A Simple and Efficient Method for Synthesis and Extraction of Ethyl Ferulate from γ-Oryzanol.

Ethyl ferulate (EF) is a ferulic acid (FA) derivative with high commercial value. It is not found naturally and is mostly synthesized from FA via esterification with ethanol. The present work aimed to synthesize the EF from γ-oryzanol, a natural antioxidant from rice bran oil via acid-catalyzed transethylation at refluxing temperature of ethanol. The reaction was optimized by central composite design (CCD) under response surface methodology. Based on the CCD, the optimum condition for the synthesis of EF from 0.50 g of γ-oryzanol was as follows: γ-oryzanol to ethanol ratio of 0.50:2 (g/mL), 12.30% (v/v) H2SO4, and a reaction time of 9.37 h; these conditions correspond to a maximum EF yield of 87.11%. Moreover, the optimized transethylation condition was further validated using 12.50 g of γ-oryzanol. At the end of the reaction time, distilled water was added as antisolvent to selectively crystallize the co-products, phytosterol and unreacted γ-oryzanol, by adjusting the ethanol concentration to 49.95% (v/v). The recovery yield of 83.60% with a purity of 98% of EF was achieved. In addition, the DPPH and ABTS assays showed similar antioxidant activities between the prepared and commercial EF.

Simulation of peak position and response profiles in comprehensive two-dimensional gas chromatography.

Approaches to simulate peak time and intensity profiles of compounds in comprehensive two dimensional gas chromatography (GC × GC) were developed, and which are demonstrated for separation of a mixture of saturated and unsaturated fatty acid methyl esters (FAME) using a range of column sets. The simulation of first and second dimension time (1tR and 2tR) of FAME relies on use of a Gibbs energy additivity approach to correlate with the structures of FAME. First and second dimension peak standard deviations (1σ and 2σ) of the compounds were further calculated from the 1tR and 2tR data according to the plate height concept which provided good agreement between the predicted and experimental peak widths at half height in one dimension GC (1DGC) with an overall R2 of 0.9628. The effect of 1σ distortion caused by the modulation process was also taken into account in the peak width simulation where the simulated 1σ data were rounded up to multiples of the scale of modulation period (PM). Two dimension Gaussian equations were then used to generate GC × GC results (2D contour plots) from simulated 1tR, 2tR, 1σ and 2σ data for FAME separation on different column sets employing ionic liquid and conventional columns. Good overall correlations between experimental and simulated 1tR and 2tR were obtained with R2 of 0.9951 and 0.9802, respectively, and the simulated 2D contour plots were an acceptable match with the experimental results.

Ionic liquid phases with comprehensive two-dimensional gas chromatography of fatty acid methyl esters.

New generation inert ionic liquid (iIL) GC columns IL60i, IL76i and IL111i, comprising phosphonium or imidazolium cationic species, were investigated for separation of fatty acid methyl esters (FAME). In general, the iIL phases provide comparable retention times to their corresponding conventional columns, with only minor selectivity differences. The average tailing factors and peak widths were noticeably improved (reduced) for IL60i and IL76i, while they were slightly improved for IL111i. Inert IL phase columns were coupled with conventional IL columns in comprehensive two-dimensional GC (GC × GC) with a solid-state modulator which offers variable modulation temperature (TM), programmable TM during analysis and trapping stationary phase material during the trap/release (modulation) process, independent of oven T and column sets. Although IL phases are classified as polar, relative polarity of the two phases comprising individual GC × GC column sets permits combination of less-polar IL/polar IL and polar IL/less-polar IL column sets; it was observed that a polar/less-polar column set provided better separation of FAME. A higher first dimension (1D) phase polarity combined with a lower 2D phase polarity, for instance 1D IL111i with 2D IL59 gave the best result; the greater difference in 1D/2D phase polarity results in increasing occupancy of peak area in the 2D space. The IL111i/IL59 column set was selected for analysis of fatty acids in fat and oil products (butter, margarine, fish oil and canola oil). Compared with the conventional IL111, IL111i showed reduced column bleed which makes this more suited to GC × GC analysis of FAME. The proposed method offers a fast profiling approach with good repeatability of analysis of FAME.

Gibbs energy additivity approaches to QSRR in generating gas chromatographic retention time for identification of fatty acid methyl ester.

The Gibbs energy additivity method was used to correlate the retention time (t R) of common fatty acid methyl esters (FAMEs) to their chemical structures. The t R of 20 standard FAMEs eluted from three capillary columns of different polarities (ZB-WAXplus, BPX70, and SLB-IL111) under both isothermal gas chromatography and temperature-programmed gas chromatography (TPGC) conditions were accurately predicted. Also, the predicted t R of FAMEs prepared from flowering pak choi seed oil obtained by multistep TPGC with the BPX70 column were within 1.0% of the experimental t R. The predicted t R or mathematical t R (t R(math)) values could possibly be used as references in identification of common FAMEs. Hence, FAMEs prepared from horse mussel and fish oil capsules were chromatographed on the BPX70 and ZB-WAXplus columns in single-step and multistep TPGC. Identification was done by comparison of t R with the t R of standard FAMEs and with t R(math). Both showed correct identifications. The proposed model has six numeric constants. Five of six could be directly transferred to other columns of the same stationary phase. The first numeric constant (a), which contained the column phase ratio, could also be transferred with the adjustment of the column phase ratio to the actual phase ratio of the transferred column. Additionally, the numeric constants could be transferred across laboratories, with similar correction of the first numeric constant. The TPGC t R predicted with the transferred column constants were in good agreement with the reported experimental t R of FAMEs. Moreover, hexane was used in place of the conventional t M marker in the calculation. Hence, the experimental methods were much simplified and practically feasible. The proposed method for using t R(math) as the references would provide an alternative to the uses of real FAMEs as the references. It is simple and rapid and with good accuracy compared with the use of experimental t R as references.