Enzymatic glycerolysis and transesterification of vegetable oil for enhanced production of feruloylated glycerols

Novel functional groups can be introduced into vegetable oils using enzymes, resulting in value-added products. The transesterification kinetics of ethyl ferulate with MAG, DAG, and TAG were examined. Transesterification was catalyzed by immobilized Candida antarctica lipase B in solventless batch and packed-bed reactors. Initial reaction rates with TAG were slightly sensitive to water activity, whereas rates with MAG and DAG were water activity independent. Transesterification was also three-to sixfold faster with MAG and DAG. These observations indicate that the reaction is rate limited by the acyl acceptor, and that oils with free hydroxyl groups are preferred acyl acceptors in comparison with TAG, which must undergo partial hydrolysis before becoming reactive.     

13C nuclear magnetic resonance spectroscopic analysis of the triacylglycerol composition ofBiota orientalis and carrot seed oil

¹³C nuclear magnetic resonance (NMR) spectroscopic analysis of the whole oil (triacylglycerols) ofBiota orientalis seeds confirms the presence of oleate [18:1(9Z)], linoleate [18:2(9Z, 12Z)], linolenate [18:3((9Z, 12Z, 15Z)], 20:3 (5Z, 11Z, 14Z), 20:4(5Z, 11Z, 14Z, 17Z), and saturated fatty acids in the acyl groups by comparing the observed carbon shifts with previously established shift data for model triacylglycerols. This technique shows that the saturated, 20:3 and 20:4 fatty acids are distributed mainly in the α-acyl positions, whereas oleate, linoleate, and linolenate are randomly acylated to the α- and β-positions of the glycerol “backbone”. Stereospecific hydrolysis of theBiota oil with pancreatic lipase, followed by chromatographic analysis of fatty esters, reveals the presence of trace amounts of 16:0(0.7%), 18:0(0.5%), 20:3 (0.4%), and 20:4 (1.3%) in the β-position of the glycerol “backbone”, which are undetectable by¹³C NMR technique on the whole oil. Semiquantitative assessment of the¹³C NMR signal intensities gives the relative percentages of the fatty acid distribution as: saturated 16:0, 18:0 (12.0% α-acyl), oleate (7.7% α-acyl 8.7% β-acyl), total linoleate and linolenate (31.7% α-acyl; 24.2% βacyl), total 20:3 and 20:4 (15.7% α-acyl). The¹³C NMR spectroscopic analysis of carrot seed oil identifies the presence of saturated (18:0), 18:1(6Z), 18:1(9Z), and 18:2(9Z, 12Z). The saturated fatty acid is found in the α-acyl positions. Semi-quantitative assessment of the signal intensities gives the relative percentages of the fatty acids as: 18:0 (4.5% α-acyl), 18:1(6Z) (49.6% α-acyl; 19.7% β-acyl), oleate (6.5% α-acyl; 8.6% β-acyl) and linoleate (5.2% α-acyl; 6.9% β-acyl).     

Nutrition of rice bran oil in relation to its purification

A comparative nutritive study was made to show that the extent of purification markedly influences the nutritive characteristics of rice bran oil. The coefficient of digestibility was 93.8% when rice bran oil that had been purified by degumming, deacidifying, bleaching and deodorizing was fed to rats; whereas it was 94.8% when extremely pure rice bran oil, which was achieved by including an additional dewaxing step, was used. Rice bran oil without deodorization, but purified by other treatments, showed a 96.2% coefficient of digestibility, which is somewhat lower than that of groundnut oil. However, after a feeding experiment over three months, the highly purified rice bran oil showed better results than the other two purified samples of rice bran oil, and was sometimes better than groundnut oil in terms of total lipid, triglyceride and especially in cholesterol content in serum, liver and heart tissues.     

Ozonation of sunflower oil: Spectroscopic monitoring of the degree of unsaturation

Consumption of ozone by unsaturated FA moieties of sunflower oil (SFO) was monitored by ¹H NMR and FTIR spectroscopy. Degradation of linoleate was found to be 1.5 and 1.8 times higher than oleate when SFO was ozonized in the absence and presence of water, respectively. Products of ozonation in both cases include aldehydes and ozonides with 1,2,4-trioxolane ring. Hydroxyl-containing compounds, which could be carboxylic acids and/or hydroperoxides, were also detected in samples ozonized in the presence of water. The extent of ozonation had very little effect on the aldehyde/ozonide ratio obtained from NMR spectra, especially in the ozonation of neast SFO. The aldehyde/ozonide ratios obtained regardless of the extent of ozonation were 10.5:89.5 and 46.6:53.4 for SFO ozonized in the absence and presence of water, respectively.     

Impact of Chronic Hepatitis C Virus Genotype 1b Infection on Triglyceride Concentration in Serum Lipoprotein Fractions

Reduced low-density lipoprotein (LDL) cholesterol level is a characteristic feature of dyslipidemia in chronic hepatitis C virus (HCV) infection. However, abnormality in serum triglyceride (TG) has not been fully investigated. To clarify the impact of HCV genotype 1b (G1b) infection and advanced fibrosis on serum TG profiles, TG concentrations in lipoprotein fractions were examined in fasting sera from 185 subjects with active or cleared HCV infection by high-performance liquid chromatography. Serum lipoproteins were fractionated into four classes: chylomicron, very low-density lipoprotein (VLDL), LDL, and high-density lipoprotein (HDL). Then, the significance of HCV G1b infection on TG levels in each lipoprotein fraction was determined using multiple regression models. We found that active HCV G1b infection was positively associated with high HDL-TG levels and low VLDL-TG levels, independent of other factors included in the regression model. In VLDL sub-fractions, active HCV infection was only found to be associated with low levels of large VLDL-TG. Similarly, advanced liver fibrosis in chronic HCV G1b infection was associated with high levels of LDL-TG, HDL-TG, and small VLDL-TG, independent of other clinical factors. These findings indicate that active HCV G1b infection and advanced fibrosis are closely associated with abnormal serum TG profiles.     

Silica-supported alloy catalysts for triglyceride hydrogenation: The preparation and properties of Pd–Ag and Pd–Ni systems

The binary metal systems Pd–Ag and Pd–Ni have been prepared on a silica support with a total metal loading of 2.5% (w/w). About a dozen catalysts were prepared in each series covering the range 0–100 at. % Pd. The catalysts were characterised by a number of techniques, principally temperature programmed reduction, differential scanning calorimetry and metal surface area measurement. The catalyst activity and selectivity were measured for the hydrogenation of soya bean oil in both stirred and shaken batch reactors at 1 atm H₂ pressure in the temperature range 100–160°C. The characterisation techniques provided strong evidence of alloying for both series of catalysts. The activity and selectivity measurements also provided supporting evidence of alloying, and the Pd–Ag system exhibited an activity maximum in the 90–100 at. % Pd range, while the Pd–Ni system maintained constant activity for alloys containing 0–60 at. % Ni. Trans-acid formation was suppressed by lower reduction temperature, and linolenate removal was improved at lower temperatures. However, it also appears that reaction rates were dominated largely by triglyceride diffusion effects.     

Molecular exchange in thermal equilibrium between dissolved and crystalline tripalmitin by NMR

An NMR technique to measure exchange kinetics at thermal equilibrium in dispersions of moderately soluble crystalline material is presented. By monitoring the exchange of molecules between pools in solid and dissolved form, one can characterize the surface specific exchange rate. Illustrative experiments were performed in a model system with β-type crystals of tripalmitin as the solid phase and tripalmitin, a fraction of it deuterated, dissolved in a medium-chain TG oil as the liquid phase. The concentration of deuterated tripalmitin in the solvent was followed by ²H NMR after the crystals, which initially lack deuterated tripalmitin, were immersed in the liquid. The variation of the ²H concentration in the solvent provided the surface specific exchange rate. No systematic errors, due to the slight difference in properties of the deuterated tripalmitin compared to hydrogenated tripalmitin, were observed. The methodology worked well between crystal concentrations of 2 and 4 wt%.     

The Influence of Lubricating Agents on the Formation of a Film of a Styrene/Butadiene Latex

The interactions between paper coating lubricants and a carboxylated styrene/butadiene latex emulsion and their effect on latex film morphology have been studied. Calcium stearate, non-ionic polyethylene emulsion and organic triglyceride lubricants showed different interaction characteristics with the latex emulsion according to viscosity, zeta potential and isothermal calorimetric measurements. Calcium stearate lowered the viscosity of the dilute latex emulsion at low concentration suggesting a strong interaction with the latex particles due to a change in the hydrodynamic dimensions of the latex particles. The exothermic enthalpy change supported the assumption of a dissociative interaction. In contrast, both non-ionic polyethylene and organic triglyceride emulsion showed less pronounced enthalpy changes, indicating lower affinity for the latex particles. The reduction in viscosity showed, however, that at low lubricant concentrations there is an interaction between the latex particles and particularly the organic triglyceride emulsion. This suggests a selective adsorption of stabilizing agents and species from the lubricant emulsion which alters the hydrodynamic radius of the latex particles. The effects of the colloidal interactions on the morphology of the latex films monitored by Atomic Force Microscopy (AFM) indicated that specific surface interaction occurring in aqueous media influenced the topography and the surface chemical heterogeneity of the latex films. Especially in the case of calcium stearate, it seems that the dissolved species arrange themselves around the latex particles inhibiting film formation. The organic triglyceride, on the other hand, showed a lower interaction potential in the aqueous phase and it had a different impact on the film formation.