Conformations of lasalocid A-lithium complexes in acetonitrile

The interaction of the ionophore antibiotic lasalocid-A with lithium perchlorate in acetonitrile has been studied by circular dichroism (c.d.) and 1H, 13C and 7Li nuclear magnetic resonance (n.m.r.) techniques. Analysis of the c.d. data has shown that both the 2:1 sandwich (ionophore-cation-ionosphore) complex and 1:1 complex coexist in solution. The n.m.r. data are consistent with a conformational model in which the carbonyl oxygen, he tetrahydrofuran and the tetrahydropyran ring oxygen atoms, two hydroxyl group oxygens and either a water or a solvent molecule coordinate to the lithium ion.

Polarized ethylenes: structures of (1,3-dimethyl-2-imidazolidinylidene)malononitrile and (1,3-dimethyl-2-perhydropyrimidinylidene)malononitrile

Crystal structures of the title compounds, (I) and (II), have been determined by three-dimensional diffraction methods. Crystals of CsHIoN 4 (I) are monoclinic, space group P21/a with Z = 4, Mr= 162, a = 7.965 (1), b = 16.232 (2), c = 7.343 (1) A, fl = 113.54 (1) °, V = 890.7 A 3, D,n = 1.218, D x = 1.208 gcm -3, g(Cu Ka, 2 = 1.5418/~) = 6.47 em -1, F(000) = 344. The crystals of C9H12N4 (II) are orthorhombic, space group P21en, with Z = 4, Mr = 176, a = 7.983 (3), b = 8.075 (2), c = 14.652 (3) ./k, V = 944.43/~3, Dm= 1.219, D x = 1.237 g cm -3, #(Mo Ka, ). = 0.7107 ,/k) = 0.868 cm -1, F(000) = 376. Both structures were solved by direct methods and refined to R = 5.8% for (I) and 5.3 % for (II). The C-C double-bond distances are 1.407 (3) in (I) and 1.429 (6)/~ in (II), appreciably longer than normal. The steric and push-pull effects result in rotation about the C=C bond, the rotation angles being 20.2 (3) in (I) and 31.5 (6) o in (II).

Interval Data Classification under Partial Information: A Chance-Constraint Approach

This paper presents a Chance-constraint Programming approach for constructing maximum-margin classifiers which are robust to interval-valued uncertainty in training examples. The methodology ensures that uncertain examples are classified correctly with high probability by employing chance-constraints. The main contribution of the paper is to pose the resultant optimization problem as a Second Order Cone Program by using large deviation inequalities, due to Bernstein. Apart from support and mean of the uncertain examples these Bernstein based relaxations make no further assumptions on the underlying uncertainty. Classifiers built using the proposed approach are less conservative, yield higher margins and hence are expected to generalize better than existing methods. Experimental results on synthetic and real-world datasets show that the proposed classifiers are better equipped to handle interval-valued uncertainty than state-of-the-art.

Pyrolysis and combustion of alpha-cellulose: effect of dihydrazinium phosphate (N2H5)2HPO4

A strip of Whatman filter paper (α-cellulose) dipped in an aqueous solution of dihydrazinium phosphate, (N2H5)2HPO4(DHP), and dried, carbonized without flame when ignited. The observed flame retardancy of DHP on α-cellulose has been studied using TG, DTA and mass spectrometry. Dihydrazinium phosphate appears to catalyze the dehydration of α-cellulose, minimizing the depolymerization which produces flammable tars, with the formation of water and char. Flame retardancy of DHP is compared with that of diammonium phosphate and phosphoric acid.

Polymorphisms in the vascular endothelial growth factor gene and the risk of familial endometriosis

Vascular endothelial growth factor (VEGF) is an endothelial cell-specific angiogenic protein suspected to be involved in the pathogenesis of endometriosis by establishing a new blood supply to the human exfoliated endometrium. Several transcription factor-binding sites are found in the VEGF 5'-untranslated region and variation within the region increases the transcriptional activity. Six previous studies which tested between one and three single nucleotide polymorphisms (SNPs) in samples comprising 105-215 cases and 100-219 controls have produced conflicting evidence for association between the SNPs in the VEGF region and endometriosis. To further investigate the reported association between VEGF variants and endometriosis, we tested the four VEGF polymorphisms (-2578 A/C, rs699947; -460 T/C, rs833061; +405 G/C, rs2010963 and +936 C/T, rs3025039) in a large Australian sample of 958 familial endometriosis cases and 959 controls. We also conducted a literature-based review of all relevant association studies of these VEGF SNPs in endometriosis and performed a meta-analysis. There was no evidence for association between endometriosis and the VEGF polymorphisms genotyped in our study. Combined association results from a meta-analysis did not provide any evidence for either genotypic or allelic association with endometriosis. Our detailed review and meta-analysis of the VEGF polymorphisms suggests that genotyping assay problems may underlie the previously reported associations between VEGF variants and endometriosis.

Cu (DPM)2-initiated vinyl polymerization

The behavior of cupric dipivaloylmethide in vinyl polymerization systems was investigated with a view to understanding the mechanism of polymerization initiation. Results of polymerization reactions together with spectral investigation data are presented. Polymerization in the presence of the chelate proceeds through a free-radical process. The corresponding kinetic and transfer constants and activation energy values suggest a normal propagation step. With the help of spectral data an attempt is made to suggest a plausible mechanism of initiation.

Inheritance of resistance to root-lesion nematodes (Pratylenchus thornei and P. neglectus) in five doubled-haploid populations of wheat

Nematode species Pratylenchus thornei and P. neglectus are the two most important root-lesion nematodes affecting wheat (Triticum aestivum L.) and other grain crops in Australia. For practical plant breeding, it will be valuable to know the mode of inheritance of resistance and whether the same set of genes confer resistance to both species. We evaluated reactions to P. thornei and P. neglectus of glasshouse-inoculated plants of five doubled-haploid populations derived from five resistant synthetic hexpaloid wheat lines, each crossed to the susceptible Australian wheat cultivar Janz. For each cross we determined genetic variance, heritability and minimum number of effective resistance genes for each nematode species. Distributions of nematode numbers for both species were continuous for all doubled-haploid populations. Heritabilities were high and the resistances were controlled by 4-7 genes. There was no genetic correlation between resistance to P. thornei and to P. neglectus in four of the populations and a significant but low correlation in one. Therefore, resistances to P. thornei and to P. neglectus are probably inherited quantitatively and independently in four of these synthetic hexaploid wheat populations, with the possibility of at least one genetic factor contributing to resistance to both species in one of the populations. Parents with the greatest level of resistance will be the best to use as donor parents to adapted cultivars, and selection of resistance to both species in early generations will be optimal to carry resistance through successive cycles of inbreeding to produce resistant cultivars for release.

Light thresholds derived from seagrass loss in the coastal zone of the northern Great Barrier Reef, Australia

There is a world-wide trend for deteriorating water quality and light levels in the coastal zone, and this has been linked to declines in seagrass abundance. Localized management of seagrass meadow health requires that water quality guidelines for meeting seagrass growth requirements are available. Tropical seagrass meadows are diverse and can be highly dynamic and we have used this dynamism to identify light thresholds in multi-specific meadows dominated by Halodule uninervis in the northern Great Barrier Reef, Australia. Seagrass cover was measured at similar to 3 month intervals from 2008 to 2011 at three sites: Magnetic Island (MI) Dunk Island (DI) and Green Island (GI). Photosynthetically active radiation was continuously measured within the seagrass canopy, and three light metrics were derived. Complete seagrass loss occurred at MI and DI and at these sites changes in seagrass cover were correlated with the three light metrics. Mean daily irradiance (I-d) above 5 and 8.4 mol m(-2) d(-1) was associated with gains in seagrass at MI and DI, however a significant correlation (R = 0.649, p < 0.05) only occurred at MI. The second metric, percent of days below 3 mol m(-2) d(-1), correlated the most strongly (MI, R = -0.714, p < 0.01 and DI, R = -0.859, p = <0.001) with change in seagrass cover with 16-18% of days below 3 mol m(-2) d(-1) being associated with more than 50% seagrass loss. The third metric, the number of hours of light saturated irradiance (H-sat) was calculated using literature-derived data on saturating irradiance (E-k). H-sat correlated well (R = 0.686, p <0.01; and DI, R = 0.704, p < 0.05) with change in seagrass abundance, and was very consistent between the two sites as 4 H-sat was associated with increases in seagrass abundance at both sites, and less than 4 H-sat with more than 50% loss. At the third site (GI), small seasonal losses of seagrass quickly recovered during the growth season and the light metrics did not correlate (p > 0.05) with change in percent cover, except for I-d which was always high, but correlated with change in seagrass cover. Although distinct light thresholds were observed, the departure from threshold values was also important. For example, light levels that are well below the thresholds resulted in more severe loss of seagrass than those just below the threshold. Environmental managers aiming to achieve optimal seagrass growth conditions can use these threshold light metrics as guidelines; however, other environmental conditions, including seasonally varying temperature and nutrient availability, will influence seagrass responses above and below these thresholds. (C) 2012 Published by Elsevier Ltd.

Low-frequency electrical stimulation combined with a cooling vest improves recovery of elite kayakers following a simulated 1000-m race in a hot environment

This study compared the effects of a low-frequency electrical stimulation (LFES; Veinoplus® Sport, Ad Rem Technology, Paris, France), a low-frequency electrical stimulation combined with a cooling vest (LFESCR) and an active recovery combined with a cooling vest (ACTCR) as recovery strategies on performance (racing time and pacing strategies), physiologic and perceptual responses between two sprint kayak simulated races, in a hot environment (∼32 wet-bulb-globe temperature). Eight elite male kayakers performed two successive 1000-m kayak time trials (TT1 and TT2), separated by a short-term recovery period, including a 30-min of the respective recovery intervention protocol, in a randomized crossover design. Racing time, power output, and stroke rate were recorded for each time trial. Blood lactate concentration, pH, core, skin and body temperatures were measured before and after both TT1 and TT2 and at mid- and post-recovery intervention. Perceptual ratings of thermal sensation were also collected. LFESCR was associated with a very likely effect in performance restoration compared with ACTCR (99/0/1%) and LFES conditions (98/0/2%). LFESCR induced a significant decrease in body temperature and thermal sensation at post-recovery intervention, which is not observed in ACTCR condition. In conclusion, the combination of LFES and wearing a cooling vest (LFESCR) improves performance restoration between two 1000-m kayak time trials achieved by elite athletes, in the heat.

Exercise and vascular function in child obesity: A meta-analysis

CONTEXT: Conduit artery flow-mediated dilation (FMD) is a noninvasive index of preclinical atherosclerosis in humans. Exercise interventions can improve FMD in both healthy and clinical populations. OBJECTIVE: This systematic review and meta-analysis aimed to summarize the effect of exercise training on FMD in overweight and obese children and adolescents as well as investigate the role of cardiorespiratory fitness (peak oxygen consumption [Vo2peak]) on effects observed. DATA SOURCES: PubMed, Medline, Embase, and Cinahl databases were searched from the earliest available date to February 2015. STUDY SELECTION: Studies of children and/or adolescents who were overweight or obese were included. DATA EXTRACTION: Standardized data extraction forms were used for patient and intervention characteristics, control/comparator groups, and key outcomes. Procedural quality of the studies was assessed using a modified version of the Physiotherapy Evidence Base Database scale. RESULTS: A meta-analysis involving 219 participants compared the mean difference of pre- versus postintervention vascular function (FMD) and Vo2peak between an exercise training intervention and a control condition. There was a significantly greater improvement in FMD (mean difference 1.54%, P < .05) and Vo2peak (mean difference 3.64 mL/kg/min, P < .05) after exercise training compared with controls. LIMITATIONS: Given the diversity of exercise prescriptions, participant characteristics, and FMD measurement protocols, varying FMD effect size was noted between trials. CONCLUSIONS: Exercise training improves vascular function in overweight and obese children, as indicated by enhanced FMD. Further research is required to establish the optimum exercise program for maintenance of healthy vascular function in this at-risk pediatric population.

Theoretical studies on penicillins, penicillin sulphones and their 1-oxa-1-dethia and 1-carba-1-dethia analogues: binding specificities of transeptidases and penicillinases

Empirical potential energy calculations have been carried out to determine the preferred conformations of penicillins and penicillin sulphones and their 1-oxa-1-dethia and 1-carba-1-dethia analogues. With the exception of 1-oxa-1-dethia penicillins, all the other compounds favour C2 and the C3 puckered conformations of their five-membered rings. Replacement of C2 methyl groups by hydrogen atoms as in bisnorpenicillin V or oxidation of sulphur in position 1 as in sulphones, makes the C3 puckered form much less favourable. Addition of an amino-acyl group at the C6 atom, however, makes the C3 puckered form more favoured in penicillin G or V and in 1-carba-1-dethia penicillins. Through the replacement of the sulphur atom at position 1 by an oxygen atom or by a -CH2 group increases the non-planarity of the lactam peptide bond, it significantly affects the relative disposition of the C3 carboxyl group with respect to the β-lactam ring. These conformational differences have been correlated with the biological activities of these compounds. The present study suggests that the conformation of the bicyclic ring system may be more important for initial binding with the crosslinking enzyme(s) involved in the biosynthesis of bacterial cell-wall peptidoglycan and that the mode of binding is influenced by the nature of the side-group at the C6 atom. These studies predict, in agreement with experimental results, that the 1-oxa-1-dethia penicillin nulceus is an inhibitor of penicillianses. The study also suggests that the stereospecificities of the crosslinking enzyme(s) and penicillinases are very similar with regard to the nature of the side-group at the 6 atom and the confirmation of the bicyclic ring system. However, the confirmational requirement for the bicyclic ring system appears to be more specific in the former enzyme than in the latter.

Iron(II, III) complexes with N, N'-DI(2-)Pyridyl Thiourea. Moumlssbauer and other spectroscopic studies

Several iron(II, III) complexes of N, N'-di(2-)pyridyl thiourea have been synthesized. The preparation of the complexes from iron(III) salts proceeds through a reduction of iron(III) to iron(II) followed by a subsequent reoxidation. The Moumlssbauer, electronic and infrared spectra of these complexes have been measured. The results are concordant with the coordination of pyridine nitrogens and thiocarbonyl sulfur yielding polymeric complexes. A variable temperature NMR study of the free ligand shows that two conformation are accessible for it in solution at subambient temperatures.

Planet of the cavendish - understanding the domination

Those seeking to bring change to cultivars sold in the banana markets of the world have encountered major difficulties over the years. Change has been sought because of production difficulties caused by banana diseases such as Fusarium wilt or a desire to invigorate a stagnant market and obtain a competitive advantage by the introduction of diversity of product. Currently the world banana scene is dominated by cultivars from the Cavendish subgroup with their production in excess of 40% of total world production of banana and plantain combined, and in most western countries Cavendish is synonymous with banana. But Cavendish production usually necessitates very regular applications of pesticides, particularly fungicides for Mycosphaerella leaf spots control. So genetic resistance to these and other diseases would be very beneficial to minimizing costs of production, as well as reducing health risks to banana workers and the general population and minimizing impacts on the environment. In recent years, the overall market sales of some crops, such as tomatoes, have increased by providing diversity of cultivars to consumers. Can the same be done for banana? Perhaps a better understanding of how we have arrived at our current situation and the forces that have shaped our preference for Cavendish will allow us to plan more strategic crop improvement research which has enhanced chances of adoption by the banana industries of the world. A scoping study was recently undertaken in Australia to determine the current market opportunity for alternative cultivars and provide a roadmap for the industry to successfully develop this market. A multidisciplinary team reviewed the literature, surveyed the supply chain, analyzed gross margins and conducted consumer and sensory evaluations of 'new' cultivars. This has provided insight on why Cavendish dominates the market, which is the focus of this paper, and we believe will provide a solid foundation for future progress.

Polarized Ethylenes: Structures of (l,3-Dimethyl-2-imidazolidinylidene)malononitrile and (l,3-Dimethyl-2-perhydropyrimidinylidene)malononitrile

Crystal structures of the title compounds, (I) and (II), have been determined by three-dimensional diffraction methods. Crystals of CsHIoN 4 (I) are monoclinic, space group P21/a with Z = 4, Mr= 162, a = 7.965 (1), b = 16.232 (2), c = 7.343 (1) A, fl = 113.54 (1) °, V = 890.7 A 3, D,n = 1.218, D x = 1.208 gcm -3, g(Cu Ka, 2 = 1.5418/~) = 6.47 em -1, F(000) = 344. The crystals of C9H12N4 (II) are orthorhombic, space group P21en, with Z = 4, Mr = 176, a = 7.983 (3), b = 8.075 (2), c = 14.652 (3) ./k, V = 44.43/~3, Dm= 1.219, D x = 1.237 g cm -3, #(Mo Ka, ). = 0.7107 ,/k) = 0.868 cm -1, F(000) = 376. Both structures were solved by direct methods and refined to R = 5.8% for (I) and 5.3 % for (II). The C-C double-bond distances are 1.407 (3) in (I) and 1.429 (6)/~ in (II), appreciably longer than normal. The steric and push-pull effects result in rotation about the C=C bond, the rotation angles being 20.2 (3) in (I) and 31.5 (6) o in (II).