An investigation of tautomeric equilibria by means of mass spectrometry

Changes in the mass spectra with inlet temperature were used in this work to demonstrate the dependence of keto-enol tautomerism of acetylacetone, 3-methyl acetylacetone and 3-allyl acetylacetone on temperature. The largest dependence of temperature were shown by the ion [M ? 42]^+. arising from a McLafferty type rearrangement and by the ion [M ? Me]⁺ resulting from simple α-cleavage. The ion [M ? 42]^+. peak increases with the temperature of the inlet system while the ion [M ? Me]⁺ peak decreases. By assuming that the ion [M ? 42]^+. represents the keto form and that the ion [M ? Me]⁺ represents the cis-enol form (stabilized by the hydrogen bond) one sees that the direction of the intensity variation of these peaks with temperature is in accord with the expected change of keto-enol tautomerism with temperature. A quantitative correlation on the basis of the above assumptions is also approached. Recording of the mass spectra of these three β-diketones at different energies of the incident electrons enables us to estimate whether or not the particular ions present in the mass spectra result from energetically favourable processes. The variation of the intensities of the peaks with the temperature of the inlet at different electron energies is also discussed.     

Preliminary characterization of anhydrous ethanol used in Brazil as automotive fuel

This work reports preliminary studies on the characterisation of anhydrous ethanol (AEA) used as an automotive fuel mixed with gasoline in Porto Alegre (South Brazil). Pre-concentration of the impurities contained in 1000 ml of AEA was carried on through solid-phase extraction using XAD4 resin. The main compounds in the extract were identified by means of spectral data from the library of the equipment. The concentrate was then fractionated using a preparative liquid chromatographic column filled with activated silica gel and the elution procedure was carried out with, n-hexane, n-hexane-benzene (1:1, v/v) and dichloromethane. Prior to analysis by GC-MS, each fraction was reduced to 1 ml with a gentle stream of nitrogen. Saturated linear hydrocarbons and aromatic hydrocarbons eluted in the first fraction and oxygenated compounds such as aldehydes. ketones and alcohols, eluted in the second one. were the main compounds detected in the sample.     

Selective extraction of benzoic acid from landfill leachate by solid-phase extraction and ion-exchange chromatography

In this work a simple method was described for selective extraction of benzoic acid from landfill leachate samples. The samples were submitted to solid-phase extraction (SPE) with XAD-4 resin as the stationary phase and ion-exchange chromatography (IEC) using the ion-exchange resin Amberlyst A-27. The instrumental analysis was performed by gas chromatography with mass spectrometric detection (GC-MSD). Benzoic acid was isolated, identified and quantified. The extraction process is rapid, simple and of low cost. It was also environmental friendly, that is, it was used a minimum amounts of hazardous organic solvents and produced also minimum quantities of residues.     

Radical anions containing the dioxidated 1,2,5‐thiadiazole heterocycle. Part II

Radical anions from several 3,4‐aryl‐disubstituted derivatives of 1,2,5‐thiadiazole 1,1‐dioxide were accumulated through chemical reduction of the substrates in aprotic solvents. The radical anions were characterized by electron spin resonance and cyclic voltammetry. DFT theoretical calculations were also performed for the 3,4‐diphenyl derivative. The course of the reductions was followed using cyclic voltammetry. Uncommon reductants, such as amides, were found to be effective under certain conditions. Copyright © 2010 John Wiley & Sons, Ltd.     

Investigation of sulphur compounds in coal tar using monodimensional and comprehensive two-dimensional gas chromatography

Coal is a non renewable fossil fuel, used mainly as a source of electrical energy and in the production of coke. It is subjected to thermal treatment, pyrolysis, which produces coke as a main product, in addition to a condensed liquid by-product, called tar. Tar is a complex mixture of organic compounds which contains different chemical classes, presenting aromatic and sulphur heterocyclic compounds. In general, identification of these compounds requires steps of isolation and fractionation, mainly due to co-elution of these compounds with polyaromatic hydrocarbons (PAH). The objective of this work is to characterize the sulphur compounds present in the coal tar obtained via pyrolysis, using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry detector (GC×GC/TOFMS). Coal samples from the State of Paraná, Brazil were subjected to laboratorial scale pyrolysis. Several experimental conditions were tested, such as sample weight (5, 10 and 15g), heating ramp (10, 25 and 100°C/min) and final temperature (500, 700 and 900°C). Samples were analyzed by one dimensional gas chromatography (1D-GC) coupled to a quadrupole mass spectrometry detector (GC/qMS) and two-dimensional gas chromatography with time-of-flight mass spectrometry detector (GC×GC/TOFMS). The higher amount of sulphur compounds was obtained at a final temperature of 700°C and a heating ramp of 100°C/min. The main classes observed in the color plot were thiophenes, benzothiophenes and alkylated dibenzothiophenes. GC×GC/TOFMS allowed the identification of the greater number of compounds and the separation of several sulphur compounds from one another. Moreover, separation of sulphur compounds from polyaromatic hydrocarbons and phenols was achieved, which was not possible by 1D-GC. Comparing GC×GC/TOFMS and 1D-GC (SIM mode) also showed that 1D-GC, one of the most employed quantification tools for sulphur compounds, can be misleading for detection, identification and quantification, as the number of isomers of sulphur compounds found was greater than theoretically possible.     

Reversible chemisorption of carbon dioxide: simultaneous production of fuel-cell grade H2 and compressed CO2 from synthesis gas

One vision of clean energy for the future is to produce hydrogen from coal in an ultra-clean plant. The conventional route consists of reacting the coal gasification product (after removal of trace impurities) with steam in a water gas shift (WGS) reactor to convert CO to CO₂ and H₂, followed by purification of the effluent gas in a pressure swing adsorption (PSA) unit to produce a high purity hydrogen product. PSA processes can also be designed to produce a CO₂ by-product at ambient pressure. This work proposes a novel concept called “Thermal Swing Sorption Enhanced Reaction (TSSER)” which simultaneously carries out the WGS reaction and the removal of CO₂ from the reaction zone by using a CO₂ chemisorbent in a single unit operation. The concept directly produces a fuel-cell grade H₂ and compressed CO₂ as a by-product gas. Removal of CO₂ from the reaction zone circumvents the equilibrium limitations of the reversible WGS reaction and enhances its forward rate of reaction. Recently measured sorption-desorption characteristics of two novel, reversible CO₂ chemisorbents (K₂CO₃ promoted hydrotalcite and Na₂O promoted alumina) are reviewed and the simulated performance of the proposed TSSER concept using the promoted hydrotalcite as the chemisorbent is reported.     

Detector technologies for comprehensive two-dimensional gas chromatography

The detector is an integral and important part of any chromatographic system. The chromatographic peak profiles (i.e. peak separation) should, ideally, be unaffected by the detector--it should only provide the sensing capacity required at the end of a column separation process. The relatively new technique of comprehensive 2-D GC (GC x GC) extends the performance of GC manyfold, but comes at a price--existing GC systems may not be adequately designed with the requirements of GC x GC in mind. This is primarily the need for precise measurement of very fast peaks entering the detector (e.g. as fast as 50 ms basewidth in some instances). The capacity of the detector to closely track a rapidly changing chromatographic peak profile depends on a number of factors, such as design of flow paths and make-up gas introduction, type of detector response mechanism, and the chemistry of the response. These factors are discussed here as a means to appreciate the technical demands of detection in GC x GC. The MS detector will not be included in this review.     

Intracellular Delivery and Triggered Release of DNA Using Biodegradable Poly(2‐hydroxypropylene imine)s Containing Cystamine Units

Poly(2‐hydroxypropylene imine)s containing segments of cystamine (PHPI‐CA) are synthesized by polycondensation of 1,3‐dibromo‐2‐propanol with a mixture of 1,3‐diamino‐2‐propanol and cystamine. High molecular weight fractions of these polymers are collected by ultrafiltration and characterized by chemical analysis, ¹H and ¹³C‐NMR spectroscopy, size‐exclusion chromatography with triple detection, and potentiometric titration, and are tested for DNA delivery in vitro. It is shown that PHPI‐CA are highly branched polymers containing disulfide linkages. Transfection efficiency of PHPI‐CA for DNA gives similar results to that of PHPI with GFP⁺ cell percent reaching 80–90%. Cytotoxicity levels for PHPI‐CA are lower than that of PHPI. Novel polymers containing different amounts of disulfide linkages are able to disintegrate and release DNA following the treatment with reducing agent 1,4‐dithiothreitol. Downstream application of PHPI‐CA transfected cells for RNA purification shows that RNA yield is not affected even after the double transfection suggesting that these polymers could be great candidates for in vitro and in vivo transfection.

     

Analysis of organic compounds of water-in-crude oil emulsions separated by microwave heating using comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry

In this work the higher peak capacity and resolution of comprehensive two-dimensional gas chromatography (GCxGC) has been successfully applied, for the first time, to tentatively identify several polar organic compounds of organic extracts of aqueous phases resulting from microwave demulsification process of water-in-crude oil emulsions. Results have shown that higher temperatures and longer exposure time to microwave irradiation produced water phases with a wider variety of polar organic compounds. The microwave process showed to be suitable for the extraction of several polar compounds classes of petroleum. The proposed microwave extraction method and GCxGC identification of polar compounds of petroleum samples are of practical interest for the petrochemical industry due to corrosion and related problems associated with these polar compounds in refinery equipments. The GCxGC/time-of-flight MS technique shows to be very important in the total separation of different classes of compounds and allows the identification of many compounds in these classes.     

Identification of alkyl carbazoles and alkyl benzocarbazoles in Brazilian petroleum derivatives

The present work describes (a) the identification and characterization of an impurity, 2,4,5,7-tetrabromo-6-hydroxy-9-(2,3,4,5-tetrachlorophenyl)-3H-xanthen-3-one (BCPX), in the color additives D&C Red Nos. 27 and 28 (phloxine B) and (b) the determination of the extent and level of BCPX contamination in certified lots of these colors. For these purposes, BCPX (a compound not previously reported in the literature) was synthetically prepared. Test portions from 42 certified lots of D&C Red Nos. 27, 28 and 27 lakes were analyzed for BCPX using an HPLC method that included gradient elution and UV-vis photodiode array detection. Those lots were submitted for certification by both domestic (six) and foreign (six) manufacturers during the past 4 years. Of the test portions analyzed, 32 (76.2%) contained BCPX in amounts ranging from 0.01 to 3.21%. The remaining 10 test portions (23.8%) contained no detectable BCPX or less than 0.008%, which is the limit of quantification for the present method. The analyses revealed substantial differences in the level of BCPX across different manufacturers. The wide range of BCPX levels found in the analyzed lots suggests that the presence of BCPX in D&C Red Nos. 27 and 28 may be avoided or significantly reduced during the manufacturing process.