Temperature dependent high-resolution infrared photoabsorption cross-sections of trifluoromethyl sulphur pentafluoride

Absolute infrared photoabsorption cross-sections have been measured over the range 600-1500 cm(-1) for the powerful greenhouse gas SF5CF3 at high resolution (0.03 cm(-1)) and at temperatures between 203 and 298 K. Our data indicate that the integrated absorption intensity shows a weak negative dependence on temperature. It is concluded therefore that previous calculations of radiative forcings and global warming potentials based on room-temperature data are reasonable estimates for the atmosphere, but may be low by a few percent. (C) 2002 Elsevier Science B.V. All rights reserved.

The adsorption geometry of sulphur on Ir{100}: a quantitative LEED study

A quantitative low energy electron diffraction (LEED) analysis has been performed for the p(2 x 2)-S and c(2 x 2)-S surface structures formed by exposing the (1 x 1) phase of Ir{100} to H2S at 750 K. S is found to adsorb on the fourfold hollow sites in both structures leading to Pendry R-factor values of 0.17 for the p(2 x 2)-S and 0.16 for the c(2 x 2)-S structures. The distances between S and the nearest and next-nearest Ir atoms were found to be similar in both structures: 2.36 +/- 0.01 angstrom and 3.33 +/- 0.01 angstrom, respectively. The buckling in the second substrate layer is consistent with other structural studies for S adsorption on fcc{100} transition metal surfaces: 0.09 angstrom for p(2 x 2)-S and 0.02 angstrom for c(2 x 2)-S structures. The (1 x 5) reconstruction, which is the most stable phase for clean Ir{100}, is completely lifted and a c(2 x 2)-S overlayer is formed after exposure to H,S at 300 K followed by annealing to 520 K. CO temperature-programmed desorption (TPD) experiments indicate that the major factor in the poisoning of Ir by S is site blocking. (c) 2005 Elsevier B.V. All rights reserved.

Towards the total synthesis of colletofragarones: constructing the macrocyclic lactone by high pressure-mediated intramolecular Diels-Alder reaction

We report herein an intramolecular Diels-Alder approach towards the construction of the macrocyclic lactone ring and the perhydrobenzofuran system of the colletofragarones, novel metabolites produced by fungi of the genus Colletotrichum that are responsible for inhibition of germination of the conidia in these species. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

Convenient route to enantiopure aryl cyclopentanes via Diels-Alder reaction of asymmetric dienes. Total synthesis of (+)-herbertene and (+)-cuparene

A general route for the synthesis of highly substituted aryl cyclopentanes has been developed involving Diels-Alder reaction of asymmetric dienes prepared from (+)-camphoric acid followed by aromatization of the resulting cyclohexene derivatives. Employing this protocol enantiospecific synthesis of (+)-herbertene and (+)-cuparene has been accomplished. (C) 2003 Elsevier Science Ltd. All rights reserved.

A stereocontrolled total synthesis of methyl (+/-)-O-methylpodocarpate

A stereocontrolled total synthesis of methyl (+/-)-O-methyl podocarpate (4) has been successfully accomplished using the trans-fused diester 21 as a key intermediate. Intramolecular Michael reaction of the enone-diester 18 afforded the cis-fused keto-diester 19 in high yield which was stereoselectively converted into 21 via the enone 20. (C) 2003 Elsevier Science Ltd. All rights reserved.

Determination of the total antioxidant activity of fruits and vegetables by a liposome assay

The effects of mixtures of antioxidants on the oxidation of phospholipids have been investigated in large unilamellar liposomes following initiation by 2,2'-azobis(2-aminopropane) dihydrochloride. The lag phase increased linearly with antioxidant concentration. The lag phases of mixtures containing alpha-tocopherol with ascorbic acid showed synergy between the antioxidants, but mixtures of beta-carotene with cc-tocopherol or ascorbic acid were not synergistic. The liposome system was used to investigate the total antioxidant activity of lipid- and water-soluble extracts from 16 samples of fruits, vegetables, and related food products. The water-soluble extracts caused greater increases in lag phase than the lipid-soluble extracts. The lag phase of liposomes containing the water-soluble extracts from fruits and vegetables increased linearly with the total phenolic concentration, with the continental salad extract having the longest lag phase. The lipid-soluble extract from apples caused the largest increase in lag phase of the lipid-soluble extracts. The lag phases of the lipid-soluble and water-soluble extracts of all fruits and vegetables studied were additive, but no synergy was detected. The lag phase of the liposomes containing both the water-soluble and lipid-soluble extracts varied from 611.5 min for the continental salad extracts to 47.5 min for the cauliflower extracts.

Consumption of soy isoflavones does not affect plasma total homocysteine or asymmetric dimethylarginine concentrations in healthy postmenopausal women

Postmenopausal women are at increased risk for cardiovascular disease because many risk factors are aggravated by menopause. Phytoestrogens may modulate risk factors favorably, involving mechanisms similar to estrogen. The effect of phytoestrogens on the atherogenic amino acids homocysteine and asymmetric dimethylarginine (ADMA) was investigated in a controlled intervention study in healthy postmenopausal women. A multicenter, double-blind, crossover intervention trial in 89 postmenopausal women from Denmark, Germany, and the UK was performed. Subjects consumed fruit cereal bars with or without soy isoflavones (50 mg/d) for 8 wk each with an 8-wk washout period in between. Urinary phytoestrogens increased significantly after isoflavone intervention (P < 0.001). lsoflavone supplementation did not affect plasma total homocysteine or ADMA. For homocysteine, changes from baseline were 0.32 mu mol/L (range: -0.31-0.92; 95% Cl 0.13-0.72), and 0.29 mu mol/L (range: 0.45-1.09;95% Cl 0.01-0.63, P = 0.286) for isoflavone treatment and placebo, respectively. For ADMA concentrations, changes from baseline were -0.02 mu mol/L (range: -0.08-0.03; 95% Cl -0.04-0.01, and 0.00 mu mol/L (range: 0,05-0.03: 95% Cl -0.03-0.01, P = 0.397) for isoflavone treatment and placebo, respectively, There was no association between plasma total homocysteine and ADMA. Changes from baseline in plasma ADMA and folate were negatively correlated (r= -0.18, P = 0.017). These results challenge the overall health effect of isoflavone supplementation in healthy postmenopausal women.

Selenium supplementation of lactating dairy cows: effects on milk production and total selenium content and speciation in blood, milk and cheese

Forty multiparous Holstein cows were used in a 16-week continuous design study to determine the effects of either selenium (Se) source, selenised yeast (SY) (derived from a specific strain of Saccharomyces cerevisiae CNCM 1-3060) or sodium selenite (SS), or Se inclusion rate in the form of SY in the diets of lactating dairy cows on the Se concentration and speciation in blood, milk and cheese. Cows received ad libitum a total mixed ration (TMR) with a 1 : 1 forage: concentrate ratio on a dry matter (DM) basis. There were four diets (T-1 to T-4), which differed only in either source or dose of Se additive. Estimated total dietary Se for T, (no supplement), T-2 (SS), T-3 (SY) and T-4 (SY) was 0.16, 0.30, 0.30 and 0.45 mg/kg DM, respectively. Blood and milk samples were taken at 28-day intervals and at each time point there were positive linear effects of Se in the form of SY on the Se concentration in blood and milk. At day 112 blood and milk Se values for T-1 to T-4 were 177, 208, 248 and 279 +/- 6.6 and 24, 38, 57 and 72 +/- 3.7 ng/g fresh material, respectively, and indicate improved uptake and incorporation of Se from SY. In whole blood, selenocysteine (SeCys) was the main selenised amino acid and the concentration of selenomethionine (SeMet) increased with the increasing inclusion rate of SY In milk, there were no marked treatment effects on the SeCys content, but Se source had a marked effect on the concentration of SeMet. At day 112 replacing SS (T-2) with SY (T-3) increased the SeMet concentration of milk from 36 to 111 ng Se/g and its concentration increased further to 157ng Se/g dried sample as the inclusion rate of SY increased further (T-4) to provide 0.45 mg Se/kg TMR. Neither Se source nor inclusion rate affected the keeping quality of milk. At day 112 milk from T-1, T-2 and T-3 was made into a hard cheese and Se source had a marked effect on total Se and the concentration of total Se comprised as either SeMet or SeCys. Replacing SS (T-2) with SY (T-3) increased total Se, SeMet and SeCys content in cheese from 180 to 340 ng Se/g, 57 to 153 ng Se/g and 52 to 92 ng Se/g dried sample, respectively. The use of SY to produce food products with enhanced Se content as a means of meeting the Se requirements is discussed

Interaction of sulphur-containing aroma compounds with proteins in both model systems and real food systems

Irreversible binding of key flavour disulphides to ovalbumin has been shown previously to occur in model systems. The extent of binding is determined by the availability of the sulphydryl groups to participate in disulphide exchange, influenced either by pH, or the state of the protein (native or heat-denatured). In this study, two further proteins, one with sulphydryl groups available in the native state (beta-lactoglobulin) and one with no sulphydryl groups in the native state (lysozyme) were used to confirm this hypothesis. When the investigation was extended to real food systems, a similar effect was shown when a commercial meat flavouring containing disulphides was added to heat-denatured ovalbumin. Furthermore, comparison of the volatiles generated from onions, cooked either alone, or in the presence of meat, showed a significant reduction of key onion-derived disulphides when cooked in the presence of meat, and an even greater reduction of trisulphides. These findings may have implications for consumer acceptance of food products; where these compounds are used as flavourings or where they occur naturally.

A randomised clinical trial to assess the effect of total enteral and total parenteral nutritional support on metabolic, inflammatory and oxidative markers in patients with predicted severe acute pancreatitis (APACHE II >= 66)

Background: Total enteral nutrition (TEN) within 48 h of admission has recently been shown to be safe and efficacious as part of the management of severe acute pancreatitis. Our aim was to ascertain the safety of immediate TEN in these patients and the effect of TEN on systemic inflammation, psychological state, oxidative stress, plasma glutamine levels and endotoxaemia. Methods: Patients admitted with predicted severe acute pancreatitis (APACHE II score 15) were randomised to total enteral (TEN; n = 8) or total parenteral nutrition (TPN; n = 9). Measurements of systemic inflammation (C-reactive protein), fatigue ( visual analogue scale), oxidative stress ( plasma thiobarbituric acid- reactive substances), plasma glutamine and anti-endotoxin IgG and IgM antibody concentrations were made on admission and repeated on days 3 and 7 thereafter. Clinical progress was monitored using APACHE II score. Organ failure and complications were recorded. Results: All patients tolerated the feeding regime well with few nutrition-related complications. Fatigue improved in both groups but more rapidly in the TEN group. Oxidative stress was high on admission and rose by similar amounts in both groups. Plasma glutamine concentrations did not change significantly in either group. In the TPN group, 3 patients developed respiratory failure and 3 developed non-respiratory single organ failure. There were no such complications in the TEN group. Hospital stay was shorter in the TEN group [ 7 (4-14) vs. 10 (7-26) days; p = 0.05] as was time to passing flatus and time to opening bowels [1 (0-2) vs. 2 (1-5) days; p = 0.01]. The cost of TEN was considerably less than of TPN. Conclusion: Immediate institution of nutritional support in the form of TEN is safe in predicted severe acute pancreatitis. It is as safe and as efficacious as TPN and may be beneficial in the clinical course of this disease. Copyright (C) 2003 S. Karger AG, Basel and IAP.

The importance of the relationship between scale and process in understanding long-term DOC dynamics

Concentrations of dissolved organic carbon have increased in many, but not all, surface waters across acid impacted areas of Europe and North America over the last two decades. Over the last eight years several hypotheses have been put forward to explain these increases, but none are yet accepted universally. Research in this area appears to have reached a stalemate between those favouring declining atmospheric deposition, climate change or land management as the key driver of long-term DOC trends. While it is clear that many of these factors influence DOC dynamics in soil and stream waters, their effect varies over different temporal and spatial scales. We argue that regional differences in acid deposition loading may account for the apparent discrepancies between studies. DOC has shown strong monotonic increases in areas which have experienced strong downward trends in pollutant sulphur and/or seasalt deposition. Elsewhere climatic factors, that strongly influence seasonality, have also dominated inter-annual variability, and here long-term monotonic DOC trends are often difficult to detect. Furthermore, in areas receiving similar acid loadings, different catchment characteristics could have affected the site specific sensitivity to changes in acidity and therefore the magnitude of DOC release in response to changes in sulphur deposition. We suggest that confusion over these temporal and spatial scales of investigation has contributed unnecessarily to the disagreement over the main regional driver(s) of DOC trends, and that the data behind the majority of these studies is more compatible than is often conveyed.

Buffering of recovery from acidification by organic acids

In the United Kingdom, as in other regions of Europe and North America, recent decreases in surface water sulphate concentrations, due to reduced sulphur emissions, have coincided with marked increases in dissolved organic carbon (DOC) concentrations. Since many of the compounds comprising DOC are acidic, the resulting increases in organic acidity may have the potential to offset the benefits of a decrease in mineral (sulphate) acidity. To test this, we used a triprotic model of organic acid dissociation to estimate the proportional organic acid buffering of reduced mineral acidity as measured in the 22 lakes and streams monitored by the UK Acid Waters Monitoring Network. For an average non-marine sulphate decrease of 30 μeq l− 1 over 15 years from 1988–2003, we estimate that around 28% was counterbalanced by rising strong organic acids, 20% by rising alkalinity (partly attributable to an increase in weak organic acids), 11% by falling inorganic aluminium and 41% by falling non-marine base cations. The situation is complicated by a concurrent decrease in marine ion concentrations, and the impact this may have had on both DOC and acidity, but results clearly demonstrate that organic acid increases have substantially limited the amount of recovery from acidification (in terms of rising alkalinity and falling aluminium) that have resulted from reducing sulphur emissions. The consistency and magnitude of sulphate and organic acid changes are consistent with a causal link between the two, possibly due to the effects of changing acidity, ionic strength and aluminium concentrations on organic matter solubility. If this is the case, then organic acids can be considered effective but partial buffers to acidity change in organic soils, and this mechanism needs to be considered in assessing and modelling recovery from acidification, and in defining realistic reference conditions. However, large spatial variations in the relative magnitude of organic acid and sulphate changes, notably for low-deposition sites in northwestern areas where organic acid increases apparently exceed non-marine sulphate decreases, suggest that additional factors, such as changes in sea-salt deposition and climatic factors, may be required to explain the full magnitude of DOC increases in UK surface waters.

Pricing inefficiencies in private real estate markets using total return swaps

Efficient markets should guarantee the existence of zero spreads for total return swaps. However, real estate markets have recorded values that are significantly different from zero in both directions. Possible explanations might suggest non-rational behaviour by inexperienced market players or unusual features of the underlying asset market. We find that institutional characteristics in the underlying market lead to market inefficiencies and, hence, to the creation of a rational trading window with upper and lower bounds within which transactions do not offer arbitrage opportunities. Given the existence of this rational trading window, we also argue that the observed spreads can substantially be explained by trading imbalances due to the limited liquidity of a newly formed market and/or to the effect of market sentiment, complementing explanations based on the lag between underlying market returns and index returns.

Effects of sulphur nutrition during potato cultivation on the formation of acrylamide and aroma compounds during cooking

Lack of sulphur nutrition during potato cultivation has been shown to have profound effects on tuber composition, affecting in particular the concentrations of free asparagine, other amino acids and sugars. This is important because free asparagine and sugars react at high temperatures to form acrylamide, a suspect carcinogen. Free amino acids and sugars also form a variety of other compounds associated with colour and flavour. In this study the volatile aroma compounds formed in potato flour heated at 180 °C for 20 min were compared for three varieties of potato grown, with and without sulphur fertiliser. Approximately 50 compounds were quantified in the headspace extracts of the heated flour, of which over 40 were affected by sulphur fertilisation and/or variety. Many of the 41 compounds found at higher concentrations in the sulphur-deficient flour were Strecker aldehydes and compounds formed from their condensation, whereas only one compound, benzaldehyde, behaved in the same way as did acrylamide and was found at higher concentrations in the sulphur-sufficient flour. The reasons for these effects are discussed.