Detailed H-1 and C-13 NMR structural assignment and relative stereochemistry determination for three closely related sesquiterpene lactones

A complete analysis of H-1 and C-13 NMR spectra of the trypanocidal sesquiterpene lactone eremantholide C and two of its analogues is described. These structurally similar sesquiterpene lactones were submitted to H-1 NMR, C-13 (H-1) NMR, gCOSY, gHSQC, gHMBC, J-resolved and DPFGSE-NOE NMR techniques. The detailed analysis of those results, correlated to some computational calculations (molecular mechanics), led to the total and unequivocal assignment of all H-1 and C-13 NMR data. The determination of all H-1/H-1 coupling constants and all signal multiplicities, together with the elimination of previous ambiguities were also achieved. Copyright (C) 2008 John Wiley & Sons, Ltd.

The cuticular hydrocarbons profiles in the stingless bee Melipona marginata reflect task-related differences

Members of social insect colonies employ a large variety of chemical signals during their life. Of these, cuticular hydrocarbons are of primary importance for social insects since they allow for the recognition of conspecifics, nestmates and even members of different castes. The objectives of this study were (1) to characterize the variation of the chemical profiles among workers of the stingless bee Melipona marginata, and (2) to investigate the dependence of the chemical profiles on the age and on the behavior of the studied individuals. The results showed that cuticular hydrocarbon profiles of workers were composed of alkanes, alkenes and alkadienes that varied quantitatively and qualitatively according to function of workers in the colony. (C) 2010 Elsevier Ltd. All rights reserved.

Ca(2+) binding to c-state of adenine nucleotide translocase (ANT)-surrounding cardiolipins enhances (ANT)-Cys(56) relative mobility: A computational-based mitochondrial permeability transition study

The oxidation of critical cysteines/related thiols of adenine nucleotide translocase (ANT) is believed to be an important event of the Ca(2+)-induced mitochondrial permeability transition (MPT), a process mediated by a cyclosporine A/ADP-sensitive permeability transition pores (PTP) opening. We addressed the ANT-Cys(56) relative mobility status resulting from the interaction of ANT/surrounding cardiolipins with Ca(2+) and/or ADP by means of computational chemistry analysis (Molecular Interaction Fields and Molecular Dynamics studies), supported by classic mitochondrial swelling assays. The following events were predicted: (i) Ca(2+) interacts preferentially with the ANT surrounding cardiolipins bound to the H4 helix of translocase, (ii) weakens the cardiolipins/ANT interactions and (iii) destabilizes the initial ANT-Cys(56) residue increasing its relative mobility. The binding of ADP that stabilizes the conformation ""m"" of ANT and/or cardiolipin, respectively to H5 and H4 helices, could stabilize their contacts with the short helix h56 that includes Cys(56), accounting for reducing its relative mobility. The results suggest that Ca(2+) binding to adenine nucleotide translocase (ANT)-surrounding cardiolipins in c-state of the translocase enhances (ANT)-Cys(56) relative mobility and that this may constitute a potential critical step of Ca(2+)-induced PTP opening. (C) 2009 Elsevier B.V. All rights reserved.

A new thrombospondin-related anonymous protein homologue in Neospora caninum (NcMIC2-like1)

Neospora caninum is an Apicomplexan protozoan that has the dog as a definitive host and cattle (among other animals) as intermediate hosts. It causes encephalopathy in dogs and abortion in cows, with significant loss in worldwide livestock. As any Apicomplexan, the parasite invades the cells using proteins contained in the phylum-specific organelles, like the micronemes, rhoptries and dense granules. The aim of this study was the characterization of a homologue (denominated NcMIC2-like1) of N. caninum thrombospondin-related anonymous protein (NcMIC2), a micronemal protein previously shown to be involved in the attachment and connection with the intracellular motor responsible for the active process of invasion. A polyclonal antiserum raised against the recombinant NcMIC2-like1 functional core (thrombospondin and integrin domains) recognized the native form of NcMIC2-like1, inhibited the in vitro invasion process and localized NcMIC2-like1 at the apical complex of the parasite by confocal immunofluorescence, indicating its micronemal localization. The new molecule, NcMIC2-like1, has features that differentiates it from NcMIC2 in a substantial way to be considered a homologue dagger.

The effect of organisational culture perceptions on the relationship between budgetary participation and managerial job-related outcomes

The impact of managers' perceptions of their organizational culture (OC) on the relationship between budgetary participation (BP) and managerial job-related outcomes, operationalized as managerial performance and job-related tension (JRT) is examined. Data supported predictions that increasing BP would lower JRT for managers perceiving a high emphasis on innovation within their OC, regardless of their perceptions of an emphasis on attention to detail. When managers perceived low innovation, however, their perception of level of attention to detail had a significant effect on the relationship between BP and JRT.

Employee adjustment to large-scale organisational change

The present study was designed to test the utility of a stress-coping model of employee adjustment to organisational change. Specifically, it was proposed that employee adjustment to this type of work stress would be influenced by the characteristics of the change situation, employees' appraisals of the situation, their coping strategies, and the extent of their personal resources. Data were collected from 140 middle managers and supervisors involved in a large-scale public sector integration. The results of the research provided some support for the proposed model: high levels of psychological distress were related to a reliance on informal sources of information, high appraised stress, low appraised certainty, and the use of avoidant rather than problem-focused strategies, whereas poor social functioning was associated with low self-esteem, high levels or disruption across the period of change, a reliance on informal sources of information, and the use of avoidant coping strategies. There was no evidence that coping strategies mediated the effects of the event characteristics, situational appraisals, and personal resources on adjustment; however, there was some evidence linking these variables to coping strategies, in particular, problem-focused coping. There was also some evidence to indicate that the experience of organisational change was different for managers and supervisors: levels of threat were higher for the managers than the supervisors, but there was no difference between the groups of employees in terms of adjustment.

Cyclic peroxides and related norterpenes from a southern Australian marine sponge, Mycale sp.

Investigation of a southern Australian marine sponge, Mycale sp., resulted in isolation of the known norsesterterpenes 1-3 as well as two new isomeric norsesterterpenes, mycaperoxide C methyl ester (4) and mycaperoxide D methyl ester (5), and six new norterpenes (6-11).

Young children, adolescents and alcohol - Part I: Exploring knowledge and awareness of alcohol and related issues

This article explores young children's and adolescents' views pertaining to: knowledge and awareness of alcohol and alcohol related issues; social situations in which. alcohol use is present; orientation to alcohol risk; perceived and actual alcohol use; social image and reputation; and short and long term health beliefs in relation to alcohol. Forty focus groups were conducted with 240 primary school students (118 males and 122 females) and 24 focus groups were conducted with 192 high school students (90 males and 102 females); the total being 64 focus groups comprising 432 school students. Participants ages ranged from five years three months to 16 years 10 months. The videotaped discussions revealed that approximately 75% of the primary school-aged children and almost all of the high school students reported that they had tasted alcohol. Parents were primarily responsible for providing the alcohol. Virtually all participants recognised and were able to correctly name a selection of alcoholic and non-alcoholic beverages, and levels of knowledge and awareness of the health and safety aspects of alcohol were relatively mixed. Presentation of bottles and cans was reported as being important in attracting young persons. These data suggest there is an urgent need for research addressed to the development of prevention/intervention education curriculum materials for use with primary school-aged children.

Mycaperoxides F and G and a related norterpene ketone from southern Australian marine sponges, Mycale species

Investigation of two southern Australian marine sponges, Mycale spp., resulted in isolation of the known norsesterterpene mycaperoxide F methyl ester (5) together with a new norsesterterpene mycaperoxide G methyl ester (10) and a new norterpene ketone 11. All structures were secured by spectroscopic analysis and chemical derivatization. The absolute stereochemistry previously assigned to 5 by application of the Horeau procedure has been revised by application of the Mosher procedure.

Coalbed methane sorption related to coal composition

Gas sorption by coal is closely related to its physical and chemical properties, which are, in turn, governed by coal type and rank. The role of coal type (sensu maceral composition) is not fully established but it is clear that coal type may affect both adsorption capacity and desorption rate. Adsorption capacity is closely related to micropore (pores <2 nm) development, which is rank and maceral dependent. Adsorption isotherms indicate that in most cases bright (vitrinite-rich) coals have a greater adsorption capacity than their dull (often inertinite-rich) equivalents. However, no differences, or even the opposing trend, may be observed in relation to coal type. Desorption rate investigations have been performed using selected bright and dull coal samples in a high pressure microbalance. Interpretation of results using unipore spherical and bidisperse pore models indicate the importance of the pore structure. Bright, vitrinite-rich coals usually have the slowest desorption rates which is associated with their highly microporous structure. However, rapid desorption in bright coals may be related to development of extensive, unmineralised fracture systems. Both macro-and micro-pore systems are implicated in the more rapidly desorbing dull coals. Some dull, inertinite-rich coals may rapidly desorb due to a predominance of large, open cell lumina. Mineral matter is essentially nonadsorbent to coal gases and acts as a simple diluent. However, mineral-rich coals may be associated with more rapid desorption. Coal rank and type (maceral composition) per se do not appear to be the critical factors in controlling gas sorption, but rather the influence they exert over pore structure development. (C) 1998 Elsevier Science B.V.

Methadone maintenance and drug-related crime

Using data from an evaluation of methadone maintenance treatment, this study investigated factors associated with continued involvement irt crime during treatment, and in particular whether there appeared to be differences in effectiveness of treatment between different methadone clinics. The methodology was an observational study, in which 304 patients attending three low-intervention, private methadone clinics in Sydney were interviewed on three occasions over a twelve month period. Outcome measures were self-reported criminal activity and police department records of convictions. By self-report, crime dropped, promptly and substantially on entry to treatment, to a level of acquisitive crime about one-eighth that reported during the last addiction period. Analysis of official records indicated that rates of acquisitive convictions were significantly lower in the in-treatment period compared to prior to entry to treatment, corroborating the changes suggested by self-report. Persisting involvement in crime in treatment was predicted by two factors: the cost of persisting use of illicit drugs, particularly cannabis, and ASPD symptom count. Treatment factors also were independently predictive of continued involvement in crime. By both self-report and official records, and adjusting for subject factors, treatment at one clinic teas associated with greater involvement in crime. This clinic operated in a chaotic and poorly organized way. it is concluded that crime during methadone treatment is substantially lower than during street addiction, although the extent of reduction depends on the quality of treatment being delivered.

Health-related quality of life in Australian children with asthma: lessons for the cross-cultural use of quality of life instruments

The development of Australian forms of the Childhood Asthma Questionnaires (CAQs) is reported. Focus group methods and psychometric analyses were used to establish the conceptual, semantic and technical equivalence of these forms with the UK versions. Both versions also provide for data collection from non-asthmatic youngsters. The internal consistency was found to be acceptable (Cronbach's alpha 0.52-0.90) and the health-related quality of life (HRQoL) scores were found to vary with asthma severity (p < 0.05). Comparison with the UK data revealed that the non-asthmatic scores were higher for Australian than British children (p < 0.001) but that the scores for children with asthma did not differ between the two countries. It was only In the Australian sample that the group with asthma reported impaired HRQoL when compared to their healthy peers. These findings were interpreted in the context of cultural expectations of life quality and conclusions are presented regarding the importance of the gap between experience and expectations. The difficulties raised by the developmental and cultural issues inherent in paediatric HRQoL research were discussed. Qual. Life Res. 7:409-419 (C) 1998 Kluwer Academic Publishers

H-ras activation is an early event in the ptaquiloside-induced carcinogenesis: Comparison of acute and chronic toxicity in rats

Bracken fern (Pteridium spp.) produces cancer of the urinary bladder and oesophagus in grazing animals and is a suspected human carcinogen, The carcinogenic principle ptaquiloside (PT), when activated to a dienone (APT), forms DNA adducts which eventually leads to tumor. Two groups of female Sprague-Dawley rats were given a chronic dose of 3 mg APT weekly for 10 weeks either by intravenous (iv) tail vein or by intragastric (ig) route, A third group was given a weekly dose of 6 mg of APT for 3 weeks by the ig route corresponding to acute dosing. Both chronic iv and ig dosed animals showed ischemic tubular necrosis in the kidney but only iv dosed animals developed adenocarcinomas of the mammary glands. Acutely dosed ig animals produced apoptotic bodies in the liver, necrosis of blood cell precursors in the bone marrow and ischemic tubular necrosis in the kidney but they did not develop tumors, No mutations were found in the H-ras and p53 genes in the mammary glands of either the ig rats or the tumor-bearing iv rats. However, the mammary glands of a fourth group of rats, which received APT by iv and killed before tumor development, carried Pu to Pu and Pu to Py double mutations in codons 58 and 59 of H-ras. This study indicates that the route of administration plays a role in the nature of the disease expression from ptaquiloside exposure. In addition to confirming the role of APT in the PT-induced carcinogenesis our finding suggests that activation of H-ras is an early event in the PT-carcinogenesis model. (C) 1998 Academic Press.

Relation of TNF-related apoptosis-inducing ligand (TRAIL) receptor and FLICE-inhibitory protein expression to TRAIL-induced apoptosis of melanoma

Past studies have shown that apoptosis mediated by TNF-related apoptosis-inducing ligand (TRAIL) is regulated by the expression of two death receptors [TRAIL receptor 1 (TRAIL-RI) and TRAIL-R2] and two decoy receptors (TRAIL-R3 and TRAIL-R4) that inhibit apoptosis, In previous studies, me have shown that TRAIL but not other members of the tumor necrosis factor family induce apoptosis in approximately two-thirds of melanoma cell lines. Here, we examined whether the expression of TRAIL-R at the mRNA and protein level in a panel of 28 melanoma cell lines and melanocytes correlated with their sensitivity to TRAIL-induced apoptosis, We report that at least three factors appear to underlie the variability in TRAIL-induced apoptosis. (a) Pour of nine cell lines that were insensitive to TRAIL-induced apoptosis failed to express death receptors, and in two instances, lines were devoid of all TRAIL-Rs. Southern analysis suggested this was due to loss of the genes for the death receptors, (b) Despite the presence of mRNA for the TRAIL-R, some of the lines failed to express TRAIL-R protein on their surface. This was evident for TRAIL-RI and more so for the TRAIL decoy receptors TRAIL-R3 and -R4, Studies on permeabilized cells revealed that the receptors were located within the cytoplasm and redistribution from the cytoplasm may represent a posttranslational control mechanism. (c) Surface expression of TRAIL-RI and -R2 (but not TRAIL-R3 and -R4) showed an overall correlation with TRAIL-induced apoptosis. However, certain melanoma cell lines and clones were relatively resistant to TRAIL-induced apoptosis despite the absence of decoy receptors and moderate levels of TRAIL-RI and -R2 expression. This may indicate the presence of inhibitors within the cells, but resistance to apoptosis could not be correlated with expression of the caspase inhibitor FLICE-inhibitory protein. mRNA for another TRAIL receptor, osteoprotegerin, was expressed in 22 of the melanoma lines but not on melanocytes. Its role in induction of apoptosis remains to be studied. These results appear to have important implications for future clinical studies on TRAIL.

Differentiation of soil properties related to the spatial association of wheat roots and soil macropores

Under certain soil conditions, e.g. hardsetting clay B-horizons of South-Eastern Australia, wheat plants do not perform as well as would be expected given measurements of bulk soil attributes. In such soils, measurement indicates that a large proportion (80%) of roots are preferentially located in the soil within 1 mm of macropores. This paper addresses the question of whether there are biological and soil chemical effects concomitant with this observed spatial relationship. The properties of soil manually dissected from the 1-3 mm wide region surrounding macropores, the macropore sheath, were compared to those that are measured in a conventional manner on the bulk soil. Field specimens of two different soil materials were dissected to examine biological differentiation. To ascertain whether the macropore sheath soil differs from rhizosphere soil, wheat was grown in structured and repacked cores under laboratory conditions. The macropore sheath soil contained more microbial biomass per unit mass than both the bulk soil and the rhizosphere. The bacterial population in the macropore sheath was able to utilise a wider range of carbon substrates and to a greater extent than the bacterial population in the corresponding bulk soil. These differences between the macropore sheath and bulk soil were almost non-existent in the repacked cores. Evidence for larger numbers of propagules of the broad host range fungus Pythium in the macropore sheath soil were also obtained.