Synthesis of novel tri- and tetrasubstituted C<Subscript>18</Subscript> furan fatty esters

A methylene-interrupted C₁₈ keto-acetylenic fatty ester (methyl 12-oxo-9-octadecynoate) was obtained from methyl ricinoleate by bromination-dehydrobromination followed by oxidation. Reaction of methyl 12-oxo-9-octadecynoate with bis(benzonitrile) palladium(II) chloride, allyl bromide, or methyl-allyl bromide furnished methyl 8-[5-hexyl-3-allyl-furan-2-yl]-octanoate (1, 56%) or methyl 8-[5-hexyl-3-(2-methyl-allyl)-furan-2-yl]-octanoate (2, 55%). Reaction of methyl 12-oxo-11-chloro-or 11-fluoro-9-octadeyynoate (prepared from methyl santalbate-methyl 11-E-9-octadecynoate, found in sandalwood, Santalum album, seed oil) with bis(benzonitrile) palladium(II) chloride gave methyl 8-(4-fluoro-5-hexyl-furan-2-yl)-octanoate (3, 50%) or methyl 8-(4-fluoro-5-hexyl-furan-2-yl)-octanoate (4, 50%), respectively. And when methyl 12-oxo-11-chloro- or 11-fluoro-9-octadecynoate was treated with a mixture of bis(benzonitrile) palladium(II) chloride, allyl bromide, or methyl-allyl bromide, the reaction yielded tetrasubstituted C₁₈ furan derivatives, viz, methyl 8-(3-allyl-4-chloro-5-hexyl-furan-2-yl)-octanoate (5, 54%), methyl 8-[4-chloro-5-hexyl-3-(2-methyl-allyl)-furan-2-yl)-octanoate (6, 54%), methyl 8-(3-allyl-4-fluoro-5-hexyl-furan-2-yl]-octanoate (7, 10%), and methyl 8-[4-fluoro-5-hexyl-3-(2-methyl-allyl)-furan-2-yl]-octanoate (8, 10%). The presence of a fluorine atom in the furan derivatives 4, 7, and 8 was readily characterized by the appearance of doublets for carbon nuclei, which were coupled to the fluorine atom in the ¹³C NMR spectra. All furan fatty derivatives from this work were characterized by NMR spectroscopic and mass spectrometric analyses. The yields of compounds 7 and 8 were very low (10%) despite attempts to improve the procedure by increasing the amounts of the reactants and catalyst.     

Methane generation from Miocene lacustrine coals and organic-rich sedimentary rocks containing different types of organic matter

Ten selected samples with varying types and amounts of organic matter from two Miocene lacustrine basins in northwestern Turkey were analyzed by programmed-temperature open-system pyrolysis to determine methane generation potential and reaction kinetics. Open-system pyrolysis was performed at heating rates 0.1, 0.7 and 5.0 K/min, where generated gases were measured using an on-line gas chromatograph. Frequency factors and activation energy distributions of reaction kinetics for methane generation from the investigated lacustrine coals and sedimentary rocks indicated that type of kerogen controls the sequential order of methane generation. Methane from Type-III kerogen is generated at lower temperatures, which will be followed by methane from Type-II and Type-I kerogen. Methane generation potentials in the range 14-35 mg CH₄/g TOC correlates also with type of organic matter. For Type-III kerogen up to 28% of the total hydrocarbon generation potential belongs to methane. The respective value is only 2% for a Type-I kerogen.     

Subsoil <Superscript>15</Superscript>N-N<Subscript>2</Subscript>O Concentrations in a Sandy Soil Profile After Application of <Superscript>15</Superscript>N-fertilizer

Studies on emissions of nitrous oxide (N₂O) from agricultural soils mostly focus on fluxes between the soil and the atmosphere or are limited to the atmosphere in the topsoil. However, in soils with shallow water tables, significant N₂O formation may occur closer to the groundwater. The aims of this study were (i) to determine the importance of subsoil N₂O formation in a sandy soil; and (ii) to obtain a quantitative insight in the contribution of subsoil N₂O to the overall losses of N₂O to the environment. We applied ¹⁵N labeled fertilizer at a rate of 5.22 kg ¹⁵N ha⁻¹; 50% as Ca(NO₃)₂ and 50% as NH₄Cl, on a mesic typic Haplaquod seeded with potatoes (Solanum tuberosum L.), and traced soil N₂O concentrations and fluxes over a one-year period. Throughout the year, total N₂O and the amount of ¹⁵N recovered in soil N₂O were highest in the subsoil, with a maximum concentration at 48 cm depth in mid-February of 19900 μl m⁻³ and 24 μg ¹⁵N m⁻³, respectively. The maximum concentration coincided with the highest water-filled pore space of 71%. The cumulative flux of N₂O was 446 g N₂O-N ha⁻¹, the recovery of ¹⁵N in this flux was 0.06%. During the summer, maximum fluxes followed high soil N₂O concentrations. During winter, no such relation was found. We concluded that the formation of N₂O was the highest in the subsoil, largely controlled by water-filled pore space rather than NO₃⁻ concentration or temperature. Although high subsoil N₂O concentrations did not lead to high surface fluxes of N₂O in the winter, artificial draining may lead to high indirect N₂O emissions through supersaturated drainage water.     

Composition and seasonal variation of fatty acids of <Emphasis Type="Italic">Diplodus vulgaris</Emphasis> L. from the Adriatic Sea

Muscle tissue from the common two-banded sea bream Diplodus vulgaris L. originating from the Adriatic Sea, Croatia, was analyzed. The FA composition of neutral (TAG) and polar (PE, PC, PI/PS) lipid classes was determined, as well as the lipid and water contents during winter and summer periods. Both the total lipid and water contents were higher in the winter period. We identified 16 different FA. The major constituents of the total FA in both seasons were saturates: palmitic (16∶0) and stearic acids (18∶0); monoenes: oleic (18∶1n−9) and palmitoleic acids (16∶1n−7); and polyunsaturates: arachidonic acid (20∶4n−6), EPA (20∶5n−3), and DHA (22∶6n−3), but their amounts and ratios differed significantly between the two seasons and between lipid fractions. The FA composition showed a noticeable pattern of seasonality that reflected fluctuations mainly in TAG. The diminution of the monounsaturated FA content in the summer was clearly followed by an increase in PUFA content. Diplodus vulgaris is a good source of natural n−3 PUFA and would therefore be suitable for inclusion in highly unsaturated low-fat diets.     

Interaction between dietary protein and fat in triglyceride metabolism in the rat: Effects of soy protein and menhaden oil

The objective of the present study was to determine the mechanisms by which dietary proteins interact with dietary lipids in the regulation of triglyceridemia in rats. Male Sprague-Dawley rats (n=56) were subjected to 28-d experimental diets containing different combinations of proteins (20% w/w) and lipid sources (14% w/w): (i) casein-menhaden oil, (ii) casein-beef tallow, (iii) soy protein-menhaden oil, and (iv) soy protein-beef tallow. Significant protein-lipid interactions were observed on triglyceridemia and hepatic cholesterol in fasted rats. The combination of casein and beef tallow was associated with high plasma TG and hepatic cholesterol concentrations, which were reduced by substitution either of soy for casein or of menhaden oil for beef tallow. Therefore, triglyceridemia and liver cholesterol remained low with soy protein feeding, independently of the lipid source, as well as with menhaden oil feeding, regardless of the protein source. The menhaden oil diets reduced plasma cholesterol, hepatic TG, and TG secretion compared with beef tallow diets independently of the dietary protein source. Modifying the source of dietary proteins and lipids had no effect on post-heparin plasma lipoprotein lipase activity. These results demonstrate that soy protein can lower rat triglyceridemia relative to casein when associated with beef tallow consumption, whereas menhaden oil can attenuate hypertriglyceridemia when rats are fed casein. The data further suggest that part of the hypotriglyceridemic effect of soy protein in the rat may be mediated by reduced hepatic lipid synthesis, as is the case for menhaden oil.     

Influence of dietary long-chain PUFA on premature baboon lung FA and dipalmitoyl PC composition

One of the major survival challenges of premature birth is production of lung surfactant. The lipid component of surfactant, dipalmitoyl PC (DPPC), increases in concentration in the period before normal term birth via a net shift in FA composition away from unsaturates. We investigated the influence of dietary DHA and arachidonic acid (AA) on lung FA composition and DPPC concentration in term and preterm baboons. Pregnant animals/neonates were randomized to one of four groups: breast-fed (B), term formula-fed (T⁻), preterm formulafed (P⁻), and preterm fed formula supplemented with DHA-AA (P⁺). Breast milk contained 0.68%wt DHA and the P⁺ group formula contained 0.61%wt DHA. In the preterm groups (P⁻ and P⁺), pregnant females received a course of antenatal corticosteroids. At the adjusted age of 4 wk, neonate lung tissue was harvested, and FA composition and DPPC were analyzed. Palmitate was ∼28%wt of lung total FA and no significant differences were found among the four treatment groups. In contrast, DPPC in the B group lung tissue was significantly greater than DPPC in the unsupplemented groups, but not compared with the P⁺ group. The B and P⁺ groups were not significantly different in DHA and AA, but were different compared with the unsupplemented (T, P⁻) groups. These results indicate that LCP supplementation increases lung DHA and AA, without compromising overall lung 16∶0 or DPPC. The shift in FA composition toward greater unsaturation in the groups consuming LCP supported improved surfactant lipid concentration in preterm neonate lungs.     

Theoretical analysis on bending behavior of functionally graded composite beam crack-controlled by ultrahigh toughness cementitious composites

Ultrahigh toughness cementitious composites (UHTCC) obviously show strain hardening property under tensile or bending loading. The failure pattern of the UHTCC components exhibits multiple fine cracks under uniaxial tensile loading with prominent tensile strain capacity in excess of 3%, with merely 60 μm average crack width even corresponding to the ultimate tensile strain state. The approach adopted is based on the concept of functionally-graded concrete, where part of the concrete, which surrounds the main longitudinal reinforcement in a RC (reinforced concrete) member, is strategically replaced with UHTCC with excellent crack-controlling ability. Investigations on bending behavior of functionally-graded composite beam crack controlled by UHTCC has been carried out, including theo- retical analysis, experimental research on long composite beams without web reinforcement, validation and comparison between experimental and theoretical results, and analysis on crack control. In addition to improving bearing capacity, the results indicate that functionally-graded composite beams using UHTCC has been found to be very effective in preventing corrosion-induced damage compared with RC beams. Therefore, durability and service life of the structure could be enhanced. This paper discusses the development of internal force and crack propagation during loading process, and presents analysis of the internal force in different stages, moment-curvature relationship from loading to damage and calculation of mid-span deflection and ductility index. In the end, the theoretical formulae have been validated by experimental results.     

The influence of pH on reaction pathways for O2 reduction on the Au(100) face

Oxygen reduction on the Au(100) face was studied by the rotating disk-ring electrode technique in solutions of anions which adsorb strongly on gold (HSO₄⁻/SO₄²⁻ and/or OH⁻) over the entire pH range. The specific adsorption of OH⁻ anions, which is a pH dependent process, is found to play the key role in determining the reaction pathways. In the absence of OH⁻ adsorption, for pHs below 6, the reduction of O₂ begins as a 2e-process. Due to the increase in local pH during O₂ reduction, the reaction pathway turns into a 4e-reduction at a certain potential depending on the pH of the solution. For pHs higher than 6, O₂ reduction begins as a 4e-process in the potential region where specifically adsorbed OH⁻ anions are present.     

Studies of surface and gas reactions in a catalytically stabilized combustor

A numerical investigation of a catalytically stabilized thermal (CST) combustor was conducted for a multichannel catalyst bed, and both the catalyst bed and thermal combustor were simultaneously modeled. The numerical model handled the coupling of the surface and gas reaction in the catalyst bed as well as the gas reaction in the thermal combustor. The behavior of the catalyst bed was investigated at a variety of operating conditions, and location of the flame in the CST combustor was investigated via an analysis of the distribution of CO concentration. Through parametric analyses of the flame position, it was possible to derive a criterion to determine whether the flame is present in the catalyst bed or the thermal combustor for a given inlet condition. The results showed that the maximum inlet temperature at which the flame is located in the thermal combustor increased with increasing inlet velocity.     

Restoration of depressed prostanoid-induced ileal contraction in spontaneously hypertensive rats by dietary fish oil

We have reported that dietary fish oil (FO) rich in n-3 PUFA modulates gut contractility. It was further demonstrated that the gut of spontaneously hypertensive rats (SHR) has a depressed contractility response to prostaglandins (PG) compared with normotensive Wistar-Kyoto (WKY) rats. We investigated whether feeding diets supplemented with n-3 PUFA increased gut contractility and restored the depressed prostanoid response in SHR gut. Thirteen-week-old SHR were fed diets containing fat at 5 g/100 g as coconut oil (CO), lard, canola oil containing 10% (w/w) n-3 FA as alpha-linolenic acid (1 8:3n-3), or FO (as HiDHA, 22:6n-3) for 12 wk. A control WKY group was fed 5 g/100 g CO in the diet. As confirmed, the SHR CO group had a significantly lower gut response to PGE2 and PGF2alpha compared with the WKY CO group. Feeding FO increased the maximal contraction response to acetylcholine in the ileum compared with all diets and in the colon compared with lard, and restored the depressed response to PGE2 and PGF2alpha in the ileum but not the colon of SHR. FO feeding also led to a significant increase in gut total phospholipid n-3 PUFA as DHA (22:6n-3) with lower n-6 PUFA as arachidonic acid (20:4n-6). Canola feeding led to a small increase in ileal EPA (20:5n-3) and DHA and in colonic DHA without affecting contractility. However, there was no change in ileal membrane muscarinic binding properties due to FO feeding. This report confirms that dietary FO increases muscarinic- and eicosanoid receptor-induced contractility in ileum and that the depressed prostanoid response in SHR ileum, but not colon, is restored by tissue incorporation of DHA as the active nutrient.