Continuum, Discrete, and Explicit Solvation Models for Describing the Low-Lying Absorption Spectrum of the Pterin Acid in Aqueous Environment

The absorption spectrum of the acid form of pterin in water was investigated theoretically. Different procedures using continuum, discrete, and explicit models were used to include the solvation effect on the absorption spectrum, characterized by two bands. The discrete and explicit models used Monte Carlo simulation to generate the liquid structure and time-dependent density functional theory (B3LYP/6-31G+(d)) to obtain the excitation energies. The discrete model failed to give the correct qualitative effect on the second absorption band. The continuum model, in turn, has given a correct qualitative picture and a semiquantitative description. The explicit use of 29 solvent molecules, forming a hydration shell of 6 angstrom, embedded in the electrostatic field of the remaining solvent molecules, gives absorption transitions at 3.67 and 4.59 eV in excellent agreement with the S(0)-S(1) and S(0)-S(2) absorption bands at of 3.66 and 4.59 eV, respectively, that characterize the experimental spectrum of pterin in water environment. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110: 2371-2377, 2010

Synthesis and structural characterization of a new polymeric zinc(II) complex with thiophene-2-carboxylic acid

A new polymeric zinc(II) complex with thiophene-2-carboxylic acid (-tpc) of composition [Zn2(C20H12O8S4)]n was obtained and structurally characterized by X-ray diffraction, thermal analysis, nuclear magnetic resonance (NMR), and infrared spectroscopies. Upfield shift in the 1H-NMR spectrum is explained by the crystalline structure, which shows the thiophene rings overlapping each other in parallel pairs. The compound crystallizes in the monoclinic system, space group P21/c, with a = 9.7074(4) angstrom, b = 13.5227(3) angstrom, c = 18.9735(7) angstrom, = 95.797(10)degrees, and Z = 4. Three -tpc groups bridge between two Zn(II) ions through oxygens and the fourth one bridges between one of these ions and the third one, symmetry related by a twofold screw axis. This arrangement gives rise to infinite chains along the crystallographic a direction. The metal atoms display an approximate tetrahedral configuration. The complex is insoluble in water, ethanol, and acetone, but soluble in dimethyl sulfoxide.

The influence of acetic acid on the ethanol electrooxidation on a platinum electrode

In the presented work, the evaluation of the influence of acetic acid in the electrochemical environment on the ethanol electro-oxidation reaction on a polycrystalline platinum electrode is presented for the first time. Using cyclic voltammetry. chronoamperometry and in situ Fourier Transformed IR spectroscopy (FTIR) it was demonstrated that an inhibition of the ethanol oxidation reaction occurs for bulk acetic acid concentrations of the order 0.1 mu mol L(-1) -5 mmol L(-1). This inhibition effect is related to the decrease of CO(2) and acetaldehyde production as confirmed by spectroscopic results. (C) 2011 Elsevier B.V. All rights reserved.

Effect of Alpha-Linolenic acid on retnal function in mammals

The retinal function of several different species is compromised by a dietary deficiency of α-linolenic acid. A review of the literature revealed that diets containing less than O. 1 gIl OOg diet as α-linolenic acid could not sustain retinal docosahexaenoic acid levels over a prolonged period and that such diets were associated with a reduced response of the retina to light. In these studies the median α-linoleinic acid intake of control animals was 1.25g/100g diet. A study on the comparative ability of dietary α-linolenic acid and dietary docosahexaenoic acid to provide for retinal docosahexaenoic acid in the guinea pig found that α-linolenic acid was only approximately 10% as effective as docosahexaenoic acid in this regard.

Modification of tissue fatty acid composition in Murray cod (Maccullochella peelii peelii, Mitchell) resulting from a shift from vegetable oil diets to a fish oil diet.

The dynamics of fatty acid composition modifications were examined in tissues of Murray cod fed diets containing fish oil (FO), canola oil (CO) and linseed oil (LO) for a 25-week period and subsequently transferred to a FO (finishing/wash-out) diet for a further 16 weeks. At the commencement of the wash-out period, following 25 weeks of vegetable oil substitution diets, the fatty acid compositions of Murray cod fillets were reflective of the respective diets. After transfer to the FO diet, differences decreased in quantity and in numerousness, resulting in a revert to the FO fatty acid composition. Changes in percentages of the fatty acids and total accumulation in the fillet could be described by exponential equations and demonstrated that major modifications occurred in the first days of the finishing period. A dilution model was tested to predict fatty acid composition. In spite of a general reliability of the model (Y=0.9234X+0.4260, R²=0.957, P<0.001, where X is the predicted percentage of fatty acid; Y the observed percentage of fatty acid), in some instances the regression comparing observed and predicted values was markedly different from the line of equity, indicating that the rate of change was higher than predicted (i.e. Y=0.4205X+1.191, R²=0.974, P<0.001, where X is the predicted percentage of α-linolenic acid; Y the observed percentage of α-linolenic acid). Ultimately, using the coefficient of distance (D), it was shown that the fatty acid composition of fish previously fed the vegetable oil diets returned to the average variability of the fillet fatty acid composition of Murray cod after 70 or 97 days (LO and CO respectively).

Effects of alternative dietary lipid sources on performance, tissues chemical composition, mitochondrial fatty acid oxidation capabilities, and sensory characteristics in brown trout (Salmo trutta L.)

The efficiency of five dietary lipid sources (fish oil as control—C; canola oil—CO; poultry fat—PF; pork lard—PL; and oleine oil—OO) were evaluated in juvenile brown trout (58.4±0.7 g) in an experiment conducted over 70 days at 14.6±0.4 °C. The best growth was observed in fish fed the C diet whereas the PL diet fed fish had the best feed utilization. Significant differences in carcass and muscle proximate composition, but not in liver, were noted among fish fed the different dietary treatments. The fatty acid composition of muscle largely reflected that of the diets, while total cholesterol was not affected. The atherogenicity and the thrombogenicity qualities of the trout flesh were modified by the lipid sources. Sensory analysis did not show any significant differences among the cooked fillets with respect to dietary treatments, while in uncooked products, some significant differences were observed. The carnitine palmitoyltransferase I and II (CPT-I and CPT-II) activities of liver and white muscle were assayed for a better understanding of the potential β-oxidation capability of the different dietary lipid sources. The hepatic, but not white muscle CPT-I and CPT-II activities were affected by dietary treatments. This study showed that alternative lipid sources could be used effectively for oil coating extruded diets for brown trout.

Quantifying effects of soil heterogeneity on groundwater pollution at four sites in the USA

Four sites located in the north-eastern region of the United States of America have been chosen to investigate the impacts of soil heterogeneity in the transport of solutes (bromide and chloride) through the vadose zone (the zone in the soil that lies below the root zone and above the permanent saturated groundwater). A recently proposed mathematical model based on the cumulative beta distribution has been deployed to compare and contrast the regions' heterogeneity from multiple sample percolation experiments. Significant differences in patterns of solute leaching were observed even over a small spatial scale, indicating that traditional sampling methods for solute transport, for example the gravity pan or suction Iysimeters, or more recent inventions such as the multiple sample percolation systems may not be effective in estimating solute fluxes in soils when a significant degree of soil heterogeneity is present. Consequently, ignoring soil heterogeneity in solute transport studies will likely result in under- or overprediction of leached fluxes and potentially lead to serious pollution of soils and/or groundwater. The cumulative beta distribution technique is found to be a versatile and simple technique of gaining valuable information regarding soil heterogeneity effects on solute transport. It is also an excellent tool for guiding future decisions of experimental designs particularly in regard to the number of samples within one site and the number of sampling locations between sites required to obtain a representative estimate of field solute or drainage flux.

Insuring cleaner oceans: the economics of oil pollution prevention

The current system of controlling oil spills involves a complex relationship of international, federal and state law, which has not proven to be very effective. The multiple layers of regulation often leave shipowners unsure of the laws facing them. Furthemore, nations have had difficulty enforcing these legal requirements. This thesis deals with the role marine insurance can play within the existing system of legislation to provide a strong preventative influence that is simple and cost-effective to enforce. In principle, insurance has two ways of enforcing higher safety standards and limiting the risk of an accident occurring. The first is through the use of insurance premiums that are based on the level of care taken by the insured. This means that a person engaging in riskier behavior faces a higher insurance premium, because their actions increase the probability of an accident occurring. The second method, available to the insurer, is collectively known as cancellation provisions or underwriting clauses. These are clauses written into an insurance contract that invalidates the agreement when certain conditions are not met by the insured The problem has been that obtaining information about the behavior of an insured party requires monitoring and that incurs a cost to the insurer. The application of these principles proves to be a more complicated matter. The modern marine insurance industry is a complicated system of multiple contracts, through different insurers, that covers the many facets of oil transportation. Their business practices have resulted in policy packages that cross the neat bounds of individual, specific insurance coverage. This paper shows that insurance can improve safety standards in three general areas -crew training, hull and equipment construction and maintenance, and routing schemes and exclusionary zones. With crew, hull and equipment, underwriting clauses can be used to ensure that minimum standards are met by the insured. Premiums can then be structured to reflect the additional care taken by the insured above and beyond these minimum standards. Routing schemes are traffic flow systems applied to congested waterways, such as the entrance to New York harbor. Using natural obstacles or manmade dividers, ships are separated into two lanes of opposing traffic, similar to a road. Exclusionary zones are marine areas designated off limits to tanker traffic either because of a sensitive ecosystem or because local knowledge is required of the region to ensure safe navigation. Underwriting clauses can be used to nullify an insurance contract when a tanker is not in compliance with established exclusionary zones or routing schemes.

Optimization of fatty acid determination in selected fish and microalgal oils

The use of ten fatty acid methyl ester reference standards coupled with a detailed quantification method was shown to significantly optimize the fatty acid determination of selected fish and microalgal oils when compared to methods that use only one reference standard (C19:0 or C23:0) as a relative response factor. When using the mixture of ten reference standards after transesterifying oils with NaOH/BF3, determination of total fatty acids, eicosapentaenoic acid and docosahexaenoic acid improved by an average of 7.3, 11.5 and 8.4%, respectively. Furthermore, improvements of 13.9, 18.9 and 6.8% of total fatty acids, EPA and DHA, respectively, were obtained when using the mixture of reference standards for fatty acid determination after directly extracting and transesterifying oil contained in microalgal cells with a mixture of methanol, HCl and chloroform. Fatty acid methyl ester standards dissolved in isooctane showed <5% variability throughout 130 days of stability testing when stored at −20 °C. The optimized method can be used for improving the quantification of fatty acids in both oils (fish and microalgal oils) and dry microalgal cells.

Trophic effects of fishing southern rock lobster Jasus edwardsii shown by combined fatty acid and stable isotope analyses

The southern rock lobster Jasus edwardsii is a commercial species that has benefited from the complete protection offered by no-take reserves, with higher abundances and larger animals recorded in reserves than in adjacent fished areas. What remains unclear is whether there is any change in the diet of lobsters in reserves, for example, as a result of increased intraspecific competition for food. We used combined chemical tracers to examine the diet of lobsters in fished and reserve areas in 2 bioregions in eastern Tasmania. δ15N values of lobsters were richer in fished than in reserve areas, indicating that lobsters eat a greater proportion of food items from higher trophic levels in fished areas. Mixing models suggest that ascidians, sea urchins and the turbinid gastropod were all important food sources for lobsters, but the importance of these food items differed between bioregions. This spatial variability may suggest that the small size of the reserve in one bioregion is inadequate at ensuring the diet of lobsters is protected from fishing pressure. Fatty acid profiles of lobsters supported the importance of these food sources to lobsters. Differences between bioregions, or inside and outside of reserves, were not apparent using fatty acids. The present study highlights that lobster fishing has the capacity to alter the trophic status of prey for generalist predators and suggests that fatty acid analyses may be limited in detecting changes in the dietary composition of such generalist feeders.

Comparison of lipid content and fatty acid composition in the edible meat of wild and cultured freshwater and marine fish and shrimps from China

The lipid content and fatty acid composition in the edible meat of twenty-nine species of wild and cultured freshwater and marine fish and shrimps were investigated. Both the lipid content and fatty acid composition of the species were specified due to their unique food habits and trophic levels. Most of the marine fish demonstrated higher lipid content than the freshwater fish, whereas shrimps had the lowest lipid content. All the marine fish and shrimps had much higher total n-3 PUFA than n-6 PUFA, while most of the freshwater fish and shrimps demonstrated much lower total n-3 PUFA than n-6 PUFA. This may be the biggest difference in fatty acid composition between marine and freshwater species. The cultured freshwater fish demonstrated higher percentages of total PUFA, total n-3 PUFA, and EPA + DHA than the wild freshwater fish. Two freshwater fish, including bighead carp and silver carp, are comparable to the marine fish as sources of n-3 PUFA.

Occurrences of cooperative breeding in the masked lapwing vanellus miles

The Masked Lapwing Vanellus miles is a common ground-nesting shorebird inhabiting grasslands, paddocks, rivers, lakes, swamps and, tidal mud flats. It is particularly common in the urban areas of Phillip Island, Victoria (Dann 1981, Marchant and Higgins 1993). The Masked Lapwing usually lays between one and four eggs (the mean number of eggs per clutch of this study was 3.6 ± 1 SD) that hatch after 31 days. Both sexes incubate eggs, brood young and defend the eggs and young. Masked Lapwings produce precocial and nidifugous chicks that remain with the adults on defended territories until fledging (Marchant and Higgins 1993, Thomas 1969). The chicks are able to feed themselves within hours of hatching and rely on their parents only for protection (alarm signals) and warmth (brooding) (Marchant and Higgins 1993). Here we report three instances of likely co-operative breeding of Vanellus miles on Phillip Island between 18 July and 13 September 2012.

Solvent extraction and purification of sugars from hemicellulose hydrolysates using boronic acid carriers

Research was performed to determine whether it was technically feasible to use boronic acid extractants to purify and concentrate the sugars present in hemicellulose hydrolysates. Initially, five types of boronic acids (phenylboronic acid, 3,5-dimethylphenylboronic acid, 4-tert-butylphenylboronic acid, trans-β-styreneboronic acid or naphthalene-2-boronic acid) dissolved in an organic diluent (Shellsol® 2046 or Exxal® 10) containing the quaternary amine Aliquat® 336 were tested for their ability to extract sugars (fructose, glucose, sucrose and xylose) from a buffered, immiscible aqueous solution. Naphthalene- 2-boronic acid was found to give the greatest extraction of xylose regardless of which diluent was used. Trials were then conducted to extract xylose and glucose from solutions derived from the dilute acid hydrolysis of sugar cane bagasse and to then strip the loaded organic solutions using an aqueous solution containing hydrochloric acid. This produced a strip solution in which the xylose concentration had been increased over 7× that of the original hydrolysate while reducing the concentration of the undesirable acid-soluble lignin by over 90%. Hence, this process can be exploited to produce high concentration xylose solutions suitable for direct fermentation.

Characterisation of lipase fatty acid selectivity using novel omega-3 pNP-acyl esters

 Lipases have applications for the industrial processing of lipids, including concentrating and/or modifying fish oil derived omega-3 fatty acids, widely used as nutritional supplement and functional food ingredients. A range of para-nitrophenol (pNP) acyl esters were synthesised as a means to rapidly screen lipases for fatty acid selectivity using spectrophotometric detection. The chosen esters were based primarily on the most abundant fatty acids present in anchovy and tuna oils. pNP derivatives of C16:1 n-7, C18:1 n-9 (OA), C18:2 n-6 (LA), C18:3 n-3 (ALA), C20:5 n-3 (EPA) and C22:6 n-3 (DHA) were synthesised. Storage stability of these pNP derivatives was shown to be at least 6 months and all pNP derivatives, including those of EPA and DHA, were shown to be stable throughout the conditions of the assay. We applied the new assay substrates for the determination of fatty acid selectivity of five widely utilised lipases. Results showed that the lipase from Candida rugosa was the most selective in terms of omega-3 specificity, preferentially hydrolysing all other medium– long chain substrates. Lipases from Rhizomucor miehei and Thermomyces lanuginosa also showed selectivity, with a significant preference for saturated fatty acids. Candida Antarctica lipase B and Aspergillus niger lipase were the least selective.

Identification of fatty acid translocase on human skeletal muscle mitochondrial membranes: essential role in fatty acid oxidation

Fatty acid translocase (FAT/CD36) is a transport protein with a high affinity for long-chain fatty acids (LCFA). It was recently identified on rat skeletal muscle mitochondrial membranes and found to be required for palmitate uptake and oxidation. Our aim was to identify the presence and elucidate the role of FAT/CD36 on human skeletal muscle mitochondrial membranes. We demonstrate that FAT/CD36 is present in highly purified human skeletal mitochondria. Blocking of human muscle mitochondrial FAT/CD36 with the specific inhibitor sulfo-N-succimidyl-oleate (SSO) decreased palmitate oxidation in a dose-dependent manner. At maximal SSO concentrations (200 μM) palmitate oxidation was decreased by 95% (P < 0.01), suggesting an important role for FAT/CD36 in LCFA transport across the mitochondrial membranes. SSO treatment of mitochondria did not affect mitochondrial octanoate oxidation and had no effect on maximal and submaximal carnitine palmitoyltransferase I (CPT I) activity. However, SSO treatment did inhibit palmitoylcarnitine oxidation by 92% (P < 0.001), suggesting that FAT/CD36 may be playing a role downstream of CPT I activity, possibly in the transfer of palmitoylcarnitine from CPT I to carnitine-acylcarnitine translocase. These data provide new insight regarding human skeletal muscle mitochondrial fatty acid (FA) transport, and suggest that FAT/CD36 could be involved in the cellular and mitochondrial adaptations resulting in improved and/or impaired states of FA oxidation.