Chemical composition and in vitro ruminal fermentation of common tree forages in the semi-arid rangelands of Swaziland

Browse plants play an important role in providing feed for livestock in semi-arid rangelands of Africa. Chemical composition and in vitro ruminal fermentation of leaves collected from Acacia burkei, Acacia tortilis, Acacia nilotica, Dichrostachys cinerea and Ehretia obtusifolia in communal grazing lands in the lowveld of Swaziland is presented. Leaves were collected from trees located on two soil types (i.e., lithosol and vertisol) in the communal land but it had no effect on the chemical composition of tree leaves. The NDFom and ADFom content were highest in D. cinerea and A. burkei and lowest in E. obtusifolia and A. nilotica. Crude protein (CP) contents ranged between 108 g/kg and 122 g/kg DM. D. cinerea had the highest Ca and Mg content, while A. tortilis had the lowest. There were marked variations in K level amongst browse species, with A. tortilis (9.1 g/kg DM) having the highest value. The P, Zn and Fe did not differ between browse species. Soil type and tree species interaction impacted in vitro fermentation parameters. Extent of fermentation, as measured by 48 h cumulative gas production, and organic matter degradability was highest in E. obtusifolia leaves and lowest in D. cinerea leaves within soil type. Fermentation efficiency, as measured by partitioning factors, was highest in A. nilotica leaves. Leaves of E. obtusifolia could be a valuable supplementary feedstuff for ruminant livestock due to its in vitro fermentation characteristics as well as low fibre and moderate CP levels. (c) 2007 Elsevier B.V. All rights reserved.

Chemical characterisation of wild populations of Thymus from different climatic regions in southeast Spain

Thymus is taxonomically a very complex genus with a high frequency of hybridisation and introgression among sympatric species. The variation in accumulation of leaf-surface flavonoids was investigated in 71 wild populations of Thymus front different putative hybrid swarm areas in Andalucia, Spain. Twenty-two flavones, five flavanones, two dihydroflavonols, a flavonol and two unknowns were detected by HPLC-DAD combined with LC-APCI-MS analysis. The majority of compounds were flavones with a lutelin-type substitution of the B-ring, in contrast to previous reports on Macedonian taxa, which predominantly accumulate flavones with apigenin-type substitution of the B-ring. Anatomical and morphometric studies, supported by cluster analysis, identified pure Thymus hyemalis and Thymus baeticus populations, and a large number of putative hybrids. Flavonoid variation was closely related to morphological variation in all populations and is suspected to be a result of genetic polymorphism. Principal component analysis identified the presence of species-specific and geographically linked chemotypes and putative hybrids with mixed morphological and chemical characteristics. Qualitative and quantitative flavonoid accumulation appears to be genetically regulated, while external factors play a secondary role. Flavonoid profiles can thus provide diagnostic markers for the taxonomy of Thymus and are also useful in detecting hybridising taxa. (C) 2007 Elsevier Ltd. All rights reserved.

Environmental oestrogens and breast cancer: long-term low-dose effects of mixtures of various chemical combinations

The incidence of breast cancer has risen worldwide to unprecedented levels in recent decades, making it now the major cancer of women in many parts of the world.1 Although diet, alcohol, radiation and inherited loss of BRCA1/2 genes have all been associated with increased incidence, the main identified risk factors are life exposure to hormones including physiological variations associated with puberty/pregnancy/menopause,1 personal choice of use of hormonal contraceptives2 and/or hormone replacement therapy.3–6 On this basis, exposure of the human breast to the many environmental pollutant chemicals capable of mimicking or interfering with oestrogen action7 should also be of concern.8 Hundreds of such environmental chemicals have now been measured in human breast tissue from a range of dietary and domestic exposure sources7 ,9 including persistent organochlorine pollutants (POPs),10 polybrominated diphenylethers and polybromobiphenyls,11 polychlorinated biphenyls,12 dioxins,13 alkyl phenols,14 bisphenol-A and chlorinated derivatives,15 as well as other less lipophilic compounds such as parabens (alkyl esters of p-hydroxybenzoic acid),16 but studies investigating any association between raised levels of such compounds and the development of breast cancer remain inconclusive.7–16 However, the functionality of these chemicals has continued to be assessed on the basis of individual chemicals rather than the environmental reality of long-term low-dose exposure to complex mixtures. This misses the potential for individuals to have high concentrations of different compounds but with a common mechanism of action. It also misses the complex interactions between chemicals and physiological hormones which together may act to alter the internal homeostasis of the oestrogenic environment of mammary tissue.

Assessing the carcinogenic potential of low-dose exposures to chemical mixtures in the environment: the challenge ahead

Lifestyle factors are responsible for a considerable portion of cancer incidence worldwide, but credible estimates from the World Health Organization and the International Agency for Research on Cancer (IARC) suggest that the fraction of cancers attributable to toxic environmental exposures is between 7% and 19%. To explore the hypothesis that low-dose exposures to mixtures of chemicals in the environment may be combining to contribute to environmental carcinogenesis, we reviewed 11 hallmark phenotypes of cancer, multiple priority target sites for disruption in each area and prototypical chemical disruptors for all targets, this included dose-response characterizations, evidence of low-dose effects and cross-hallmark effects for all targets and chemicals. In total, 85 examples of chemicals were reviewed for actions on key pathways/mechanisms related to carcinogenesis. Only 15% (13/85) were found to have evidence of a dose-response threshold, whereas 59% (50/85) exerted low-dose effects. No dose-response information was found for the remaining 26% (22/85). Our analysis suggests that the cumulative effects of individual (non-carcinogenic) chemicals acting on different pathways, and a variety of related systems, organs, tissues and cells could plausibly conspire to produce carcinogenic synergies. Additional basic research on carcinogenesis and research focused on low-dose effects of chemical mixtures needs to be rigorously pursued before the merits of this hypothesis can be further advanced. However, the structure of the World Health Organization International Programme on Chemical Safety 'Mode of Action' framework should be revisited as it has inherent weaknesses that are not fully aligned with our current understanding of cancer biology.

Astrophysical S factors for fusion reactions involving C, O, Ne, and Mg isotopes

Using the Sao Paulo potential and the barrier penetration formalism we have calculated the astrophysical factor S(E) for 946 fusion reactions involving stable and neutron-rich isotopes of C, O, Ne, and Mg for center-of-mass energies E varying from 2 to approximate to 18-30 MeV (covering the range below and above the Coulomb barrier). We have parameterized the energy dependence, S(E), by an accurate universal 9-parameter analytic expression and present tables of fit parameters for all the reactions. We also discuss the reduced 3-parameter version of our fit which is highly accurate at energies below the Coulomb barrier, and outline the procedure for calculating the reaction rates. The results can be easily converted to thermonuclear or pycnonuclear reaction rates to simulate various nuclear burning phenomena, in particular, stellar burning at high temperatures and nucleosynthesis in high density environments. (C) 2010 Elsevier Inc. All rights reserved

Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Chemical variability within the marine sponge Aplysina fulva

Dibromotyrosine-derived metabolites are of common occurrence within marine sponges belonging to the order Verongida. However, previous chemical analysis of crude extracts obtained from samples of the verongid sponge Aplysina fulva collected in Brazil did not provide any dibromotyrosine-derived compounds. In this investigation, five samples of A. fulva from five different locations along the Brazilian coastline and one sample from a temperate reef in the South Atlantic Bight (SAB) (Georgia, USA) were investigated for the presence of bromotyrosine-derived compounds. All six samples collected yielded dibromotyrosine-derived compounds, including a new derivative, named aplysinafulvin, which has been identified by. analysis of spectroscopic data. These results confirm previous assumptions that dibromotyrosine-derived metabolites can be considered as chemotaxonomic markers of verongid sponges. The isolation of aplysinafulvin provides additional support for a biogenetic pathway involving an arene oxide intermediate in the biosynthesis of Verongida metabolites. It cannot yet be established if the chemical variability observed among the six samples of A.fulva collected in Brazil and the SAB is the result of different environmental factors, distinct chemical extraction and isolation protocols, or a consequence of hidden genetic diversity within the postulated morphological plasticity of this species. (C) 2007 Elsevier Ltd. All rights reserved.

Human Sulfotransferases and Their Role in Chemical Metabolism

Sulfonation is an important reaction in the metabolism of numerous xenobiotics, drugs, and endogenous compounds. A supergene family of enzymes called sulfotransferases (SULTs) catalyze this reaction. In most cases, the addition of a sulfonate moiety to a compound increases its water solubility and decreases its biological activity. However, many of these enzymes are also capable of bioactivating procarcinogens to reactive electrophiles. In humans three SULT families, SULT1, SULT2, and SULT4, have been identified that contain at least thirteen distinct members. SULTs have a wide tissue distribution and act as a major detoxification enzyme system in adult and the developing human fetus. Nine crystal structures of human cytosolic SULTs have now been determined, and together with site-directed mutagenesis experiments and molecular modeling, we are now beginning to understand the factors that govern distinct but overlapping substrate specificities. These studies have also provided insight into the enzyme kinetics and inhibition characteristics of these enzymes. The regulation of human SULTs remains as one of the least explored areas of research in the field, though there have been some
recent advances on the molecular transcription mechanism controlling the individual SULT promoters. Interindividual variation in sulfonation capacity may be important in determining an individual’s response to xenobiotics, and recent studies have begun to suggest roles for SULT polymorphism in disease susceptibility. This review aims to provide a summary of our present understanding of the function of human cytosolic sulfotransferases.

Chemical, biological and radiological incidents : preparedness and perceptions of emergency nurses

Despite their important role in chemical, biological and radiological (CBR) incident response, little is known about emergency nurses' perceptions of these events. The study aim was to explore emergency nurses' perceptions of CBR incidents and factors that may influence their capacity to respond. Sixty-four nurses from a metropolitan Emergency Department took part. The majority were willing to participate in CBR incidents and there was a positive association between willingness to participate and postgraduate qualification in emergency nursing. Willingness decreased, however, with unknown chemical and biological agents. One third of participants reported limitations to using personal protective equipment. Few participants had experience with CBR incidents although 70.3 per cent of participants had undergone CBR training. There were significant differences in perceptions of choice to participate and adequacy of training between chemical, biological and radiological incidents. The study results suggest that emergency nurses are keen to meet the challenge of CBR incident response.

Chemical modification of timber decking : assessing the parameters of acceptability

The criteria for accepting or rejecting a technology extend beyond the intrinsic properties of the finished product such as physical performance. There are also extrinsic factors such as the history of the product and trust in the manufacturers and suppliers, as well as the perceptions and risk management strategies of various stakeholder groups. A methodology was trialled to take into account the extended supply chain of the product, while simultaneously engaging stakeholders to determine and to understand their perceptual frameworks. Three pine decking products manufactured using different amounts and types of chemical modification were compared using life cycle assessment and the comments of 114 respondents from six stakeholder groups in New Zealand. The results of the perceptual research include a quadrant diagram which allows a visual comparison of the responses of different stakeholders to actual or hypothetical products, aiding the identification of when and why certain technologies may be disqualified from acceptability or become the topic of public debate.

Effects of dietary constituents on coronary heart disease risk factors

Coronary Heart Disease (CHD) is a major cause of death in Western countries. Mediterranean and Asian populations have a lower risk of death from CHD compared to Westernised population, as do vegetarian versus omnivorous populations. Dietary constituents of traditional diets consumed by these populations are thought to influence both the classical risk factors for CHD, and the more recently identified risk factors, such as oxidative modification of low density lipoprotein (LDL), LDL particle size, arterial compliance and haemostatic factors. The aim of this thesis was to examine the effects of several food components, particularly soybean and monounsaturated fat (MUFA), on CHD risk factors through 3 carefully controlled dietary interventions, and a cross-sectional study. A randomised crossover dietary intervention study was conducted in 42 healthy males to investigate the effect on CHD risk factors of replacing lean meat with tofu, a soybean product regularly consumed by Asian populations, while controlling all other dietary factors. The tofu diet resulted in significantly lower total cholesterol and triacylglycerol levels compared to the lean meat diet, and LDL particles that were more resistant to in vitro oxidative modification. However, insulin, fibrinogen, factor VII, and lipoprotein (a) were not significantly different on the 2 diets. A postprandial study was subsequently conducted to investigate any acute effects of a tofu test meal on the oxidative modification of LDL in 16 male subjects. There was no significant difference between the susceptibility of LDL to oxidative modification before and after the tofu meal. Twenty eight healthy subjects completed a separate randomised crossover dietary intervention comparing a high MUFA fat diet, using an Australian high oleic sunflower oil, with a low fat, high carbohydrate diet on CHD risk factors. The high MUFA oil diet significantly increased high density lipoprotein cholesterol compared to the low fat diet as well as producing LDL that were more resistant to oxidative modification. Neither the size of the LDL particle nor arterial compliance were significantly different on the 2 diets. Twelve matched pairs of vegetations and omnivores were also studies to compare the habitual diet of a low and higher risk population group, to compare their risk factors and identify dietary constituents that may explain the differences. The vegetarians consumed less saturated fat (SFA) and dietary cholesterol while consuming more polyunsaturated fat, dietary fibre and vitamin E compared to omnivores. The vegetarians had lower total cholesterol, LDL cholesterol and triacylglycerol levels compared to the omnivores and had LDL particles that were more resistant to in vitro oxidation. These findings contribute to our knowledge about the dietary constituents that can alter some CHD risk factors in healthy subjects, and which could reduce the risk of developing CHD. Investigations in high risk groups might reveal even more benefits.

Stress response of juvenile rainbow trout (Oncorhynchus mykiss)to chemical cues released from stressed conspecifics

The objective of this study was to determine whether exposure of rainbow trout (Oncorhynchus mykiss) to water containing a stressed trout or skin extract from stressed and non-stressed trout would elicit a stress response in conspecifics. Juvenile rainbow trout were exposed for 1 hour to water containing a stressed fish, homogenized skin extracts from a non-stressed fish, skin extract from a stressed fish and water with none of these factors. The stress response was measured over a 24-h period (1, 6, 12, 24 h after exposure). Plasma cortisol levels increased at 12 h in fish exposed to water from a stressed fish and skin extract from a stressed fish. Plasma glucose and hepatic hsp70 levels were not affected by treatments. The results suggest that rainbow trout elicit a stress response when exposed to stress-related alarm cues released from conspecifics.

Estimating hydrogen sulphide dissipation rate constant under the influence of different chemical dosing

Sewer odour and corrosion is caused by the reduction of sulphide ions and the release of hydrogen sulphide gas (H2S) into the sewer atmosphere. The reduction of sulphide is determined by its dissipation rate which depends on many processes such as emission, oxidation and precipitation that prevail in wastewater environments. Two factors that mainly affect the dissipation of sulphide are sewer hydraulics and wastewater characteristics; modification to the latter by dosing certain chemicals is known as one of the mitigation strategies to control the dissipation of sulphide. This study investigates the dissipation of sulphide in the presence of NaOH, Mg(OH)2, Ca(NO3)2 and FeCl3 and the dissipation rate is developed as a function of hydraulic parameters such as the slope of the sewer and the velocity gradient. Experiments were conducted in a 18m experimental sewer pipe with adjustable slope to which, firstly no chemical was added and secondly each of the above mentioned chemicals was supplemented in turn. A dissipation rate constant of 2×10^-6 for sulphide was obtained from experiments with no chemical addition. This value was then used to predict the sulphide concentration that was responsible for the emission of H2S gas in the presence of one of the above mentioned four chemicals. It was found that the performance of alkali substances (NaOH and Mg(OH)2) in suppressing the H2S gas emission was excellent while ferric chloride showed a moderate mitigating effect due to its slow reaction kinetics. Calcium nitrate was of little value since the wastewater used in this study experienced almost no biological growth. Thus the effectiveness of selected chemicals in suppressing H2S gas emission had the following order: NaOH ≥ Mg(OH)2 ≥ FeCl3 ≥ Ca(NO3)2.