Comparison of Three Methods for Extraction of Volatile Lipid Oxidation Products from Food Matrices for GC–MS Analysis

The aim of this study was to compare three different collection methods; purge and trap, solid phase micro extraction and automated dynamic headspace/thermal desorption, all followed by GC–MS analysis used for the measurements of concentrations of volatile oxidation products in three different food matrices, namely oil, emulsion and milk. The linearity ranges of calibration curves obtained by the three different methods were compared for oil samples. Overall, the results showed that the three collection methods were comparable, although there were large differences in the linearity range of the calibration curves depending on the collection method. However, some challenges were observed for solid phase micro extraction and automated dynamic headspace/thermal desorption, namely, competition problems and overestimation of concentration by calibration curves, respectively. Based on the results, we suggest mainly to apply solid phase micro extraction on simple matrices and to be cautious with more complex matrices such as enriched milk and highly oxidized oils. Thereby, the study confirmed some challenges observed by other authors regarding competition problems on the fiber when using solid phase micro extraction. Furthermore, we observed that purge and trap, and automated dynamic headspace/thermal desorption were excellent for extraction of volatile compounds in all three matrices. However, automated dynamic headspace/thermal desorption calibration curves did provide an overestimation for oil samples so results must be interpreted with caution.     

Women and Smokers Have Elevated Urinary F2-Isoprostane Metabolites: A Novel Extraction and LC–MS Methodology

F(2)-Isoprostanes (F(2)-IsoPs), regio- and stereoisomers of prostaglandin F(2alpha) (PGF(2alpha)), and urinary F(2)-IsoP metabolites including 2,3-dinor-5,6-dihydro-8-iso-PGF(2alpha) [2,3-dinor-8-iso-PGF(1alpha) (2,3-dinor-F1)] and 2,3 dinor-8-iso-PGF(2alpha) (2,3-dinor-F2), have all been used as biomarkers of oxidative stress. A novel method was developed to measure these biomarkers using a single solid phase extraction (SPE) cartridge, separation by HPLC, and detection by negative mode selected reaction monitoring (SRM) mass spectrometry (MS), using authentic standards of PGF(2alpha); 8-iso-PGF(2alpha); 2,3-dinor-F1 and 2,3-dinor-F2 to identify specific chromatographic peaks. The method was validated in a population of healthy, college-aged nonsmokers (n = 6 M/8F) and smokers (n = 6 M/5F). Urinary F(2)-IsoP concentrations were approximately 0.2-1.5 microg/g creatinine, 2,3-dinor-F1 was approximately1-3 microg/g and 2,3-dinor-F2 was approximately 3-5 microg/g. Additional F(2)-IsoPs metabolites were identified using SRM. The sum of all urinary F(2)-IsoP metabolites was 50-100 microg/g creatinine indicating their greater abundance than F(2)-IsoPs. Women had higher F(2)-IsoP metabolite concentrations than did men (MANOVA, main effect P = 0.003); cigarette smokers had higher concentrations than did nonsmokers (main effect P = 0.036). For men or women, respectively, smokers had higher metabolite concentrations than did nonsmokers (P < 0.05). Thus, our method simultaneously allows measurement of urinary F(2)-IsoPs and their metabolites for the determination of oxidative stress.     

Combination of Refractometry and Densimetry – A Promising Option for Fast Raw Methanol Analysis

Besides water, raw methanol produced from steel mill gases within the Carbon2Chem® project contains dissolved carbon dioxide. Refractometry and densimetry were investigated as analysis methods to analyze raw methanol samples quickly and reliably. To verify existing calibration curves, a set of standard solutions from pure chemicals was produced. Experimental results differed significantly from published refractive index data, especially in the range of high methanol weight fractions, which are of particular interest for the Carbon2Chem® project.     

A Comprehensive GC–MS Sub-Microscale Assay for Fatty Acids and its Applications

Fatty acid analysis is essential to a broad range of applications including those associated with the nascent algal biofuel and algal bioproduct industries. Current fatty acid profiling methods require lengthy, sequential extraction and transesterification steps necessitating significant quantities of analyte. We report the development of a rapid, microscale, single-step, in situ protocol for GC–MS lipid analysis that requires only 250 μg dry mass per sample. We furthermore demonstrate the broad applications of this technique by profiling the fatty acids of several algal species, small aquatic organisms, insects and terrestrial plant material. When combined with fluorescent techniques utilizing the BODIPY dye family and flow cytometry, this micro-assay serves as a powerful tool for analyzing fatty acids in laboratory and field collected samples, for high-throughput screening, and for crop assessment. Additionally, the high sensitivity of the technique allows for population analyses across a wide variety of taxa.     

An Improved Method for Analysis of Glucosylceramide Species Having cis-8 and trans-8 Isomers of Sphingoid Bases by LC–MS/MS

High-performance liquid chromatography–electrospray ionization tandem mass spectrometry (HPLC–ESI–MS/MS) approaches have enabled high selectivity and sensitivity for the identification and quantification of glucosylceramide molecular species. Here we demonstrate that HPLC–ESI–MS/MS is an efficient method for characterizing plant glucosylceramide species having the cis-8 and trans-8 isomers of sphingoid bases. Complete baseline separation was achieved using a high-carbon-content octadecylsilyl column and a simple binary gradient comprising methanol and water. The result of 2-hydroxy fatty acid composition achieved by HPLC–ESI–MS/MS was compared with that achieved by gas chromatography with flame ionization detection (GC–FID), indicating that the two methods yield similar molar compositions. The current method should be applicable to seeking the active components of glucosylceramide species from plant materials in response to biological challenges.     

SFC–MS/MS for identification and simultaneous estimation of the isoniazid and pyrazinamide in its dosage form

An ecofriendly and sensitive SFC–MS/MS method (using TurboIonSpray probes) has been developed to measure Isonaizid (INH) and pyrazinamide (PYZ) in fix dosage combination (FDC) by dissolving in dichloromethane:methanol:formic acid (50:50:0.1 v/v/v). Supercritical carbon dioxide (SC-CO₂) is used as mobile phase at a flow rate of 2 ml/min and modifier used is dichloromethane:methanol:formic acid (50:50:0.1 v/v/v) at a flow rate of 0.3 ml/min. High penetration power, low viscosity, negligible toxicity makes the obvious choice for environment friendly mobile phase. The separation of INH and PYZ was achieved in less than 5 min using a C18 reverse-phase fused-core column (Inertsil ODS-5 μm C18, 150 mm × 4.6 mm). The method was validated as per international standards in terms of selectivity, linearity, precision and recovery. The method was found to be linear and % recovery was found to be 98.89–100.33% and 99.27–100.06% for INH and PYZ, respectively. Lower limits of detection and quantification could be achieved for INH was 11.87 ng/ml and 35.97 ng/ml, respectively, and for PYZ was 35.42 ng/ml and 107.36 ng/ml, respectively. The proposed method was applied to the marketed formulation of different manufacturers.     

CFD Simulation of Liquid–Liquid Two-Phase Hydrodynamics and Axial Dispersion Analysis for a Non-Pulsed Disc and Doughnut Solvent Extraction Column

A two-phase computational fluid dynamics (CFD) simulation for a non-pulsed disc and doughnut solvent extraction column has been developed with commercial CFD software FLUENT. Simulated hydrodynamic results including phase distribution, velocity fields, and holdup are given, which enables predicted holdup to be compared with experimental data. Average absolute relative deviation (AARD) of experimental data and CFD prediction in this study is found to be 10.8%, which is comparable to the estimated error in the experimental data and the predictions from traditional correlations in the literature. To estimate the extent of axial dispersion, a species transport model is used for the continuous phase with a small amount of tracer introduced in the continuous phase, when Sauter mean diameter of the dispersed phase is set to be 3.5 mm. A two-point monitoring method is used to estimate a Peclet number. The tracer concentration distribution in the two-dimensional distance–time space is interpreted with MATLAB along with the experimental measurement. The simulated Peclet numbers are compared with column experiments, and in general the simulation underestimates the experimental data by 60%. Introducing a modified drag law improves the predictions. This work shows that CFD can successfully model the performance of a non-pulsed disc and doughnut solvent extraction column.     

One-Step Flame Synthesis of an Active Pt/TiO2 Catalyst for SO2 Oxidation—A Possible Alternative to Traditional Methods for Parallel Screening

Flame synthesis as a route for production of composite metal oxides has been employed for the one-step synthesis of a supported noble metal catalyst, i.e., a Pt/TiO₂ catalyst, by simultaneous combustion of Ti-isopropoxide and platinum acetylacetonate in a quench-cooled flame reactor. The average size of the platinum particles supported on aggregated nanoparticles of TiO₂ is approximately 2 nm. The high SO₂ oxidation activity of the catalyst proves that platinum is not “hidden” in the titania matrix. The flame-produced catalyst showed catalytic activity similar to that of samples prepared by wet platinum impregnation of pure titania.     

Development of an LC–MS/MS Method for the Analysis of Free Sphingoid Bases Using 4-Fluoro-7-nitrobenzofurazan (NBD-F)

The molecular species of sphingoid bases were tagged with the fluorescent amino group reagent, 4-fluoro-7-nitrobenzofurazan (NBD-F). The NBD-sphingoid bases were analyzed by a highly selective and sensitive liquid chromatography–electrospray ionization tandem mass spectrometry (LC–ESI–MS/MS) technique capable of reliable detection of several fmol of the derivatives. Lipid extracts from plant samples were derivatized with NBD-F, and all nine species of free sphingoid bases present in plant sphingolipids were separated and quantified for the first time; a complete baseline resolution was achieved for cis-8 and trans-8 isomers of sphingoid bases by reversed phase HPLC on a C₁₈ column. The extraction and derivatization procedures and LC–MS/MS method can facilitate the progress of the studies for seeking the active components of sphingoid bases species in response to biological challenges.     

Fabrication and properties of 2D C/C–ZrB2–ZrC–SiC composites by hybrid precursor infiltration and pyrolysis

Abstract

Two dimensional C/C–ZrB₂–ZrC–SiC composites were fabricated through precursor infiltration and pyrolysis process using a mixture of polycarbosilane and ZrB₂ precursor and ZrC precursor as the impregnant. The microstructures, mechanical properties and ablation properties of the composites were investigated. The results showed that the homogeneity of the composite improved on using novel precursors that can dissolve with polycarbosilane through the formation of nanocomposite matrix. The flexural strength and fracture toughness first increased and then decreased on increasing the pyrocarbon content in the composite. Compared with the C/C–SiC composite, the ablation resistance of C/C–ZrB₂–ZrC–SiC composite was greatly enhanced. The mass loss rate and linear recession rate exposed to the plasma torch were 1?7 mg/s and 1?8 μm/s, respectively. The formation of a ZrO₂–SiO₂ glassy layer on the surface significantly contributed to the excellent ablative property of the composite.     

Analysis of CO2–NH3 reaction dynamics in an aqueous phase by PCA and 2D IR COS

Both carbamation and bicarbonation are of prime importance in the absorption reactions of CO₂ in an aqueous NH₃ solution, as they are related to the CO₂ working capacity, regeneration energy, and the critical problem of blocking the gas pathway for the CO₂ capture process. Herein, the influence of reaction temperature on the CO₂ and NH₃ reaction in an aqueous solution is demonstrated by a principal component analysis (PCA) and a two dimensional correlation analysis (2D IR COS) obtained from FT-IR, dependent on the reaction time. In contrast to the reaction at 298 K, conversion of the dominant reaction from carbamation to bicarbonation and respective conformational changes were observed at 278 K by PCA and 2D IR COS. The PCA results elucidate that two major reactions following the dependence of reaction time were divided into two regions, I and II. The turnover point was subsequently tracked in these two regions, where precipitation of ammonium bicarbonate occurred due to the limitation of solubility at this turning point. The interrelation and sequential variation of conformations in regions I and II were investigated by synchronous and asynchronous 2D correlation analyses. The combination of PCA and 2D IR COS provides a powerful and useful analytic method to capture and monitor the dynamics of complex chemical reactions.     

Zr- and Li-Modified Ru/Sio2 Catalysts for Fischer–Tropsch Synthesis

We have found that Zr- and Li-modified Ru/SiO₂ catalysts (Q-15) are extremely stable and can be used in FT synthesis to maintain the conversion rate of CO constant even after 33 h. Modification of Ru/SiO₂ by Zr (5 wt%) and Li (0.1 wt%) resulted in a remarkable increase in the stability of the catalyst. Taking into account surface acidity and reducibility, we assumed that this remarkable stability is due to the cooperative effects of Ru, Zr, Li, and the SiO₂ support.     

A Modified Method for Determining Tannin–Protein Precipitation Capacity Using Accelerated Solvent Extraction (ASE) and Microplate Gel Filtration

The protein precipitation assay used by Robbins et al., (1987) Ecology 68:98–107 has been shown to predict successfully the reduction in protein availability to some ruminants due to tannins. The procedure, however, is expensive and laborious, which limits its utility, especially for quantitative ecological or nutritional applications where large numbers of assays may be required. We have modified the method to decrease its cost and increase laboratory efficiency by: (1) automating the extraction by using Accelerated Solvent Extraction (ASE); and (2) by scaling and automating the precipitation reaction, chromatography, and spectrometry with microplate gel filtration and an automated UV–VIS microplate spectrometer. ASE extraction is shown to be as effective at extracting tannins as the hot methanol technique. Additionally, the microplate assay is sensitive and precise. We show that the results from the new technique correspond in a nearly 1:1 relationship to the results of the previous technique. Hence, this method could reliably replace the older method with no loss in relevance to herbivore protein digestion. Moreover, the ASE extraction technique should be applicable to other tannin–protein precipitation assays and possibly other phenolic assays.     

A ZrB2–SiC/SiC oxidation protective dual-layer coating for carbon/carbon composites

In order to improve the oxidation resistance of C/C composites, a ZrB₂–SiC/SiC oxidation protective dual-layer coating was prepared by a pack cementation combined with the slurry paste method. The phase and microstructure of the coating were characterised by X-ray diffraction, scanning electron microscope and energy-dispersive spectrometer analyses. The anti-oxidation and thermal shock resistance of the coating were also investigated. It was found that the ZrB₂–SiC/SiC coating could effectively improve the oxidation resistance of the C/C composites. The weight loss of the coated samples was only 1.8% after oxidation at 1773?K for 18?h in air. The coating endured 20 thermal shock cycles between 1773?K and room temperature with only 4.6% weight loss.     

Comparative Study on Reactive Extraction of Nicotinic Acid with Amberlite LA‐2 and D2EHPA

Abstract

The comparative study of reactive extraction of nicotinic acid with Amberlite LA‐2 and D2EHPA in three solvents with different polarity indicated that the extractant type and solvent polarity control the extraction mechanism. Thus, the reactive extraction with Amberlite LA‐2 in low‐polar solvents occurs by means of the interfacial formation of an aminic adduct with 3 or 2 extractant molecules. If solvents with higher polarity are used, each reactant participates with one molecule to the interfacial reaction. The mechanism of reactive extraction with D2EHPA involves in all cases the formation of a salt as the product of the interfacial reaction between one molecule of each reactant.