2-pyrazinylnitrene and 4-pyrimidylnitrene. Ring expansion to 1,3,5-triazacyclohepta-1,2,4,6-tetraene and ring opening to (2-isocyanovinyl)carbodiimide

Tetrazolo[1,5-a]pyrazine/2-azidopyrazine 9T/9A undergo photolysis in Ar matrix at cryogenic temperatures to yield 1,3,5-triazacyclohepta-1,2,4,6-tetraene 21 as the first observable intermediate, and 1-cyanoimidazole 11 and (2-isocyanovinyl)carbodiimide 22 as the final products. The latter tautomerizes to 2-(isocyanovinyl)cyanamide 23 on warming to 40 K. The same intermediate 21 and the same final products are obtained on matrix photolysis of the isomeric tetrazolo[1,5-c]pyrimidine/4-azidopyrimidine 24T/24A. These photolysis results as well as those of the previously reported thermal ring contraction of N-15-labeled 2-pyrazinyl- and 4-pyrimidylnitrenes to 1-cyanoimidazoles can all be rationalized in terms of selective ring opening of 21 or nitrine 10 to a nitrile ylide zwitterion 28 prior to formation of the final products, 11 and 22. The results are supported by high-level ab initio and DFT calculations (CASPT2-CASSCF(6,6), G3(MP2), and B3LYP/6-31+G*) of the energies and IR spectra of the intermediates and products.

Epizootic activity of Murray Valley encephalitis virus in an aboriginal community in the southeast Kimberley region of western Australia: Results of cross-sectional and longitudinal serologic studies

Murray Valley encephalitis (MVE) virus is a mosquito-borne flavivirus causing severe encephalitis with a resultant high morbidity and mortality. In the period 1989-1993. we undertook a cross-sectional and longitudinal studs by annually screening members of a small remote Aboriginal community in northwestern Australia for MVE virus antibodies. Of the estimated 250-300 people in the community. 249 were tested, and 52.6% had positive serology to MVE. The proportion testing positive increased with increasing age group. and males were slightly more likely to be positive than females. During the study period. a high proportion of the population seroconverted to MVE: the clinical/subclinical ratio seems to be lower than previously reported. Although MVE is mostly asymptomatic, the devastating consequences of clinical illness indicate that advice should be provided regarding the avoidance of mosquito bites. Our longitudinal study showed that the risk of seroconversion was similar for each age group. not just the young.

The metamorphosis of lambda-fold K-3,K-3-designs into lambda-fold 6-cycle systems

In this paper necessary and sufficient conditions are given for the metamorphosis of a lambda-fold K-3,K-3-design of order n into a lambda-fold 6-cycle system of order n, by retaining one 6-cycle subgraph from each copy of K-3,K-3, and then rearranging the set of all the remaining edges, three from each K-3,K-3, into further 6-cycles so that the result is a lambda-fold 6-cycle system.

Dynamic Behavior of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion in Cu2+ doped Cs-2[Zn(H2O)(6)](ZrF6)(2) and the crystal structure of the host lattice

The temperature dependence of the X- and Q-band EPR spectra of Cs-2[Zn(H2O)(6)](ZrF6)(2) containing similar to1% Cu2+ is reported. All three molecular g-values vary with temperature, and their behavior is interpreted using a model in which the potential surface of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion is perturbed by an orthorhombic strain induced by interactions with the surrounding lattice. The strain parameters are significantly smaller than those reported previously for the Cu(H2O)(6)(2+) ion in similar lattices. The temperature dependence of the two higher g-values suggests that in the present compound the lattice interactions change slightly with temperature. The crystal structure of the Cs-2[Zn(H2O)(6)](ZrF6)(2) host is reported, and the geometry of the Zn(H2O)(6)(2+) ion is correlated with lattice strain parameters derived from the EPR spectrum of the guest Cu2+ complex.

Seasonal Effects on Transient Evoked Otoacoustic Emission Screening Outcomes in Infants versus 6-Year-Old Children

The purpose of this study was to compare transient evoked otoacoustic emission (TEOAE) screening outcomes (pass/fail) across the seasons (spring, autumn, and winter) between infants and schoolchildren. A total of 526 infants (275 boys, 251 girls) with a mean age of 2.0 months (SD = 0.38 months) and 975 schoolchildren (513 boys, 462 girls) with a mean age of 6.2 years (SD = 0.36 years) were screened using the ILO Otodynamics Quickscreen program. The same TEOAE pass/fail criterion was applied to the two groups. The results indicated a significant difference in pass rates between infants (91.2% of 1052 ears) and schoolchildren (86.0% of 1950 ears). A seasonal effect was found only for schoolchildren, with a significantly lower pass rate in winter than in spring or autumn. There was no difference in pass rates between spring and autumn. Implications for the seasonal effect on TEOAE screening outcomes for infants and schoolchildren are discussed.

Hydrolytic kinetic resolution of terminal mono- and bis-epoxides in the synthesis of insect pheromones: routes to (-)-(R)- and (+)-(S)-10-methyldodecyl acetate, (-)-(R)-10-methyl-2-tridecanone, (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol), (-)-(1R,7R)-1,7-dime

Hydrolytic kinetic resolution (HKR) of functionalised epoxides using (salen)Co(OAc) complexes provides enantiomerically enriched epoxides and diols, which have been transformed into important insect sex pheromones. In this general approach, (-)-(R)- and (+)-(S)-10-methyldodecyl acetates from the smaller tea tortrix moth were obtained, as was (-)-(R)-10-methyltridecan-2-one from the southern corn rootworm. The (S)-epoxide obtained from undec-1-en-6-yne was transformed to (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol) from ant-lions. HKR of appropriate bisepoxides was also investigated, and transformations of the resulting bisepoxides and epoxydiols provided (-)-(1R,7R)-1,7-dimethylnonylpropanoate from corn rootworms, (-)-(6R,12R)-6,12-dimethylpentadecan-2-one from the female banded cucumber beetle, and (-)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane from female pea-midges. (C) 2002 Elsevier Science Ltd. All rights reserved.

Variation in coumarin 7-hydroxylase activity associated with genetic polymorphism of cytochrome P450 2A6 and the body status of iron stores in adult Thai males and females

The relationships between catalytic activity of cytochrome P450 2A6 (CYP2A6), polymorphism of CYP2A6 gene, gender and levels of body iron stores were analysed in a sample group of 202 apparently healthy Thais, aged 1947 years. Eleven individuals were found to have high activity of CYP2A6, judged by the relatively large amounts (11.2-14.6 mg) of 7-hydroyxcoumarin (7-OHC) excreted 3 h following administration of 15 mg of coumarin. Ten individuals, however, did not excrete any 7-OHC. Of these 10, four were found to have no CYP2A6 gene (whole gene deletion; CYP2A6*4 allele). The frequency of the CYP2A6 alleles; *1A, *1B and *4 in the whole sample group was 52, 40 and 8% while the frequency of the CYP2A6 gene types; *1A/* 1A, *1A/* 1B, *1B/* 1B, *1A/* 4, *1BI* 4, *4/* 4 was 29, 41, 16, 7, 5 and 2%. Subjects having CYP2A6* 1A/* 1B gene-type group were found to have higher rates of coumarin 7-hydroxylation compared with those of the CYP2A6* 1B/* 1B and CYP2A6* 1A/* 4 gene types. The inter-individual variability in CYP2A6 catalytic activity was therefore attributed in part to the CYP2A6 genetic polymorphism. Variation in CYP2A6 activity in this sample group was not associated with gender but, interestingly, it did show an inverse association with plasma ferritin; an indicator of body iron stores. Higher rates of coumarin 7-hydroxylation were found in individuals with low body iron stores (plasma ferritin < 20 μg/l) compared with subjects having normal body iron store status. Subjects (n = 16) with iron overload (plasma ferritin > 300 mug/l) also tended to have elevated rates of coumarin 7-hydroxylation. These results suggest an increased CYP2A6 expression in subjects who have excessive body iron stores. Further investigations into the underlying factors that may lead to increased expression of CYP2A6 in association with abnormal body iron stores are currently in progress in our laboratory. Pharmacogenetics 12:241-249 (C) 2002 Lippincott Williams Wilkins.

Outcome of stroke patients admitted to intensive care: Experience from an Australian teaching hospital

The objective of this study was to determine the mortality rate and the functional outcomes of stroke patients admitted to the intensive care unit (ICU) and to identify predictors of poor outcome in this population. The records of all patients admitted to the ICU with the diagnosis of stroke between January 1994 and December 1999 were reviewed. Patients with subarachnoid haemorrhage were excluded. Data were collected on clinical and biological variables, risk factors for stroke and the presence of comorbidities. Mortality (ICU, in-hospital and three-month) and functional outcome were used as end-points. In the six-year-period, 61 patients were admitted to the ICU with either haemorrhagic or ischaemic stroke. Medical records were available for only 58 patients. There were 23 ischaemic and 35 haemorrhagic strokes. The ICU, in-hospital and three-month mortality rates were 36%, 47% and 52% respectively. There were no significant differences in the prevalence of premorbid risk factors between survivors and non-survivors. The mean Barthel score was significantly different between the independent and dependent survivors (94 +/- 6 vs 45 +/- 26, P < 0.001). A substantial number of patients with good functional outcomes had lower Rankin scores (92% vs 11%, P < 0.001). Only 46% of those who were alive at three months were functionally independent. Intensive care admission was associated with a high mortality rate and a high likelihood of dependent lifestyle after hospital discharge. Haemorrhagic stroke, fixed dilated pupil(s) and GCS < 10 during assessment were associated with increased mortality and poor functional outcome.

Longitudinal study of veterinarians from entry to the veterinary course to ten years after graduation: career paths

Objective To map out the career paths of veterinarians during their first 10 years after graduation, and to determine if this could have been predicted at entry to the veterinary course. Design Longitudinal study of students who started their course at The University of Queensland in 1985 and 1986, and who completed questionnaires in their first and fifth year as students, and in their second, sixth and eleventh year as veterinarians. Methods Data from 129 (96%) questionnaires completed during the eleventh year after graduation were coded numerically then analysed, together with data from previous questionnaires, with SAS System 7 for Windows 95. Results Ten years after they graduated, 80% were doing veterinary work, 60% were in private practice, 40% in small animal practice and 18% in mixed practice. The equivalent of 25% of the working time of all females was taken up by family duties. When part-time work was taken into account, veterinary work constituted the equivalent of 66% of the group working full-time. That 66% consisted of 52% on small animals, 7% on horses, 6% on cattle/sheep and 1% on pigs/poultry. Those who had grown up on farms with animals were twice as likely to be working with farm animals as were those from other backgrounds. Forecasts made on entry to the veterinary course were of no value in predicting who would remain in mixed practice. Conclusions Fewer than one-fifth of graduates were in mixed practice after 10 years, but the number was higher for those who grew up on farms with animals. Forecasts that may be made at interview before entry to the course were of little value in predicting the likelihood of remaining in mixed veterinary practice.

The impact of positive peritoneal washings and serosal and adnexal involvement on survival in patients with stage IIIA uterine cancer

Objective. The aim of this study was to determine the prognostic significance of serosal involvement (SER), adnexal involvement (ADN), and positive peritoneal washings (PPW) in patients with Stage IIIA uterine cancer. We also sought to determine patterns of recurrence in patients with this disease. Methods. The records of 136 patients with Stage IIIA uterine cancer treated at the Queensland Centre for Gynecological Cancer between March 1983 and August 2001 were reviewed. One hundred thirty-six patients underwent surgery and 58 (42.6%) had full surgical staging. Seventy-five patients (55.2%) had external beam radiotherapy and/or brachytherapy postoperatively. Overall survival was the primary statistical endpoint. Statistical analysis included univariate and multivariate Cox models. Results. Forty-six patients (33.8%) had adnexal involvement, 23 (16.9%) had serosal involvement, and 40 (29.4%) had positive peritoneal washings. Median follow-up was 55.1 months (95% confidence interval, 36.9 to 73.4 months) after which time 71 patients (52.2%) remained alive. For patients with endometrioid adenocarcinoma, ADN and SER were associated with impaired survival on multivariate analysis (odds ratio 2.8 and 3.2, respectively). In the subgroup of patients with high-risk tumors (including papillary serous carcinomas, clear cell carcinomas, and uterine sarcomas), neither ADN, nor SER, nor PPW influenced survival. Conclusion. Patients with Stage IIIA uterine cancer constitute a heterogeneous group. For patients with endometrioid adenocarcinoma, both ADN and SER, but not PPW, were associated with impaired prognosis. For patients with high-risk histological types, prognosis is poor for all three factors. (C) 2002 Elsevier Science (USA).

Applications of accurate, high-precision Pb isotope ratio measurement by multi-collector ICP-MS

The isotope composition of Ph is difficult to determine accurately due to the lack of a stable normalisation ratio. Double and triple-spike addition techniques provide one solution and presently yield the most accurate measurements. A number of recent studies have claimed that improved accuracy and precision could also be achieved by multi-collector ICP-MS (MC-ICP-MS) Pb-isotope analysis using the addition of Tl of known isotope composition to Pb samples. In this paper, we verify whether the known isotope composition of Tl can be used for correction of mass discrimination of Pb with an extensive dataset for the NIST standard SRM 981, comparison of MC-ICP-MS with TIMS data, and comparison with three isochrons from different geological environments. When all our NIST SRM 981 data are normalised with one constant Tl-205/Tl-203 of 2.38869, the following averages and reproducibilities were obtained: Pb-207/Pb-206=0.91461+/-18; Pb-208/Ph-206 = 2.1674+/-7; and (PbPh)-Pb-206-Ph-204 = 16.941+/-6. These two sigma standard deviations of the mean correspond to 149, 330, and 374 ppm, respectively. Accuracies relative to triple-spike values are 149, 157, and 52 ppm, respectively, and thus well within uncertainties. The largest component of the uncertainties stems from the Ph data alone and is not caused by differential mass discrimination behaviour of Ph and Tl. In routine operation, variation of sample introduction memory and production of isobaric molecular interferences in the spectrometer's collision cell currently appear to be the ultimate limitation to better reproducibility. Comparative study of five different datasets from actual samples (bullets, international rock standards, carbonates, metamorphic minerals, and sulphide minerals) demonstrates that in most cases geological scatter of the sample exceeds the achieved analytical reproducibility. We observe good agreement between TIMS and MC-ICP-MS data for international rock standards but find that such comparison does not constitute the ultimate. test for the validity of the MC-ICP-MS technique. Two attempted isochrons resulted in geological scatter (in one case small) in excess of analytical reproducibility. However, in one case (leached Great Dyke sulphides) we obtained a true isochron (MSWD = 0.63) age of 2578.3 +/- 0.9 Ma, which is identical to and more precise than a recently published U-Pb zircon age (2579 3 Ma) for a Great Dyke websterite [Earth Planet. Sci. Lett. 180 (2000) 1-12]. Reproducibility of this age by means of an isochron we regard as a robust test of accuracy over a wide dynamic range. We show that reliable and accurate Pb-isotope data can be obtained by careful operation of second-generation MC-ICP magnetic sector mass spectrometers. (C) 2002 Elsevier Science B.V. All rights reserved.