Project description:In the dinuclear title complex, [Cu(2)(C(30)H(38)N(4)O(2))(H(2)O)(2)](ClO(4))(2), the coordination cation has crystallographically imposed twofold rotational symmetry. The Cu(II) ion is five-coordinated by two N and two O atoms from the macrocylic ligand and one O atom from a water mol-ecule, forming a square-pyramidal N(2)O(3) geometry with the water mol-ecule in the apical position. The distance between the two Cu(II) atoms is 3.0930?(5)?Å. Hydrogen bonds between water mol-ecules and between water mol-ecules and perchlorate anions assemble two cations and four anions into discrete supermolecules of S(4) symmetry. Intramolecular O-H?N hydrogen bonds are also observed. The perchlorate anion and the tert-butyl group are disordered over two positions, with occupancies of the major positions of 0.527?(11) and 0.592?(9), respectively.
Project description:(23S)-23,25-Dihydroxycholecalciferol was converted into at least five metabolites in kidney homogenates prepared from 1,25-dihydroxycholecalciferol-treated chickens. One of these has been positively identified as 23,25,26-trihydroxycholecalciferol by u.v.-absorbance analysis, mass spectrometry and chemical formation of derivatives. 23,25,26-Trihydroxycholecaciferol produces 25-hydroxycholecalciferol-26,23-lactone when incubated in chick kidney homogenates.
Project description:The spatial distribution of radiation damage (assayed by increases in atomic B factors) to thaumatin and urease crystals at temperatures ranging from 25 to 300 K is reported. The nature of the damage changes dramatically at approximately 180 K. Above this temperature the role of solvent diffusion is apparent in thaumatin crystals, as solvent-exposed turns and loops are especially sensitive. In urease, a flap covering the active site is the most sensitive part of the molecule and nearby loops show enhanced sensitivity. Below 180 K sensitivity is correlated with poor local packing, especially in thaumatin. At all temperatures, the component of the damage that is spatially uniform within the unit cell accounts for more than half of the total increase in the atomic B factors and correlates with changes in mosaicity. This component may arise from lattice-level, rather than local, disorder. The effects of primary structure on radiation sensitivity are small compared with those of tertiary structure, local packing, solvent accessibility and crystal contacts.
Project description:BackgroundSince the mid-1990s, excess mortality has increased markedly for adults aged 25-44 years in the north compared with the south of England. We examined the underlying causes of this excess mortality and the contribution of socioeconomic deprivation.MethodsMortality data from the Office of National Statistics for adults aged 25-44 years were aggregated and compared between England's five most northern versus five most southern government office regions between Jan 1, 1981, and Dec 31, 2016. Poisson regression models, adjusted for age and sex, were used to quantify excess mortality in the north compared with the south by underlying cause of death (accidents, alcohol related, cardiovascular disease and diabetes, drug related, suicide, cancer, and other causes). The role of socioeconomic deprivation, as measured by the 2015 Index of Multiple Deprivation, in explaining the excess and regional variability was also explored.FindingsA mortality divide between the north and south appeared in the mid-1990s and rapidly expanded thereafter for deaths attributed to accidents, alcohol misuse, and drug misuse. In the 2014-16 period, the northern excess was incidence rate ratio (IRR) 1·47 (95% CI 1·39-1·54) for cardiovascular reasons, 2·09 (1·94-2·25) for alcohol misuse, and 1·60 (1·51-1·70) for drug misuse, across both men and women aged 25-44 years. National mortality rates for cardiovascular deaths declined over the study period but a longstanding gap between north and south persisted (from 33·3 [95% CI 31·8-34·8] in 1981 to 15·0 [14·0-15·9] in 2016 in the north vs from 23·5 [22·3-24·8] to 9·9 [9·2-10·5] in the south). Between 2014 and 2016, estimated excess numbers of death in the north versus the south for those aged 25-44 years were 1881 (95% CI 726-2627) for women and 3530 (2216-4511) for men. Socioeconomic deprivation explained up to two-thirds of the excess mortality in the north (IRR for northern effect reduced from 1·15 [95% CI 1·14-1·15; unadjusted] to 1·05 [1·04-1·05; adjusted for Index of Multiple Deprivation]). By 2016, in addition to the persistent north-south gap, mortality rates in London were lower than in all other regions, with IRRs ranging from IRR 1·13 (95% CI 1·12-1·15) for the East England to 1·22 (1·20-1·24) for the North East, even after adjusting for deprivation.InterpretationSharp relative rises in deaths from cardiovascular reasons, alcohol misuse and drug misuse in the north compared with the south seem to have created new health divisions between England's regions. This gap might be due to exacerbation of existing social and health inequalities that have been experienced for many years. These divisions might suggest increasing psychological distress, despair, and risk taking among young and middle-aged adults, particularly outside of London.FundingMedical Research Council and Wellcome Trust.
Project description:PurposeTo determine inter-observer variability in target volume definition of cervical cancer in radical and adjuvant radiotherapy (RT) settings.MethodsEight physicians contoured CTVs of 2 patients underwent definitive and postoperative RT. Each volume was analyzed using the individual/median volume ratio and generalized conformity index (CIgen). And center of mass (COM) of each contour was calculated. Expert agreement was quantified using an expectation maximization algorithm for Simultaneous Truth and Performance Level Estimation (STAPLE).ResultsFor definitive RT, the individual/median volume ratio ranged from 0.51 to 1.41, and CIgen was 0.531. Mean 3-dimensional distances of average to each COM were 7.8 mm. For postoperative RT setting, corresponding values were 0.65-1.38, 0.563, and 5.3 mm. Kappa value of expert agreement was 0.65 and 0.67, respectively. STAPLE estimates of the sensitivity, specificity, and kappa measures of inter-physician agreement were 0.73, 0.98, and 0.65 for the definitive and 0.75, 0.98, and 0.67 for the adjuvant radiotherapy setting. The largest difference was observed in the superior-inferior direction, particularly in the upper vagina and the common iliac area.ConclusionAs there was still some variability in target delineation, more detailed guidelines for target volume delineation and continuing education would help to reduce this uncertainty.
Project description:The title 22-crown-6 unit, C(26)H(28)O(6), comprising of three benzo groups and triethyl-ene glycol, was prepared by the reaction of ?,?'-dibromo-p-xylene with 1,8-bis-(2-hydroxy-phen-oxy)-3,6-dioxaoctane in the presence of Cs(2)CO(3) with tetra-hydro-furan (THF) and recrystallized from dichloro-methane-hexane (1:20 v/v) at room temperature. In the mol-ecular structure, two O atoms of the central ethyl-ene glycol in the triethyl-ene glycol unit exhibit exo conformations due to intra-molecular C-H?O inter-actions. A number of C-H?O and C-H?? inter-molecular inter-actions contribute to the stabilization of the crystal packing.