Simulating the formation of secondary organic aerosol from the photooxidation of aromatic hydrocarbons

The formation and composition of secondary organic aerosol (SOA) from the photooxidation of benzene, p-xylene, and 1,3,5-trimethylbenzene has been simulated using the Master Chemical Mechanism version 3.1 (MCM v3.1) coupled to a representation of the transfer of organic material from the gas to particle phase. The combined mechanism was tested against data obtained from a series of experiments conducted at the European Photoreactor (EUPHORE) outdoor smog chamber in Valencia, Spain. Simulated aerosol mass concentrations compared reasonably well with the measured SOA data only after absorptive partitioning coefficients were increased by a factor of between 5 and 30. The requirement of such scaling was interpreted in terms of the occurrence of unaccounted-for association reactions in the condensed organic phase leading to the production of relatively more nonvolatile species. Comparisons were made between the relative aerosol forming efficiencies of benzene, toluene, p-xylene, and 1,3,5-trimethylbenzene, and differences in the OH-initiated degradation mechanisms of these aromatic hydrocarbons. A strong, nonlinear relationship was observed between measured (reference) yields of SOA and (proportional) yields of unsaturated dicarbonyl aldehyde species resulting from ring-fragmenting pathways. This observation, and the results of the simulations, is strongly suggestive of the involvement of reactive aldehyde species in association reactions occurring in the aerosol phase, thus promoting SOA formation and growth. The effect of NO, concentrations on SOA formation efficiencies (and formation mechanisms) is discussed.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Water-soluble, unimolecular containers based on amphiphilic multiarm star block copolymers

A new class of water-soluble, amphiphilic star block copolymers with a large number of arms was prepared by sequential atom transfer radical polymerization (ATRP) of n-butyl methacrylate (BMA) and poly( ethylene glycol) methyl ether methacrylate (PEGMA). As the macroinitiator for the ATRP, a 2-bromoisobutyric acid functionalized fourth-generation hyperbranched polyester (Boltorn H40) was used, which allowed the preparation of star polymers that contained on average 20 diblock copolymer arms. The synthetic concept was validated by AFM experiments, which allowed direct visualization of single molecules of the multiarm star block copolymers. DSC and SAXS experiments on bulk samples suggested a microphase-separated structure, in agreement with the core-shell architecture of the polymers. SAXS experiments on aqueous solutions indicated that the star block copolymers can be regarded as unimolecular micelles composed of a PBMA core and a diffuse PPEGMA corona. The ability of the polymers to encapsulate and release hydrophobic guests was evaluated using H-1 NMR spectroscopy. In dilute aqueous solution, these polymers act as unimolecular containers that can be loaded with up to 27 wt % hydrophobic guest molecules.

Intermediate ion stability and regio selectivity polymerization using neutral salicyladiminato in propene nickel(II) and palladium(II) complexes as catalysts

The mechanism of the Heck reaction has been studied with regard to transition metal catalysis of the addition of propene and the formation of unsaturated polymers. The reactivity of nickel and palladium complexes with five different bidentate ligands with O,N donor atoms has been investigated by computational methods involving density functional theory. Hence, it is possible to understand the electronic and steric factors affecting the reaction and their relative importance in determining the products formed in regard of their control of the regiochemistry of the products. Our results show that whether the initial addition of propene is trans to O or to N of the bidentate ligand is of crucial importance to the subsequent reactions. Thus when the propene is trans to 0, 1,2-insertion is favoured, but when the propene is trans to N, then 2,1-insertion is favoured. This difference in the preferred insertion pathway can be related to the charge distribution engendered in the propene moiety when the complex is formed. Indeed charge effects are important for catalytic activity but also for regioselectivity. Steric effects are shown to be of lesser importance even when t-butyl is introduced into the bidentate ligand as a substituent. (C) 2007 Elsevier B.V. All rights reserved.

Design, testing, and simulation of fibre composite leaf springs for heavy axle loads

This paper summarizes the design, manufacturing, testing, and finite element analysis (FEA) of glass-fibre-reinforced polyester leaf springs for rail freight vehicles. FEA predictions of load-deflection curves under static loading are presented, together with comparisons with test results. Bending stress distribution at typical load conditions is plotted for the springs. The springs have been mounted on a real wagon and drop tests at tare and full load have been carried out on a purpose-built shaker rig. The transient response of the springs from tests and FEA is presented and discussed.

Evolution of the eye-end design of a composite leaf spring for heavy axle loads

This paper presents the design evolution process of a composite leaf spring for freight rail applications. Three designs of eye-end attachment for composite leaf springs are described. The material used is glass fibre reinforced polyester. Static testing and finite element analysis have been carried out to obtain the characteristics of the spring. Load-deflection curves and strain measurement as a function of load for the three designs tested have been plotted for comparison with FEA predicted values. The main concern associated with the first design is the delamination failure at the interface of the fibres that have passed around the eye and the spring body, even though the design can withstand 150 kN static proof load and one million cycles fatigue load. FEA results confirmed that there is a high interlaminar shear stress concentration in that region. The second design feature is an additional transverse bandage around the region prone to delamination. Delamination was contained but not completely prevented. The third design overcomes the problem by ending the fibres at the end of the eye section.

Biomechanics of a branch-stem junction in softwood

Direct measurement of strain field in a mechanically loaded Norway spruce branch-stem junction was performed by means of electronic speckle pattern analysis. Results were compared with strain distribution in a polyester cast of identical shape as the branch-stem junction, and a simplified polyester model consisting of two half-cylinders. Compared to polyester models, the branch-stem junction was characterised by a very homogeneous distribution of strain, which can be interpreted as a homogeneous distribution of stress in terms of fraction of material strength. This optimised transfer of mechanical load from the branch to the stem is achieved by a combination of naturally optimised shape with, additionally, optimised mechanical wood properties in the junction area.

Effects of lipid emulsions on lipid body formation and eicosanoid production by human peripheral blood mononuclear and polymorphonuclear cells

Background & aims: This study investigated the influence of four commercial lipid emulsions, Ivelip, ClinOleic, Omegaven and SMOFlipid (R), on lipid body formation, fatty acid composition and eicosanoid production by cultured human peripheral blood polymorphonuclear cells (PMN) and mononuclear cells (PBMC). Methods: PMN and PBMC were exposed to emulsions at concentrations ranging from 0.01 to 0.04%. Lipid body formation was assessed by microscopy, fatty acid composition by gas chromatography and eicosanoids by ELISA. Results: Stimulation of inflammatory cells and exposure to lipid emulsions promoted the formation of lipid bodies, but there did not appear to be differential effects of the emulsions tested. In contrast, there were differential effects of lipid emulsions on eicosanoid formation, particularly with regards to LTB4 production by PMN. Omegaven dramatically increased production of eicosanoids compared with the other emulsions in a dose-dependent manner. This effect was associated with a significantly higher level of lipid peroxides in the supernatants of cells exposed to Omegaven. Conclusions: Stimulation of inflammatory cells and exposure to lipid emulsions promotes lipid body formation and eicosanoid production, although the differential effects of different emulsions appear to be largely due to lipid peroxidation of unsaturated fatty acids in some emulsions in this in vitro system. (C) 2009 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

Dietary fat composition and cardiovascular disease

Cardiovascular disease (CVD), which includes coronary heart disease and stroke, remains the major killer in the EU, being responsible for 42% of total mortality. The amount and composition of dietary fat is arguably the most important dietary factor contributing to disease risk. A significant body of consistent evidence indicates that a decrease in dietary saturated fat:unsaturated (polyunsaturated + monounsaturated) ratio and an increased intake of long-chain n-3 polyunsaturated fatty acids (LC n-3 PUFA) found in fish, is cardioprotective. Furthermore, although the evidence is currently less convincing, such a strategy is also likely to improve insulin sensitivity, the central metabolic defect in diabetes. Currently in the UK only 12% of men, 17% of women and 8% of children have an SFA intakes <10% of energy. The average intake of LC n-3 PUFA is <0.2 g/day, which is less than half the current conservative recommendation of a minimum of 0.45 g/day. Public health strategies to reverse these dietary fatty acid imbalances, aimed at educating and motivating the consumer and making affordable and acceptable food products with an ‘enhanced’ fatty acid profile more widely available, must remain a public health priority in the ‘fight’ against CVD.

Influence of sulfur amino acids on the volatile and nonvolatile components of cooked salmon (Salmo salar)

Volatile and nonvolatile compounds, which could contribute to flavor, were analyzed in salmon. One hundred twenty-three volatile compounds were identified in the headspace of two different samples of cooked salmon, including lipid-derived volatiles, Maillard-derived volatiles, sulfur volatiles, Strecker aldehydes, nitrogen heterocyclic compounds, terpenes, and trimethylamine. Significant differences between samples were found for 104 of the volatiles. Although the levels of free cysteine and methionine were low in the salmon, sulfur volatiles were formed in the cooked fish, demonstrating that there were sufficient sulfur amino acids present for their formation. Notable differences in sulfur compounds between the samples suggested that small changes in sulfur amino acids could be responsible. When this hypothesis was tested, salmon heated with cysteine had increased levels of many thiophenes, thiazoles, alicyclic sulfides, and nitrogen heterocycles. With the addition of methionine, levels of dimethyl sulfides, two alicyclic sulfides, pyrazines, some unsaturated aldehydes, and alcohols and 2-furanmethanethiol increased. The largest difference found among the nonvolatile (low molecular weight water-soluble) compounds was in inosine monophosphate.

Physiological changes in Campylobacter jejuni on entry into stationary phase

Campylobacter jejuni NCTC 11168 does not exhibit the general increase in cellular stress resistance on entry into stationary phase that is seen in most other bacteria. This is consistent with the lack of global stationary phase regulatory elements in this organism. deduced from an analysis of its genome sequence. We now show that C. jejuni NCTC 11168 does undergo certain changes in stationary phase, of a pattern not previously described. As cells entered stationary phase there was a change in membrane fatty acid composition, principally a decrease in the proportion of unsaturated fatty acids and an increase in the content of cyclopropane and short-chain fatty acids. These changes in membrane composition were accompanied by an increase in the resilience of the cell membrane towards loss of integrity caused by pressure and an increase in cellular pressure resistance. By contrast. there were no major changes in resistance to acid or heat treatment. A similar pattern of changes in stress resistance on entry, into stationary phase was seen in C. jejuni NCTC 11351, the type strain. These changes appear to represent a restricted Physiological response to the conditions existing in stationary phase cultures, in an organism having limited capacity for genetic regulation and adaptation to environment. © 2004 Elsevier B.V. All rights reserved.

Apolipoprotein E enrichment of immuno-separated chylomicron and chylomicron remnants following saturated fatty acids

Aim: We examined the effect of meat fatty acids on lipid and apolipoprotein concentrations of very low density lipoprotein (VLDL) and chylomicron/chylomicron remnants in lipid fractions with a Svedberg flotation rate (S-f) 60-400 and S-f 20-60. Methods and results: Six healthy middle-aged men received in random order mixed meals enriched with saturated (SFA), polyunsaturated (PUFA) or monounsaturated (MUFA) fatty acids on 3 occasions. VLDL and chylomicron/chylomicron remnants in the lipid fractions were separated by immunoaffinity chromatography against apo B-100. In the S-f 60-400 chylomicron/chylomicron remnants, triacylglycerol and cholesterol concentrations were significantly tower following PUFA compared with SFA and MUFA (P <= 0.05). Apolipoprotein (apo) E responses were significantly higher after SFA in chylomicron/chylomicron remnants and VLDL compared with PUFA and MUFA (P < 0.007). However, apo B responses (particle number) were higher following MUFA than SFA (P = 0.039 for chylomicron/chylomicron remnants). Composition of the chylomicron/chylomicron remnants (expressed per particle) revealed differences in their triacylglycerol and apo E contents; in the Sf 60-400 fraction, SFA-rich chylomicron/chylomicron remnants contained significantly more triacylglycerol than MUFA (P = 0.028), more apo E than PUFA- and MUFA-rich particles (P < 0.05) and in the S-f 20-60 fraction, more apo E than MUFA (P = 0.009). Conclusion: There are specific differences in the composition of chylomicron/ chylomicron remnants formed after saturated compared with unsaturated fatty acid-rich meals which could determine their metabolic fate in the circulation and subsequent atherogenicity. (C) 2005 Elsevier B.V. All rights reserved.

Impact of saturated, polyunsaturated and monounsaturated fatty acid-rich micelles on lipoprotein synthesis and secretion in Caco-2 cells

Meal fatty acids have been shown to modulate the size and composition of triacylglycerol (TAG)-rich lipoproteins influencing the magnitude and duration of the postprandial plasma TAG response. As a result there is considerable interest in the origin of these meal fatty-acid induced differences in particle composition. Caco-2 cells were incubated over 4 days with fatty acid mixtures resembling the composition of saturated (SFA), monounsaturated (MUFA) and polyunsaturated fatty acid (PUFA)-rich meals fed in a previous postprandial study to determine their impact on lipoprotein synthesis and secretion. The MUFA- and PUFA-rich mixtures supported greater intracellular TAG, but not cholesterol accumulation compared with the SFA-rich mixture (P < 0.001). The MUFA-rich mixture promoted significantly greater TAG and cholesterol secretion than the other mixtures and significantly more apolipoprotein B-100 secretion than the PUFA-rich mixture (P < 0.05). Electron microscopy revealed the SFA-rich mixture had led to unfavourable effects on cellular morphology, compared with the unsaturated fatty acid-rich mixtures. Our findings suggest the MUFA-rich mixture, may support the formation of a greater number of TAG-rich lipoproteins, which is consistent with indirect observations from our human study. Our electron micrographs are suggestive that some endocytotic uptake of MUFA-rich taurocholate micelles may promote greater lipoprotein synthesis and secretion in Caco-2 cells.

Gastrointestinal tract: intestinal fatty acid metabolism and implications for health

Short-chain fatty acids (SCFA) are formed from the fermentation of sugars by intestinal bacteria. Acetate is the most abundant SCFA, with lower amounts of propionate and butyrate formed. Propionate and butyrate are also formed from the products of carbohydrate fermentation by other bacteria, for example from lactate and acetate. SCFA play a role in regulating transit of digesta through the intestine, and butyrate formation is thought to be beneficial to health because butyrate decreases the risk of colon cancer. Major butyrate-producing species are among the most abundant present in the colon, including Roseburia and Faecalibacterium spp. Metabolism of longer-chain fatty acids occurs mainly by hydration or hydrogenation of unsaturated fatty acids. Hydroxystearic acids are formed in the intestine, particularly under disease conditions. Metabolism of linoleic acid results in the formation of conjugated linoleic acids (CLA) by several species, including Roseburia hominis and Roseburia inulinovorans. Enhancement of intestinal CLA formation, possibly using probiotics, may be useful in preventing or treating inflammatory bowel disease.

Effects of plant sulfur nutrition on acrylamide and aroma compounds in cooked wheat

Wheat flour from plants deficient in sulfur has been shown to contain substantially higher levels of free amino acids, particularly asparagine and glutamine, than flour from wheat grown where sulfur nutrition was sufficient. Elevated levels of asparagine resulted in acrylamide levels up to 6 times higher in sulfur-deprived wheat flour, compared with sulfur-sufficient wheat flour, for three varieties of winter wheat. The volatile compounds from flour, heated at 180 degrees C for 20 min, have been compared for these three varieties of wheat grown with and without sulfur fertilizer. Approximately 50 compounds were quantified in the headspace extracts of the heated flour; over 30 compounds were affected by sulfur fertilization, and 15 compounds were affected by variety. Unsaturated aldehydes formed from aldol condensations, Strecker. aldehydes, alkylpyrazines, and low molecular weight alkylfurans were found at higher concentrations in the sulfur-deficient flour, whereas low molecular weight pyrroles and thiophenes and sugar breakdown products were found at higher concentrations in the sulfur-sufficient flour. The reasons for these differences and the relationship between acrylamide formation and aroma volatile formation are discussed.