alcoholate intermediates produced enantiomerically enriched homoallyl alcohols with an enantiomeric excess of up to 32%. This observation not only supports that the proposed OMPV oxidation‐reduction equilibrium plays a crucial role in Nozaki–Hiyama reactions, but also proves its involvement in enantioselective versions.
Synthesis of Substituted Mandelic Acid Derivatives via Enantioselective Hydrogenation: Homogeneous versus Heterogeneous Catalysis
Authors: Cederbaum Fredrik , Lamberth Clemens , Malan Christophe , Naud Fred , Spindler Felix , Studer Martin , Blaser Hans‐Ulrich
Published: July 2004

An extensive screening of both homogeneous and heterogeneous catalysts was carried out for the enantioselective hydrogenation of p‐chlorophenylglyoxylic acid derivatives. For p‐chlorophenylglyoxylic amides only homogeneous Rh‐diphosphine complexes gave satisfactory results, ees up to 87% were observed for the cy‐oxo‐pronop ligand. For methyl p‐chlorophenylglyoxylate both a homogeneous as well as a heterogeneous catalyst performed with ees >90%. A Pt catalyst modified with cinchona derivatives achieved 93% ee for the (R)‐ and 87% ee for the (S)‐methyl p‐chloromandelate. A Ru‐MeObiphep catalyst also reached 93% ee with TONs up to 4000 and TOFs up to 210 h−1. For all catalytic systems the effects of the metal, the nature of the chiral auxiliary and the solvent as well as of the reaction conditions were investigated. The homogeneous process was scaled up to the kg scale and the enantiomeric purity of the product was enhanced to >99% ee by two recrystallizations of the free p‐chlorophenylmandelic acid.
Ruthenium‐Catalyzed O‐Allylation of Phenols from Allylic Chlorides via Cationic [Cp*(η3‐allyl)(MeCN)RuX][PF6] Complexes
Authors: Mbaye Mbaye D. , Demerseman Bernard , Renaud Jean‐Luc , Toupet Loïc , Bruneau Christian
Published: July 2004

The [Cp*(MeCN)3Ru(II)][PF6] complex is an efficient catalyst precursor for the O‐allylation of phenols with allylic chlorides in the presence of K2CO3 under mild conditions. This ruthenium precursor affords branched allyl aryl ethers according to a regioselective reaction, which contrasts with the uncatalyzed nucleophilic substitution from the same substrates. Stable (η3‐allyl)Ru(IV) cationic complexes resulting from the reaction of [Cp*(MeCN)3Ru][PF6] with allylic halides were identified as intermediate catalytic species. An X‐ray structure determination of the complex [Cp*(MeCHCHCH2)(MeCN)RuBr][PF6] disclosed an (endo‐trans‐MeCHCHCH2) allylic ligand. The structural information obtained from the study of Cp*(allyl)Ru(IV) complexes indicated that electronic effects at the coordinated allylic ligand likely account for the better regioselectivity obtained from cinnamyl chloride as compared to aliphatic allylic chlorides.
Cyclopropyl Building Blocks for Organic Synthesis, Part 100. Advanced Syntheses of Cyclopropylideneacetates –Versatile Multifunctional Building Blocks for Organic Synthesis
Authors: Limbach Michael , Dalai Suryakanta , de Meijere Armin
Published: July 2004

A well reproducible and inexpensive preparation of the cyclopropylideneacetates 2–4 has been developed. The key intermediate 2‐(1′‐mesyloxycyclopropyl)acetic acid (8), produced either from methyl phenylacetate (1) or 3,3‐dimethoxypropionate (5‐Me) and 3,3‐diethoxypropionate (5‐Et) in a sequence of Kulinkovich reductive cyclopropanation, mesylation and oxidative cleavage or cleavage and oxidation, respectively, was either converted to the benzyl ester 11b, or chlorinated (brominated) via the in situ formed acid chloride. The α‐chloro‐ 12a and α‐bromo ester 12b were dehydromesylated by treatment with triethylamine to furnish methyl 2‐chloro‐2‐cyclopropylideneacetate (3‐Me) and the 2‐bromo analogue 4‐Me with an overall yield of 68% (65%, 68%) and 52% (49%, 51%) respectively, starting from 1 (5‐Me, 5‐Et). The parent benzyl cyclopropylideneacetate 2‐Bn was obtained by dehydromesylation of 11b with potassium t‐butoxide in t‐butyl methyl ether with an overall yield of 60% (57%, 9%) from 1 (5‐Me, 5‐Et).
Alkyne Metatheses in Transition Metal Coordination Spheres: Convenient Tungsten‐ and Molybdenum‐Catalyzed Syntheses of Novel Metallamacrocycles
Authors: Bauer Eike B. , Hampel Frank , Gladysz J. A.
Published: July 2004

Reactions of (CO)5Re(Br), (η5‐C5H5)Ru(Cl)(PPh3)2, and [Pt(μ‐Cl)(C6F5)(S(CH2CH2‐)2)]2 with the alkyne‐containing phosphine Ph2P(CH2)6C≡CCH3 give the bis(phosphine) complexes fac‐(CO)3Re(Br)(Ph2P(CH2)6C≡CCH3)2 (5), (η5‐C5H5)Ru(Cl)(Ph2P(CH2)6C≡CCH3)2 (6), and trans‐(Cl)(C6F5)Pt(Ph2P(CH2)6C≡CCH3)2 (7). Alkyne metatheses with the catalyst (t‐BuO)3W(≡C‐t‐Bu) (10–15 mol %, chlorobenzene, 80 °C) give the seventeen‐membered metallamacrocycles fac‐(CO)3Re(Br)(Ph2P(CH2)6CC(CH2)6PPh2) (8), (η5‐C5H5)Ru(Cl)(Ph2P(CH2)6CC(CH2)6PPh2) (9), and trans‐(Cl)(C6F5)Pt(PPh2(CH2)6CC(CH2)6PPh2) (10). 31P NMR analyses show 90–75% conversions to 8–10 (59–47% isolated after chromatography). The identity of 8 was confirmed by a crystal structure, and 10 was hydrogenated over Pd/C to fac‐(CO)3Re(Br)(Ph2P(CH2)6CC(CH2)6PPh2) (12, 87%), which was crystallographically characterized earlier. A catalyst derived from Mo(CO)6/4‐chlorophenol effects a slower conversion of 7 to 10 at 140 °C. In the case of 5, a mer, trans isomer of 8 is isolated (11, 44%), as established by NMR and IR data. In 10–12, the diphosphines span trans positions. These results, together with previous examples involving group VIII metallocenes, establish the wide viability of the title reaction.
Optically Pure 1,2‐Bis[(o‐alkylphenyl)phenylphosphino]ethanes and Their Use in Rhodium‐Catalyzed Asymmetric Hydrogenations of α‐(Acylamino)acrylic Derivatives
Authors: Wada Yoshiyuki , Imamoto Tsuneo , Tsuruta Hideyuki , Yamaguchi Kentaro , Gridnev Ilya D.
Published: July 2004

Optically pure (S,S)‐1,2‐bis[(o‐alkylphenyl)phenylphosphino]ethanes 1a–d were prepared in four steps from phenyldichlorophosphine via phosphine‐boranes as the intermediates. The rhodium complexes 5a–d of these diphosphines were used for the asymmetric hydrogenations of α‐(acylamino)acrylic derivatives including β‐disubstituted derivatives. Markedly high enantioselectivity (78–>99%) was observed for the reduction of β‐monosubstituted derivatives. β‐Disubstituted derivatives were also reduced in considerably high enantioselectivity (up to 90%). The single crystal X‐ray analysis of the rhodium complex 5c of (S,S)‐1,2‐bis[phenyl(5′,6′,7′,8′‐tetrahydronaphthyl)phosphino]ethane (1c) revealed its δ‐type structure with face orientation of the two tetrahydronaphthyl groups and edge orientation of the two phenyl groups. This conformation corresponds to that of the rhodium complex of 1,2‐bis[(o‐methoxyphenyl)phenylphosphino]ethane (DIPAMP); the rhodium complex of (R,R)‐DIPAMP, whose chirality at phosphorus is opposite that of 5c, exhibits a λ‐type structure with the face orientation of the two o‐methoxyphenyl groups and the edge orientation of the two phenyl groups. The conformational similarity of these rhodium complexes as well as the stereochemical outcome in the asymmetric hydrogenations means that the coordinative interaction of the methoxy group of DIPAMP with rhodium metal is not the main factor that affects asymmetric induction.
Allylation of Carbon Pronucleophiles with Alkynes in the Presence of Palladium/Acetic Acid Catalyst
Authors: Patil Nitin T. , Kadota Isao , Shibuya Akinori , Gyoung Young Soo , Yamamoto Yoshinori
Published: July 2004

We have developed an efficient and eco‐chemical process for the allylation of carbon pronucleophiles with alkynes. The reaction of alkynes with various active methynes and methylenes in the presence of Pd(PPh3)4/acetic acid gave the corresponding allylated products in high yields and high regioselectivities. In the present catalytic system, the key is the use of carboxylic acid which dramatically enhances the rate of the reactions. One of the important features of this process is that neither a leaving group is liberated nor is a stoichiometric amount of base needed to generate the nucleophiles.
Enantiomerically Pure Cyclopropane Building Blocks: Synthesis and Transformations of 2‐Iodocyclopropylboronic Esters
Authors: Hohn Erwin , Pietruszka Jörg
Published: July 2004

Enantiomerically pure 2‐iodocyclopropylboronic esters 6 and 8 have been synthesized from the readily available allylic alcohol 2 via an oxidation‐radical decarboxylation sequence. These unique building blocks have been demonstrated to be versatile intermediates for a consecutive Suzuki‐coupling with aryl‐, heteroaryl‐, alkenyl‐, and cyclopropylboron derivatives (1 example each).
Room Temperature Aerobic Copper–Catalysed Selective Oxidation of Primary Alcohols to Aldehydes
Authors: Gamez Patrick , Arends Isabel W. C. E. , Sheldon Roger A. , Reedijk Jan
Published: July 2004

A novel and very mild method for the oxidation of primary alcohols to aldehydes with excellent conversions has been developed. The reaction is carried out under air at room temperature and is catalysed using a [copper(II)‐(N ligand)n] complex with TEMPO and a base as co‐catalysts. In this paper, the performance of a series of N‐containing ligands, as well as different copper(II) salt precursors in different solvents are reported. Best results are obtained in acetonitrile/water as solvent using a copper(II) catalyst generated in situ from a Cu(II) salt with weak or non‐coordinating anions and bipyridine ligands with electron‐donating substituents. A reaction mechanism is postulated which resembles that of galactose oxidase, and in which TEMPO seems to be involved as a hydrogen acceptor.