Organic geochemistry of sediments from sapropel 94 of ODP Hole 161-974C

Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC * GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products

Uso da cromatografia gasosa bidimensional abrangente (GC×GC) na caracterização de misturas biodiesel/diesel: aplicação ao biodiesel de sebo bovino

The growth of biodiesel market and the implementation of regulations related to biodiesel production and biodiesel/diesel blending has encouraged the development of appropriate analytical methods to control the composition of this type of mixture. In this study, an evaluation of the potential of GC×GC for the characterization of samples of beef tallow biodiesel and the composition of blends of biodiesel/diesel is presented. The methodology was applied to beef tallow biodiesel and its mixtures with petrodiesel, ranging from B2 to B50. Results allowed not only the identification and quantification of the biodiesel esters, but also the biodiesel percentage in biodiesel/diesel blends.

UPLC-ESI-TOFMS-based metabolomics and gene expression dynamics inspector self-organizing metabolomic maps as tools for understanding the cellular response to ionizing radiation

Global transcriptomic and proteomic profiling platforms have yielded important insights into the complex response to ionizing radiation (IR). Nonetheless, little is known about the ways in which small cellular metabolite concentrations change in response to IR. Here, a metabolomics approach using ultraperformance liquid chromatography coupled with electrospray time-of-flight mass spectrometry was used to profile, over time, the hydrophilic metabolome of TK6 cells exposed to IR doses ranging from 0.5 to 8.0 Gy. Multivariate data analysis of the positive ions revealed dose- and time-dependent clustering of the irradiated cells and identified certain constituents of the water-soluble metabolome as being significantly depleted as early as 1 h after IR. Tandem mass spectrometry was used to confirm metabolite identity. Many of the depleted metabolites are associated with oxidative stress and DNA repair pathways. Included are reduced glutathione, adenosine monophosphate, nicotinamide adenine dinucleotide, and spermine. Similar measurements were performed with a transformed fibroblast cell line, BJ, and it was found that a subset of the identified TK6 metabolites were effective in IR dose discrimination. The GEDI (Gene Expression Dynamics Inspector) algorithm, which is based on self-organizing maps, was used to visualize dynamic global changes in the TK6 metabolome that resulted from IR. It revealed dose-dependent clustering of ions sharing the same trends in concentration change across radiation doses. "Radiation metabolomics," the application of metabolomic analysis to the field of radiobiology, promises to increase our understanding of cellular responses to stressors such as radiation.

Characterization of the volatile profile of Brazilian Merlot wines through comprehensive two dimensional gas chromatography time-of-flight mass spectrometric detection.

Wine aroma is an important characteristic and may be related to certain specific parameters, such as raw material and production process. The complexity of Merlot wine aroma was considered suitable for comprehensive two-dimensional gas chromatography (GCGC), as this technique offers superior performance when compared to one-dimensional gas chromatography (1D-GC). The profile of volatile compounds of Merlot wine was, for the first time, qualitatively analyzed by HS-SPME-GCxGC with a time-of-flight mass spectrometric detector (TOFMS), resulting in 179 compounds tentatively identified by comparison of experimental GCxGC retention indices and mass spectra with literature 1D-GC data and 155 compounds tentatively identified only by mass spectra comparison. A set of GCGC experimental retention indices was also, for the first time, presented for a specific inverse set of columns. Esters were present in higher number (94), followed by alcohols (80), ketones (29), acids (29), aldehydes (23), terpenes (23), lactones (16), furans (14), sulfur compounds (9), phenols (7), pyrroles (5), C13-norisoprenoids (3), and pyrans (2). GCxGC/TOFMS parameters were improved and optimal conditions were: a polar (polyethylene glycol)/medium polar (50% phenyl 50% dimethyl arylene siloxane) column set, oven temperature offset of 10ºC, 7 s as modulation period and 1.4 s of hot pulse duration. Co-elutions came up to 138 compounds in 1D and some of them were resolved in 2D. Among the coeluted compounds, thirty-three volatiles co-eluted in both 1D and 2D and their tentative identification was possible only due to spectral deconvolution. Some compounds that might have important contribution to aroma notes were included in these superimposed peaks. Structurally organized distribution of compounds in the 2D space was observed for esters, aldehydes and ketones, alcohols, thiols, lactones, acids and also inside subgroups, as occurred with esters and alcohols. The Fischer Ratio was useful for establishing the analytes responsible for the main differences between Merlot and non-Merlot wines. Differentiation among Merlot wines and wines of other grape varieties were mainly perceived through the following components: ethyl dodecanoate, 1-hexanol, ethyl nonanoate, ethyl hexanoate, ethyl decanoate, dehydro-2-methyl-3(2H)thiophenone, 3-methyl butanoic acid, ethyl tetradecanoate, methyl octanoate, 1,4 butanediol, and 6-methyloctan-1-ol.

Assessment Of Robustness On Analysis Using Headspace Solid-phase Microextraction And Comprehensive Two-dimensional Gas Chromatography Through Experimental Designs.

Plackett-Burman experimental design was applied for the robustness assessment of GC×GC-qMS (Comprehensive Two-Dimensional Gas Chromatography with Fast Quadrupolar Mass Spectrometric Detection) in quantitative and qualitative analysis of volatiles compounds from chocolate samples isolated by headspace solid-phase microextraction (HS-SPME). The influence of small changes around the nominal level of six factors deemed as important on peak areas (carrier gas flow rate, modulation period, temperature of ionic source, MS photomultiplier power, injector temperature and interface temperature) and of four factors considered as potentially influential on spectral quality (minimum and maximum limits of the scanned mass ranges, ions source temperature and photomultiplier power). The analytes selected for the study were 2,3,5-trimethylpyrazine, 2-octanone, octanal, 2-pentyl-furan, 2,3,5,6-tetramethylpyrazine, and 2-nonanone e nonanal. The factors pointed out as important on the robustness of the system were photomultiplier power for quantitative analysis and lower limit of mass scanning range for qualitative analysis.

Synthesis and structural characterization of block and random low molecular weight copolymers composed of L-lactic acid and isosorbide succinate moieties

Isosorbide succinate moieties were incorporated into poly(L-lactide) (PLLA) backbone in order to obtain a new class of biodegradable polymer with enhanced properties. This paper describes the synthesis and characterization of four types of low molecular weight copolymers. Copolymer I was obtained from monomer mixtures of L-lactide, isosorbide, and succinic anhydride; II from oligo(L-lactide) (PLLA), isosorbide, and succinic anhydride; III from oligo(isosorbide succinate) (PIS) and L-lactide; and IV from transesterification reactions between PLLA and PIS. MALDI-TOFMS and 13C-NMR analyses gave evidence that co-oligomerization was successfully attained in all cases. The data suggested that the product I is a random co-oligomer and the products II-IV are block co-oligomers.

Enhanced fibroblast adhesion and proliferation on electrospun fibers obtained from poly(isosorbide succinate-b-L-lactide) block copolymers

Block copolymers containing isosorbide succinate and L-lactic acid repeating units with different mass compositions were synthesized in two steps: bulk ring-opening copolymerization from L-lactide and poli(isosorbide succinate) (PIS) preoligomer, in the presence of tin(II) 2-ethylhexanoate as catalyst. followed by chain extension in solution by using hexamethylene diisocyanate. Poly(L-lactide) (PLLA) and a chain extension product from PIS were also obtained, for comparison. SEC, (1)H and (13)C NMR, MALDI-TOFMS, WAXD, DSC, TG, and contact angle measurements were used in their characterization. The incorporation of isosorbide succinate into PLLA main backbone had minor effect on the thermal stability and the T(g) of the products. However, it reduced the crystallinity and increased the surface energy in relation to PLLA. Nonwoven mats of the block copolymers and PLLA obtained by electrospinning technique were submitted to fibroblasts 3T3-L1 cell culture. The copolymers presented enhanced cell adhesion and proliferation rate as revealed by MTT assay and SEM images. (C) 2009 Elsevier Ltd. All rights reserved.

Non-volatile analysis in fruits by laser resonant ionization spectrometry: application to resveratrol (3,5,4 -trihydroxystilbene) in grapes

Applied Physics B Lasers and Optics, vol.71

First day of an oil spill on the open sea: early mass transfers of hydrocarbons to air and water.

During the first hours after release of petroleum at sea, crude oil hydrocarbons partition rapidly into air and water. However, limited information is available about very early evaporation and dissolution processes. We report on the composition of the oil slick during the first day after a permitted, unrestrained 4.3 m(3) oil release conducted on the North Sea. Rapid mass transfers of volatile and soluble hydrocarbons were observed, with >50% of ≤C17 hydrocarbons disappearing within 25 h from this oil slick of <10 km(2) area and <10 μm thickness. For oil sheen, >50% losses of ≤C16 hydrocarbons were observed after 1 h. We developed a mass transfer model to describe the evolution of oil slick chemical composition and water column hydrocarbon concentrations. The model was parametrized based on environmental conditions and hydrocarbon partitioning properties estimated from comprehensive two-dimensional gas chromatography (GC×GC) retention data. The model correctly predicted the observed fractionation of petroleum hydrocarbons in the oil slick resulting from evaporation and dissolution. This is the first report on the broad-spectrum compositional changes in oil during the first day of a spill at the sea surface. Expected outcomes under other environmental conditions are discussed, as well as comparisons to other models.

Development of a liquid chromatographic time-of-flight mass spectrometric method for the determination of unlabelled and deuterium-labelled alpha-tocopherol in blood components

A method is described for the analysis of deuterated and undeuterated alpha-tocopherol in blood components using liquid chromatography coupled to an orthogonal acceleration time-of-flight (TOF) mass spectrometer. Optimal ionisation conditions for undeuterated (d0) and tri- and hexadeuterated (d3 or d6) alpha-tocopherol standards were found with negative ion mode electrospray ionisation. Each species produced an isotopically resolved single ion of exact mass. Calibration curves of pure standards were linear in the range tested (0-1.5 muM, 0-15 pmol injected). For quantification of d0 and d6 in blood components following a standard solvent extraction, a stable-isotope-labelled internal standard (d3-alpha-tocopherol) was employed. To counter matrix ion suppression effects, standard response curves were generated following identical solvent extraction procedures to those of the samples. Within-day and between-day precision were determined for quantification of d0- and d6-labelled alpha-tocopherol in each blood component and both averaged 3-10%. Accuracy was assessed by comparison with a standard high-performance liquid chromatography (HPLC) method, achieving good correlation (r(2) = 0.94), and by spiking with known concentrations of alpha-tocopherol (98% accuracy). Limits of detection and quantification were determined to be 5 and 50 fmol injected, respectively. The assay was used to measure the appearance and disappearance of deuterium-labelled alpha-tocopherol in human blood components following deuterium-labelled (d6) RRR-alpha-tocopheryl acetate ingestion. The new LC/TOFMS method was found to be sensitive, required small sample volumes, was reproducible and robust, and was capable of high throughput when large numbers of samples were generated. Copyright (C) 2003 John Wiley Sons, Ltd.

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), (1)H and (13)C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, (13)C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.