<Superscript>13</Superscript>C-NMR Regioisomeric Analysis of EPA and DHA in Fish Oil Derived Triacylglycerol Concentrates

The regio-isomeric distribution of the omega-3 polyunsaturated fatty acids (PUFA) cis-5,8,11,14,17-eicosapentaenoic acid (EPA) and cis-4,7,10,13,16,19-docosahexaenoic acid (DHA) in the triacylglycerols (TAG) of anchovy/sardine fish oil was determined by ¹³C nuclear magnetic resonance (NMR) analysis under quantitative conditions. From the measurements of sn-1,3 and sn-2 carbonyl peak areas it was established that EPA was mainly located in the sn-1,3 positions, whereas DHA primarily occupied the sn-2 position. Reconstituted TAG prepared by Candida antarctica lipase-B (CALB) glycerolysis of the ethyl ester (EE) or the free fatty acid (FFA) forms of anchovy/sardine fish oil, displayed a different pattern: EPA was equally distributed, while DHA was preferentially attached to the sn-1,3 positions. TAG concentrates of varying EPA and DHA molar fractions were prepared by CALB-catalyzed glycerolysis of the corresponding EE and FFA. ¹³C-NMR analysis of the purified products revealed a lack of CALB regioselectivity for EPA and a slight sn-1,3 regioselectivity for DHA. Since this pattern was observed in all cases of this study, it was concluded that the lipase regioselectivity during TAG synthesis is independent of both the acyl donor type (carboxylic acid or ester) and the fatty acid content of the oil substrate.     

Differentiation of Fish Oils According to Species by <Superscript>13</Superscript>C-NMR Regiospecific Analyses of Triacyglycerols

The aim of this study was to use ¹³C-nuclear magnetic resonance (NMR) regiospecific analyses of triacylglycerols to distinguish fish oils from different fish species for authentication purposes. ¹³C-NMR data of muscle lipids from Atlantic salmon (Salmo salar L.), mackerel (Scomber scombrus) and herring (Clupea harengus) were obtained, and the distribution of omega-3 polyunsaturated fatty acids between the sn-1,3 and sn-2 glycerol chains calculated from the carbonyl region. The results show that there were significant differences in the sn-2 position specificity of the fatty acids 22:6n-3, 20:5n-3 and 18:4n-3 among the species investigated. The most pronounced difference was that herring had a higher proportion of its 22:6n-3 in the sn-2 position compared to the two other species. Principal component analysis of data points in the carbonyl-region showed that there were also differences in the level and regiospecific distribution of monounsaturated/saturated fatty acids, which made it possible to distinguish oils of these three species solely from the carbonyl region of ¹³C-NMR spectra.     

Linseed oil and mixture with maleic anhydride: <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR

It was shown that ¹H NMR allowed a rapid determination of the ratio of the linolenic residues over all the others (linoleic + oleic + saturated) and ¹³C NMR allowed a rapid determination of the ratio of linolenic over (linoleic + oleic) residues as well as the linoleic/oleic ratio in a few minutes on less than 20 mg of crude LO. After thermal treatment (220°C for 2 h, followed by cooling to room temperature), a 1∶1 mixture of linseed oil (LO) and maleic anhydride (MA), which was a suspension, became limpid and remained limpid. Moreover, the viscosity of the mixture was higher than that of pure LO treated in the same way. It was shown by ¹³C NMR and quantitative recovery of the constituents (LO and MA) through solvent separation that no reaction occurred between LO and MA during this thermal treatment. This result is in accord with DSC analysis of such a 1∶1 LO/MA mixture that exhibited an exothermic effect too small (about 34 kcal/mol) to correspond to formation of a C−C bond.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR characterization and stereochemical assignments of bile acids in aqueous media

The unconjugated bile acids cholic acid, deoxycholic acid, and chenodeoxycholic acid; their glycine and taurine conjugated glycocholic acid, glycodeoxycholic acid, glycochenodeoxycholic acid, taurocholic acid, taurodeoxycholic acid, and taurochenodeoxycholic acid; and a taurine conjugated ursodeoxycholic acid, tauroursodeoxycholic acid, were characterized through ¹H and ¹³C NMR in aqueous media under the physiological pH region (7.4±0.1). Assignments of ¹H and ¹³C signals of all the bile acids were made using a combination of several one- and two-dimensional, homonuclear (¹H−¹H) and heteronuclear (¹H−¹³C) correlations as well as spectral editing NMR methods. Stereochemical assignment of the five-membered ring of the bile acids is reported here for the first time. The complete characterization of various bile acids in aqueous media presented here may have implications in the study of the pathophysiology of biliary diseases through human biliary fluids using NMR spectroscopy.     

Reliability of <Superscript>1</Superscript>H NMR Analysis for Assessment of Lipid Oxidation at Frying Temperatures

The reliability of a method using ¹H NMR analysis for assessment of oil oxidation at frying temperatures was examined. During heating and frying at 180 °C, changes of soybean oil signals in the ¹H NMR spectrum including olefinic (5.16–5.30 ppm), bisallylic (2.70–2.88 ppm), and allylic (1.94–2.15 ppm) proton signals relative to glyceride backbone CH₂ (5.30–5.46 ppm) and aliphatic CH₂ (1.05–1.71 ppm) signals showed strong correlations with conventional analytical methods including total polar compounds, polymerized triacylglycerols, and changes of linoleic acid and linolenic acid peaks in gas chromatography. For oils rich in oleic acid, mid‐oleic sunflower oil (NuSun) and high oleic soybean oil, only the olefinic and allylic proton signals are recommended for analysis due to the relatively low intensity of the bisallylic proton signal. Under these heating and frying conditions, signals indicating intermediate oxidation products, hydroperoxides, were not detected while very small signals corresponding to a variety of aldehydes including alkanal, branched alkenal, 2‐alkenal, and aldehydes of conjugated dienes and epoxides were observed. In this study, it was found that the ¹H NMR method is a fast, convenient, and reliable analytical method to determine the oxidation state of frying oil.     

1H- and 13C-NMR of tactic polymethallylalcohols and polymethallylurethanes

Summary The reduction of syndiotactic or isotactic polymethyl-methacrylate yields the tactic polymethallylalcohols. Degree of conversion and tacticity can be determined by ¹H-and ¹³C-NMR. The polymethallylalcohols are reacted with isocyanates to obtain the corresponding polymethallyl urethanes whose ¹³C-NMR spectra are also studied.     

Field-assisted diffusion of K<Superscript>+</Superscript>, Rb<Superscript>+</Superscript>, Cs<Superscript>+</Superscript>, Ag<Superscript>+</Superscript>, and Tl<Superscript>+</Superscript> ions in sodium silicate glass

The composition of the diffusion zone formed during the interaction between 20Na₂O · 80SiO₂ glass and molten silver, rubidium, cesium, and thallium nitrates with and without imposition of a constant electric field was determined using X-ray microanalysis. The interdiffusion coefficients and values of electrical mobility were calculated, and the parameters of temperature dependence were determined. The electrical mobility was almost independent of the size and chemical nature of a cation and was determined by the mobility of the cation included into the initial glass.     

Recoveries of rat lymph FA after administration of specific structured <Superscript>13</Superscript>C-TAG

The potential of the specific structured TAG MLM [where M-caprylic acid (8∶0) and L=linoleic acid (18∶2n−6)] is the simultaneous delivery of energy and EFA. Compared with long-chain TAG (LLL), they may be more rapidly hydrolyzed and absorbed. This study examined the lymphatic recoveries of intragastrically administered L^*L^*, M^*M^*M^*, ML^*M, and ML^*L^* (where ^*=¹³C-labeled FA) in rats. Lymph lipids were separated into lipid classes and analyzed by GC combustion isotope ratio MS. The recoveries of lymph TAG 18∶2n-6 8 h after administration of L^*L^*L^*, ML^*M, and ML^*L^* were 38.6, 48.4, and 49.1%, respectively, whereas after 24 h the recoveries were approximately 50% in all experimental groups. The exogenous contribution to lymph TAG 18∶2n-6 was approximately 80 and 60% at maximum absorption of the specific structured TAG and L^*L^*L^*, respectively, 3–6 h after administration. The tendency toward more rapid recovery of exogenous long-chain FA following administration of specific structured TAG compared with long-chain TAG was probably due to fast hydrolysis. The lymphatic recovery of 8∶0 was 2.2% 24 h after administration of M^*M^*M^*. This minor lymphatic recovery of exogenous 8∶0 was probably due to low stimulation of chylomicron formation. These results demonstrate tendencies toward faster lymphatic recovery of long-chain FA after administration of specific structured TAG compared with long-chain TAG.     

Determination of Gasoline Octane Numbers by 1H- and 13C-NMR spectroscopy

An equation describing the relationship between the research octane number (RON) and the ¹H-and ¹³C-NMR is proposed. This equation relates the RON to the aliphatic, olefinic and aromatic hydrogen and carbon, respectively. To check this relationship 60 samples were investigated with RON values between 65 and 96. The fitting procedure yielded good agreement between the RON measured with the ASTM method and the RON calculated from both the ¹H-and the ¹³C-NMR.     

Quantification of soybean oil ethanolysis with <Superscript>1</Superscript>H NMR

In this study, proton NMR spectroscopy (200 MHz) was used for quantifying the content of ethyl esters in known mixtures of soybean oil and ethyl soyate (biodiesel). For this purpose, the peak areas of ester ethoxy and glycerol methylenic peaks in the region of 4.05–4.40 ppm were measured and a calibration plot of the respective peak areas vs. the known composition of the oil/ethyl ester mixtures was used. The transesterification values determined in this way were compared with viscosity and total glycerol determinations and a good correlation was obtained. Therefore, for routine analysis, the conversion (in %) of oil to ethyl esters was determined. The methodology presented in this work proved to be quicker and simpler than others reported in the literature, such as GC and/or HPLC.     

1 H- and 13 C-NMR Studies on Phenol-Formaldehyde Prepolymers for Tannin-Based Adhesives

Abstract

The number average structure and the molecular weight distribution of phenol-formaldehyde prepolymers for use in synthesis of tannin-based adhesive resins were determined with ¹H- and ¹³C-NMR spectroscopy and gel permeation chromatography of acetylated resins. These methods were used to determine differences in phenol-formaldehyde prepolymens prepared under different reaction conditions. Quantitative ¹³C-NMR techniques provided a detailed analysis of the structure of a phenol-formaldehyde prepolymer.     

Visible up-conversion luminescence of CaWO<Subscript>4</Subscript>: Er<Superscript>3+</Superscript>,Yb<Superscript>3+</Superscript> and emission enhancement by tri-doping of Li<Superscript>+</Superscript> ions

Er³⁺,Yb³⁺ co-doped CaWO₄ polycrystalline powders were prepared by a solid-state reaction and their up-conversion (UC) luminescence properties were investigated in detail. Under 980 nm laser excitation, CaWO₄: Er³⁺,Yb³⁺ powder exhibited green UC emission peaks at 530 and 550 nm, which were due to the transitions of Er³⁺ (²H_11/2)→Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2)→Er³⁺ (⁴I_15/2), respectively. Effects of Li+ tri-doping into CaWO₄: Er³⁺,Yb³⁺ were investigated. The introduction of Li⁺ ions reduced the optimum calcinations temperature about 100 °C by a liquid-phase sintering process and the UC emission intensity was remarkably enhanced by Li⁺ ions, which could be attributed to the lowering of the symmetry of the crystal field around Er³⁺ ions.     

Kinetics of <Superscript>14</Superscript>C distribution after tracer dose of <Superscript>14</Superscript>C-lutein in an adult woman

Lutein is an oxygenated carotenoid (xanthophyll) found in dark green leafy vegetables. High intakes of lutein may lower the risk of age-related macular degeneration. Current understanding of human lutein metabolism as it might occur in vivo is incomplete. Therefore, we conducted a feasibility study where we dosed a normal adult woman with ¹⁴C-lutein (125 nmol, 36 nCi ¹⁴C), dissolved in olive oil (0.5 g/kg body weight) and mixed in a banana shake. Blood, urine, and feces collected before the dose was administered served to establish baseline values. There-after, blood was collected for 63 d following the dose, while feces and urine were collected for 2 wk post-dose. The ¹⁴C contents in plasma, urine, and feces were measured by accelerator MS. The ¹⁴C first appeared in plasma 1 h after dosing and reached its highest level,≈2.08% of dose/L plasma, at 14 h post-dose. The plasma pattern of ¹⁴C did not include a chylomicrons/VLDL (intestinal) peak like that when the same subject received ¹⁴C-β-carotene (a previous test), suggesting that lutein was handled differently from β-carotene by plasma lipoproteins. Lutein had an elimination half-life (t _1/2) of≈10 d. Forty-five percent of the dose of ¹⁴C was eliminated in feces and 10% in urine in the first 2 d after dosing. Quantifying human lutein metabolism is a fertile area for future research.     

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.     

Structural and Activity Investigation into Al<Superscript>3+</Superscript>, La<Superscript>3+</Superscript> and Ce<Superscript>3+</Superscript> Addition to the Phosphomolybdate Heteropolyanion for Isobutane Selective Oxidation

Abstract  

Twelve phosphomolybdate compounds were synthesized via cationic exchange and were of the form: M _x H_3–3x [PMo₁₂O₄₀] (M = Al, La or Ce; 0 ≤ x ≤ 1). These compounds were analyzed by XRD and adsorption isotherm. Aluminum addition causes a primitive cubic phase, while lanthanum and cerium yield body-centered structures. La and Ce addition reduces surface area of phosphomolybdate structure. Temperature-programmed experiments for the selective oxidation of isobutane yielded methacrolein, 3-methyl-2-oxetanone (lactone), acetic acid (not with aluminous compounds), propene (only with aluminous compounds), carbon dioxide and water. The preference for propene rather than acetic acid formation with Al³⁺ may be due to the smaller cation size, or primitive cubic structure. These products form via two distinct reaction processes, labeled categories 1 and 2. Category 1 formation is associated with isobutane forming products on the surface, but reaction rate determined by bulk migration of charged particles. Category 2 formation is concerned with isobutane penetrating deep within the bulk of the substrate and forming products which subsequently desorb in a series of bell-shaped humps. Methacrolein forms via both category 1 and 2, whilst all other products form via category 2 exclusively. Kinetic analysis showed apparent activation barriers for category 1 methacrolein formation range from 67 ± 2 kJ mol⁻¹ to >350 kJ mol⁻¹, and occur in groups with small, medium and large activation barriers. The addition of +3 metal cations to the phosphomolybdate anion increase thermal stability, significantly decreasing deactivation; IR spectroscopy shows that the Keggin structure remains intact during temperature-programmed experiments with the Al, La and Ce salts.     

Hydrothermal synthesis of zeolite L in a Na<Superscript>+</Superscript>/K<Superscript>+</Superscript> mixed alkali system

Zeolite L was prepared from the substrate system of Na₂O-K₂O-Al₂O₃-SiO₂-H₂O at temperatures of 373–443 K by hydrothermal crystallization. The influence of various synthesis parameters such as the concentration ratios of the components, starting raw materials, synthesis temperature, gel aging, and stirring on the crystallization was investigated. Investigations revealed that the crystallinity of zeolite L crystals depends on molar ratios of the components such as SiO₂/Al₂O₃, (K₂O+Na₂O)/SiO₂, Na₂O/(K₂O+Na₂O), and H₂O/(K₂O+Na₂O). Pure and highly crystalline zeolite L could be obtained from a gel with the molar composition 5.4K₂O–5.7Na₂O-Al₂O₃-30SiO₂-500H₂O after 24 h at 443 K. It was found that the silica source affected the crystal size of zeolite L, and as the synthesis temperature increased, the average crystal size became larger. The crystal size could be decreased significantly by stirring the gel or subjecting the substrate mixture to an aging treatment at room temperature prior to the hydrothermal treatment. Thermal stability of the zeolite L crystals obtained was also briefly investigated.