Separation of conjugated linoleic acid methyl esters by silver-ion high performance liquid chromatography in semi-preparative mode

Silver-ion HPLC (Ag-HPLC) has been utilized to separate a variety of unsaturated fatty acid methyl esters (FAMEs) by configuration, location or number of olefinic or acetylenic bonds. Two analytical Ag-HPLC columns connected in series and an isocratic solvent system of acetonitrile (ACN) in hexane were used to fractionate 10-15 mg samples of a mixture of two deuterium-labeled isomers of conjugated linoleic acid (Z9.E11- and Z9,Z11-octadecadienoic acid-17,17,18,18-d4). "Baseline" (> 95%) resolution of the two isomers, which decreased with increasing weights of sample injected, was maintained by careful adjustment of the percentage of ACN in the ACN/hexane solvent system. Chemical purities of the isolated FAME were > 96%.     

Kinetics and mechanism of the oxidation of hydrogen peroxide by the octacyanotungstate(V) ion in alkaline aqueous media

Summary The oxidation of H₂O₂ by [W(CN)₈]^3– has been studied in aqueous media between pH 7.87 and 12.10 using both conventional and stopped-flow spectrophotometry. The reaction proceeds without generation of free radicals. The experimental overall rate law, , strongly suggests two types of mechanisms. The first pathway, characterized by the pH-dependent rate constant k _s, given by , involves the formation of [W(CN)₈· H₂O₂]^3–, [W(CN)₈· H₂O₂·W(CN)₈]^6– and [W(CN)₈· HO]^3– intermediates in rapid pre-equilibria steps, and is followed by a one-electron transfer step involving [W(CN)₈·HO]^3– (k _a) and its conjugate base [W(CN)₈·O]^4– (k _b). At 25 °C, I = 0.20 m (NaCl), the rate constant with H _a =40±6kJmol^–1 and S _a =–151±22JK^–1mol^–1; the rate constant with H _b =36±1kJmol^–1 and S _b =–136±2JK^–1mol^–1 at 25 °C, I = 0.20 m (NaCl); the acid dissociation constant of [W(CN)₈·HO]^3–, K ₅ =(5.9±1.7)×10^–10 m, with and is the first acid dissociation constant of H₂O₂. The second pathway, with rate constant, k _f, involves the formation of [W(CN)₈· HO₂]^4– and is followed by a formal two-electron redox process with [W(CN)₈]^3–. The pH-dependent rate constant, k _f, is given by . The rate constant k ₇ =23±6m ^–1 s ^–1 with and at 25°C, I = 0.20 m (NaCl).     

Thermal decomposition and stability of fatty acid methyl esters in supercritical methanol

In recent years, non-catalytic supercritical processes for biodiesel production have been proposed as alternative environmentally friendly technologies. However, conditions of high temperature and pressure that occur while biodiesel is in supercritical fluid can cause fuel degradation, resulting in low yield. In this study, we performed the thermal decomposition of fatty acid methyl esters (FAMEs) in supercritical methanol at temperatures ranging from 325 °C to 420 °C and pressure of 23 MPa to investigate the degradation characteristics and thermal stability of biodiesel. The primary reactions we observed were isomerization, hydrogenation, and pyrolysis of FAMEs. The main pathway of degradation was deduced by analyzing the contents of degradation products. We found that if FAME has shorter chain length or is more saturated, it has higher thermal stability in supercritical methanol. All FAMEs remained stable at 325 °C or below. Based on these results, we recommend that transesterification reactions in supercritical methanol should be carried out below 325 °C (at 23 MPa) and 20 min, the temperature at which thermal decomposition of FAMEs begins to occur, to optimize high-yield biodiesel production.     

Development and application of an analytical method for the determination of storage lipids, fatty acids and fatty alcohols in Calanus finmarchicus

A method was developed for the determination of the major storage lipids, wax ester and triglycerides, in the copepod Calanus finmarchicus. A variation of the Folch method was used to extract the lipid. The method was scaled down to enable the extraction of either pooled (-1 mg) or individual (approximately 200 microg) copepods. The major lipid classes were identified using TLC and quantified using HPLC coupled with evaporative light scattering detection. Analysis of laboratory reference materials indicated that this method underestimated the minor triglyceride component, but gave a good estimate of the major wax ester component. The fatty acid and fatty alcohol composition of the C. finmarchicus were determined following trans-esterification of the lipid extract in methanol. Fatty acids and fatty alcohols were initially identified by comparison with authentic standard and by mass spectroscopy. Using GC with flame ionisation detection the normalised area percentage of the fatty alcohols and fatty acid methyl esters was determined simultaneously in one run for either pooled or individual copepod samples. These methods were applied to C. finmarchicus collected from the Irminger Sea, North Atlantic in 2001 and 2002.     

A new process for preparing dialdehyde by catalytic oxidation of cyclic olefins with aqueous hydrogen peroxide

A. novel peroxo-niobophosphate was synthesized for the first time and used as a catalyst in the oxidation reaction of cyclic olefins with aqueous hydrogen peroxide to prepare dialdehy-des. The catalyst was characterized by elemental analysis, thermographic analyses, IR, UV/vis, 31P NMR and XPS spectra as [ π-C5H5N(CH2 )13 CH3 ]2 [ Nb4O6 (O2 )2 (PO4 )2 ] ·6H2O (PTNP). It showed high selectivity to glutaraldehyde in the catalytic oxidation of cyclopentene with aqueous hydrogen peroxide in ethanol.     

Quantification of fatty acids as methyl esters and phospholipids in cheese samples after separation of triacylglycerides and phospholipids

Determination of the individual fatty acid composition of neutral- and phospholipids as well as the phospholipid content of dairy food and other foodstuffs are important tasks in life sciences. For these purposes, a method was developed for the separation of lipids (standards of triolein and diacylphosphatidylcholines as well as three cheese samples) by solid-phase extraction using a self-packed column filled with partly deactivated silica. Non-halogenated solvents were used for the elution of the lipid classes. Cyclohexane/ethyl acetate (1:1, v/v) served for the elution of neutral lipids, while polar lipids were eluted with three solvents (ethyl acetate/methanol, methanol, and methanol/water) into one fraction. The separated lipid fractions were transesterified and the individual fatty acids were quantified by using gas chromatography coupled to electron ionization mass spectrometry (GC/EI-MS) in the selected ion monitoring (SIM) mode. The recovery rate for standard phosphatidylcholines was ∼90% and cross-contamination from neutral lipids was negligible. The method was applied to cheese samples. Quantitative amounts of individual fatty acids in the phospholipid fraction were <0.002-0.29% of total lipids from camembert, <0.002-0.12% of total lipids from mozzarella, and <0.002-0.18% of total lipids in a goat cream cheese. Differences in the fatty acid pattern of neutral and polar lipids were detected. The quantity of the fatty acids determined in the phospholipid fraction was divided by the factor 0.7 in order to convert the fatty acid content into the phospholipid content of the cheese samples. This factor is based on the contribution of 16:0 to dipalmitoylphosphatidylcholine (DPPC). The resulting DPPC equivalents (DPPC_eq) were found to be representative for the average contribution of fatty acids to all classes of phospholipids in dairy products. Using this approach, the phospholipid content of lipids from mozzarella, camembert, and goat cream cheese was 0.60%, 1.42% and 0.79%, respectively.     

Dioxaborirane: a highly reactive peroxide that is the likely intermediate in borate catalysed electrophilic reactions of hydrogen peroxide in alkaline aqueous solution

This paper reports on a kinetic and theoretical study into the borate mediated reaction of dimethyl sulfide with hydrogen peroxide in both acid and alkaline conditions. At high pH, whilst the kinetic data is consistent with the catalytic species being monoperoxoborate, formed from the rapid equilibrium between hydrogen peroxide and boric acid, DFT calculations show that this species is in fact less reactive than hydrogen peroxide, requiring us to seek an alternative catalytic mechanism. DFT provides an important insight for this, showing that although boric acid and peroxoboric acid are primarily Lewis acids, they can exhibit a small degree of Br?nsted acidity, allowing, respectively, the B(O)(OH)(2)(-) and HOOB(OH)(O)(-) anions to exist in small concentrations. Whilst the peroxoborate anion, HOOB(OH)(O)(-), is predicted to have only marginal catalytic activity, its tautomer, dioxaborirane, (HO)(2)BO(2)(-), a three membered cyclic peroxide, has a very low activation barrier of 2.8 kcal/mol. Hence, even though dioxaborirane is likely to be present in very low concentrations, it is still sufficiently reactive for overall rate enhancements to be observed for this system. This is the first literature report of this species. The observed low selectivity observed for borate catalysed reactions of hydrogen peroxide with a range of substituted phenyl methyl sulfides in our previous study (D. M. Davies, M. E. Deary, K. Quill and R. A. Smith, Chem.-Eur. J. 2005, 11, 3552-3558) is further evidence in favour of a highly reactive catalytic species. At low pH, kinetic data shows that borate catalyses the reaction between hydrogen peroxide and dimethyl sulfide; this is supported by DFT calculations that predict peroxoboric acid to be an effective catalytic intermediate, with an energy barrier of 7.4 kcal mol(-1) compared to 10.1 kcal mol(-1) for the uncatalysed system. Nevertheless, the overall contribution of this pathway is small because of the unfavourable equilibrium between hydrogen peroxide and boric acid to form peroxoboric acid.     

Chlorotrimethylsilane, a reagent for the direct quantitative analysis of fats and oils present in vegetable and meat samples

Acylglycerides present in oil seeds and meat can be transformed into volatile fatty esters using chlorotrimethylsilane (CTMS) and 1-pentanol as reagents. The volatile esters can then be analysed by GC. The method is quantitative and involves only minor sample manipulation. It often permits major recoveries of the total saponifiable lipids present in solid samples. A 40 min reaction time is enough to ensure the total conversion of saponifiable lipids to the corresponding FAPEs.     

Fast and simple method for determination of fatty acid methyl esters (FAME) in biodiesel blends using X-ray spectrometry

The determination of fatty acid methyl esters (FAME) in diesel fuel blends is an important aspect of production and blending process as well as quality control of distribution operations. In this study, energy-dispersive X-ray fluorescence spectrometer (EDXRF) is used for the first time for determination of FAME in biodiesel blends. The principle of the method is based on intensity difference of X-ray radiation scattered from hydrocarbons and from FAME. The experiment shows that coherent and incoherent radiation, commonly applied for evaluation of the average atomic number of the sample with light matrix, cannot be applied for FAME determination. However, the application of scattered continuous radiation gives excellent correlation between FAME concentration and intensity of scattered radiation. The best results are obtained if continuum is collected in the range of energy between 10.5 and 15.0 keV for rhodium X-ray tube, operated at 35 kV. Linear relationship between the FAME concentration and the inverse of scattered continuous radiation is obtained with the correlation coefficients of 0.999. Standard deviation of measurement is ca. 0.46% (v/v) of FAME and detection limit is 1.2% (v/v) for 600 s counting time and 50% dead-time loss using Si-PIN detector. The investigation shows that crucial issue in determination of FAME in biodiesel blends using EDXRF spectrometer is the precision of measurements resulting from the counting statistics. Therefore, much better results (0.20% (v/v) standard deviation and 0.52% (v/v) detection limit) can be expected if higher intensity of primary radiation is applied and X-ray spectrum is collected by silicon drift detector of high input count rate. For concentration of FAME from 10 to 100% (v/v), the differences between reference method (Fourier transform infrared spectrometry) and the proposed method usually do not exceed 1% (v/v) of FAME. The proposed method is fast, simple and enables FAME determination in wide range of concentration up to 100% of FAME without any sample treatment.     

Quantification of trace fatty acid methyl esters in diesel fuel by using multidimensional gas chromatography with electron and chemical ionization mass spectrometry

Measurement of contamination of marine and naval diesel fuels (arising from product mixing or adulteration) with biodiesel or fatty acid methyl esters can be problematic, especially at very low levels. A suitable solution for this task for trace amounts of individual fatty acid methyl esters with resolution and quantification can be achieved by using a multidimensional gas chromatographic approach with electron and chemical ionization mass spectrometric detection. A unique column set comprising a 100 m methyl‐siloxane nonpolar first dimension column and high‐temperature ionic liquid column in the second dimension enabled identification of individual fatty acid methyl esters at below the lowest concentrations required to be reported in a diesel fuel matrix. Detection limits for individual fatty acid methyl esters compounds ranged from 0.5 to 5.0 mg/L, with excellent linearity up to 5000 mg/L and repeatability of the method from 1.3 to 3.2%. The method was applied to the analysis of diesel fuel samples with suspected biodiesel contamination. Contamination at 568 mg/L was calculated for an unknown sample and interpretation of the results permitted the determination of a likely source of the contamination.     

Evaluation of the separation characteristics of application-specific (fatty acid methyl esters) open-tubular columns for gas chromatography

The solvation parameter model is used to characterize the separation properties of the polar stationary phases EC-Wax and PAG with a poly(ethylene oxide) backbone (substituted with propylene oxide in the case of PAG) and the cyanopropyl-substituted polysilphenylene-siloxane stationary phase BPX90 at five equally spaced temperatures between 60 and 140 degrees C. The separation characteristics of these stationary phases are compared to four PEG and two poly(cyanopropylsiloxane) stationary phases (HP-20M, HP-Innowax, SolGel-Wax, DB-WAXetr, HP-88, and SP-2340) characterized in the same way. The database of system constants for these polar stationary phases is used to provide insight into the separation mechanism for fatty acid methyl esters and to determine selectivity differences that can be expected for generically similar stationary phase types. The discussion is not structured to indicate which stationary phase should be used for a particular separation but to provide a general framework to demonstrate the relationship between the retention mechanism and stationary phase chemistry.     

Experimental designs for modeling retention patterns and separation efficiency in analysis of fatty acid methyl esters by gas chromatography-mass spectrometry

The retention behavior of components analyzed by chromatography varies with instrumental settings. Being able to predict how changes in these settings alter the elution pattern is useful, both with regards to component identification, as well as with regards to optimization of the chromatographic system. In this work, it is shown how experimental designs can be used for this purpose. Different experimental designs for response surface modeling of the separation of fatty acid methyl esters (FAME) as function of chromatographic conditions in GC have been evaluated. Full factorial, central composite, Doehlert and Box-Behnken designs were applied. A mixture of 38 FAMEs was separated on a polar cyanopropyl substituted polysilphenylene-siloxane phase capillary column. The temperature gradient, the start temperature of the gradient, and the carrier gas velocity were varied in the experiments. The modeled responses, as functions of chromatographic conditions, were retention time, retention indices, peak widths, separation efficiency and resolution between selected peak pairs. The designs that allowed inclusion of quadratic terms among the predictors performed significantly better than factorial design. Box-Behnken design provided the best results for prediction of retention, but the differences between the central composite, Doehlert and Box-Behnken designs were small. Retention indices could be modeled with much better accuracy than retention times. However, because the errors of predicted tR of closely eluting peaks were highly correlated, models of resolution (Rs) that were based on retention time had errors in the same range as corresponding models based on ECL.     

(Vapor + liquid) equilibrium for the binary systems {water + glycerol} and {ethanol + glycerol, ethyl stearate, and ethyl palmitate} at low pressures

This work reports the experimental measurements {(vapor + liquid) equilibrium} for the systems {water(1) + glycerol(2)}, {ethanol(1) + glycerol(2)}, {ethanol(1) + ethyl stearate(2)}, and {ethanol(1) + ethyl palmitate(2)}. Boiling temperatures were measured using an Othmer-type ebulliometer over a pressure range of 14 kPa to 96 kPa. The experimental data were well correlated using the NRTL and UNIQUAC models. The performance of the UNIFAC-Dortmund model in relation to predicting the phase equilibrium of the systems was also studied.     

Rapid procedure for the isolation and analysis of fatty acid and fatty alcohol fractions from wax esters of marine zooplankton

A rapid and simple method for the isolation of fatty acid methyl esters and fatty alcohols from the lipid fraction of marine zooplankton is described. Wax esters are the dominant lipid class in most calanoid copepods and trans-esterification results in a high fatty alcohol content in the analytical extract. Current procedures for the separation and purification of lipid classes by preparative thin-layer chromatography are time-consuming and are subject to low recovery of the analytes. In this method, fatty acid methyl esters and fatty alcohols were separated by liquid chromatography using silica or honded amino-silica as the stationary phase. The procedure is equally applicable to the analysis of zooplankton with low wax ester (and hence fatty alcohol) content, for example, a number of species of euphausiid and, generally, for samples of low mass.     

Ground and electronically excited states of methyl hydroperoxide: comparison with hydrogen peroxide

Equilibrium geometries of the ground states of hydrogen peroxide (H(2)O(2)) and methyl hydroperoxide (CH(3)OOH) have been obtained using quadratic configuration interaction methods with correlation-consistent basis sets. These results are compared with experiments and prior calculations. The dipole moments of the ground states of these two molecules have been calculated. The results illustrate the sensitivity of this quantity to molecular geometry. Several excited states of H(2)O(2) and CH(3)OOH were calculated using the equation-of-motion coupled-cluster singles-and-doubles method. Aside from vertical excitation energies, excited state energies along the O-O, O-H, and C-O dissociation pathways were calculated. The results are expected to be of assistance in resolving discrepancies in the experimental interpretation of the UV absorption spectrum and photodissociation of CH(3)OOH.     

Effect of temperature on hydrogen peroxide photolysis in aqueous solutions

The photolysis of hydrogen peroxide in dilute aqueous solution (1 × 10⁻⁴ M) at various temperatures (15–85°C) and pH (ph 2.5–7) was studied by flash photolysis. The rate of oxygen production under continuous photolysis conditions was measured at room temperature. The rate constants and activation parameters are reported. Evidence for the formation of complexes between hydrogen peroxide and intermediate radicals is presented. The liquid phase data are discussed and compared with those available for the gas phase.