Abstract  We have compared two sample preparation methods for the analysis of plasma acylcarnitines by tandem mass spectrometry. Extraction from liquid plasma using acetonitrile was compared with the widely used methanol extraction from plasma...

Abstract  The whole life of methanol fuel, produced by microalgae biomass which is a kind of renewable energy, is evaluated by using a method of life cycle assessment (LCA). LCA has been used to identify and quantify the environment emissions and energy efficiency of the system throughout the whole life cycle, including microalgae cultivation, methanol conversion, transport, and end-use. Energy efficiency, defined as the ratio of the energy of methanol produced to the total required energy, is 1.24, the results indicate that it is plausible as an energy producing process. The environmental impact loading of microalgae-based fuel methanol is 0.187mPFT(2000) in contrast to 0.828mPET(2000) for gasoline. The effect of photochemical ozone formation is the highest of all the calculated categorization impacts of the two fuels. Utilization of microalgae an raw material of producing methanol fuel is beneficial to both production of renewable fuels and improvement of the ecological environment. This Fuel methanol is friendly to the environment, which should take an important role in automobile industry development and gasoline fuel substitute. (C) 2008 Elsevier Ltd. All rights reserved.

Abstract  Abstract: A two-step technique combining pre-esterification catalyzed by cation exchange resin with transesterification catalyzed by base alkali was developed to produce biodiesel from rapeseed oil deodorizer distillate (RDOD). The free fatty acids (FFAs) in the feedstock were converted to methyl esters in the pre-esterification step using a column reactor packed with cation exchange resin. The acid value of oil was reduced from the initial 97.60 mg-KOH g^{−1} oil to 1.12 mg-KOH g^{−1} oil under the conditions of cation exchange resin D002 catalyst packed dosage 18 wt.% (based on oil weight), oil to methanol molar ratio 1:9, reaction temperature 60 °C, and reaction time 4 h. The biodiesel yield by transesterification was 97.4% in 1.5 h using 0.8 wt.% KOH as catalyst and a molar ratio of oil to methanol 1:4 at 60 °C. The properties of RDOD biodiesel production in a packed column reactor followed by KOH catalyzed transesterification were measured up the standards of EN14214 and ASTM6751-03. [Copyright 2009 Elsevier] Copyright of Fuel Processing Technology is the property of Elsevier Science Publishers B.V. and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Abstract  Sample preparation is one of the major issues in 2-DE for the separation of proteins. Although a 100% representation of cellular proteins onto a 2-DE is virtually impossible, maximum representation of cellular proteins compared with the original cell lysate is important in the subsequent analysis. We demonstrate that lysis of cells in urea/thiourea solution with subsequent sonication to disrupt the nucleic acids and concentration of the lysate using centri-con led to enrichment of proteins. The procedure resulted in minimal nucleic acid contamination with better resolution of spots. 2-DE spot patterns of proteins prepared using urea-thiourea solubilization/centri-con method to other protein enrichment methods such as phenol/chloroform/isoamyl alcohol extraction, methanol/ammonium acetate precipitation, acetone precipitation and ethanol precipitation were compared. Urea-thiourea solubilization combined with centri-con method of protein enrichment represented higher number/unique spots particularly in the 50-250 kDa M(r) compared with others. Lysis of cells in urea/thiourea from the beginning of lysate preparation preserves the proteins from protease activity due to denaturation of proteases. Thus, we demonstrate that the centri-con methodology is simple and effective for the preparation of high-quality sample that can be used for a qualitative representation of cellular proteins on a 2-DE for proteomic analysis.

Abstract  A high-performance thin-layer chromatographic method with fluorescence detection was developed for the qualitative determination of ronidazole, dimetridazole and their major metabolite, hydroxydimetridazole, in pork and poultry muscle. After extraction with dichloromethane and evaporation, the nitroimidazoles are redissolved in ammonium acetate buffer. The buffer phase is washed with hexane. The sample is cleaned-up by solid-phase extraction and the eluate evaporated. The final extract is resuspended in methanol and then spotted on an HPTLC plate. After multiple development with methanol and ethylacetate, the plate is dried, sprayed with pyridine and observed on an UV box (312 nm). The detection limits of this method are about 2 mug/kg for ronidazole, 5 mug/kg for dimetridazole and less than 5 mug/kg for hydroxydimetridazole. Validation was performed to levels of 10 mug/kg for dimetridazole, 5 mug/kg for ronidazole and 5 mug/kg for hydroxydimetridazole.

Abstract  A method of analysis of 21 coal tar dyes in foods by HPLC was developed. After adjustment of the pH to 3.5 similar to 4.0 with acetic acid, the dye solution was applied to a Sep-pak Vac Cls cartridge, and the cartridge was washed with water. The cartridge was eluted with 50% methanol (fraction A), and then with methanol (fraction B). The dyes in each eluate were determined by high performance liquid chromatograph with a UV-VIS detector. The HPLC separation was carried out on a COSMOSIL 5C18-AR column using 0.025 M ammonium acetate (containing 0.01 M tetrabutylammonium bromide (TBA))-acetonitrile-methanol (62: 28:10) as a mobile phase for fraction A, and 0.025 M ammonium acetate (containing 0.01 M TBA)-acetonitrile-methanol (50:40:10) as a mobile phase for fraction B. Recoveries of dyes added to a soft drink, a jelly and a candy at 10 mu g/g were 85 similar to 103%, 76 similar to 99%, and 73 similar to 103%, respectively. Recovery of dyes added to pickles was 64 similar to 99%, except for Black PN. The detection limits of dyes were 0.1 similar to 0.5 mu g/ml.

Abstract  A high-performance liquid chromatographic (HPLC) assay for methyl 5-hydroxy-2-benzimidazole carbamate (5-HBC) in urine was developed in order to assess the exposure of workers to the pesticide carbendazim. 5-HBC is measured in urine after hydrolysis, sample clean-up through a strong cation-exchange (SCX) column and extraction with ethyl acetate. HPLC with electrochemical detection provides selective and sensitive determination of 5-HBC with a detection limit of 5 μg/l. A C18 reversed-phase column was used with 0.06 M ammonium acetate solution (pH 8)—methanol (73:27) as mobile phase. The method was validated with respect to hydrolysis of urine samples, analytical recovery of spiked 5-HBC, stability of 5-HBC conjugates, limit of detection, background and precision. The overall analytical recovery from urine was better than 60%. 5-HBC, excreted in urine as a conjugate, was stable for at least one year when stored at − 20°C. A background of ca. 5 μg/l was detected in urine from some non-occupationally exposed persons. Between-day coefficients of variation as calculated from the results of the stability test were 7, 4 and 4% for concentrations of 61, 244 and 295 μg/l 5-HBC, respectively (n = 16).

Abstract  Several studies indicated that chloral hydrate can prolong the disappearance time of ethanol from blood in mice. This seems to result from inhibition of the enzyme alcohol dehydrogenase by chloral hydrate and trichloroethanol, its main metabolite. We examined the effect of both these compounds on the disappearance time of methanol in mice. Also the effect of a combination of ethanol and chloral hydrate on the disappearance time of methanol was examined. Several groups of six mice each received methanol (1 g/kg i.p.) followed immediately by one of the following treatments: saline (10 ml/kg); chloral hydrate (0.4 g/kg); trichloroethanol (0.36 g/kg); ethanol (4 g/kg); or a combination of chloral hydrate (0.2 g/kg) and ethanol (4 g/kg). The concentrations of methanol in blood were measured at 1, 2, 4, and 8 h after its administration and were used to calculate some approximate indicators of methanol elimination in each group. The results show that all the above treatments do prolong the disappearance time of methanol in the blood of mice to varying extents. The ethanol-chloral hydrate combination produced the most pronounced effect.

Abstract  Trace gas and particle emissions were measured from 47 laboratory fires burning 16 regionally to globally significant fuel types. Instrumentation included the following: open-path Fourier transform infrared spectroscopy; proton transfer reaction mass spectrometry; filter sampling with subsequent analysis of particles with diameter < 2.5 μm for organic and elemental carbon and other elements; and canister sampling with subsequent analysis by gas chromatography (GC)/flame ionization detector, GC/electron capture detector, and GC/mass spectrometry. The emissions of 26 compounds are reported by fuel type. The results include the first detailed measurements of the emissions from Indonesian fuels. Carbon dioxide, CO, CH4, NH3, HCN, methanol, and acetic acid were the seven most abundant emissions ( in order) from burning Indonesian peat. Acetol ( hydroxyacetone) was a major, previously unobserved emission from burning rice straw (21-34 g/kg). The emission factors for our simulated African fires are consistent with field data for African fires for compounds measured in both the laboratory and the field. However, the higher concentrations and more extensive instrumentation in this work allowed quantification of at least 10 species not previously quantified for African field fires ( in order of abundance): acetaldehyde, phenol, acetol, glycolaldehyde, methylvinylether, furan, acetone, acetonitrile, propenenitrile, and propanenitrile. Most of these new compounds are oxygenated organic compounds, which further reinforces the importance of these reactive compounds as initial emissions from global biomass burning. A few high-combustion-efficiency fires emitted very high levels of elemental ( black) carbon, suggesting that biomass burning may produce more elemental carbon than previously estimated.

Abstract  Abstract: Using hydrogen peroxide as a key oxidant, catalytic oxidative amidation between aldehydes and amines was effectively carried out with PdCl2–xantophos as a catalyst in methanol under acidic conditions. The new protocol is mechanistically different from the previous one through β-hydride elimination. [Copyright 2008 Elsevier] Copyright of Tetrahedron Letters: International Organ for the Rapid Publication of Preliminary Communications in Organic Chemistry is the property of Pergamon Press - An Imprint of Elsevier Science and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts)

Abstract  In this study, a remarkable promotion of ethanol electrooxidation by a Pt-Ru-W alloy is reported for an improvement of the anodic reaction of a direct ethanol fuel cell (DEFC). Pt-based binary and ternary electrocatalysts including Pt-Ru-W...

Abstract  During in vitro culture of murine preimplantation embryos, we have observed that exposure to 0.1% ethanol induces an immediate increase in intracellular calcium levels and subsequently accelerates embryogenesis. If the observed effects of ethanol on developing embryos is mediated by its membrane disordering potency, we hypothesized that the relative membrane disordering potencies of related alcohols would correspondingly effect embryonic intracellular calcium levels and developmental rates. Two-cell embryos were exposed to 0.1% ethanol or 0.05 to 1.0% (w/v) n-butanol, n-propanol, isopropanol, 1,2-propanediol, glycerol, or methanol for 24 hr at 37 degrees C, and development to the blastocyst stage was monitored after 5 days. n-Butanol, n-propanol, isopropanol, and methanol treatment caused a dose-dependent inhibition (p < 0.01) of development to the blastocyst stage, whereas 1,2-propanediol or glycerol neither accelerated nor inhibited development. In a second experiment, 8-cell morulae were treated with 1,2-propanediol or glycerol, and cavitation rates were examined. There was no significant difference from control embryos in the onset of cavitation or the blastocoel expansion rate of 1,2-propanediol- or glycerol-exposed embryos, whereas exposure to 0.1% ethanol accelerate cavitation (p > 0.05). In a third experiment, morulae were exposed to 0.1% or 1.0% of each alcohol and were monitored for changes in intracellular calcium levels using the fluorescent indicator, fluo-3-acetoxymethyl ester. There was an immediate increase in intracellular calcium levels when morulae were treated with 1.0% ethanol or n-butanol, but only ethanol induced an increase (p < 0.05) in the level of intracellular calcium at 0.1%. These data suggest that ethanol is unique in its ability to accelerate embryogenesis and that the membrane disordering potency of ethanol does not directly underlie its effects on intracellular calcium release and the acceleration of preimplantation development.

Abstract  In this study free fatty acids present in Azadirachta indica (Neem) oil were esterified with our synthesized phosphoric acid modified catalyst. During the esterification, the acid value was reduced from 24.4 to 1.8 mg KOH/g oil. Synthesized catalyst was characterized by NH(3) TPD, XRD, SEM, FTIR and TGA analysis. During phosphoric acid modification hydrophobic character and weak acid sites of the mordenite were increased, which lead to better esterification when compared to H-mordenite. A kinetic study demonstrates that the esterification reaction followed pseudo-first order kinetics. Thermodynamic studies were also done based on the Arrhenius model.

Abstract  In this study, micellar electrokinetic chromatographic (MEKC) methods were developed for the detection of traces of melamine and its related by-products (ammeline, ammelide, and cyanuric acid). Two on-line sample concentration steps namely reversed electrode polarity stacking mode (REPSM) and cation-selective injection (CSI) were used for improving the detection sensitivity. For REPSM, a borate-NaOH buffer (pH 10, 35mM) composed of 60mM SDS and 10% (v/v) methanol, was used as carrier electrolyte, and samples were prepared in an aqueous solution of 10mM NaOH. In CSI, a phosphate buffer (pH 2, 50mM) containing 41mM SDS was used as the carrier electrolyte, and samples were prepared with an aqueous solution of 10mM NaOH and a phosphate buffer (pH 2.0, 25mM) in a volume ratio of 1:9. The results indicated that REPSM enhanced all analyte signals except for melamine, which could be concentrated only by the CSI. The detection limit was reduced from 1.7mgL(-1) to 2.8mugL(-1) for melamine by the optimal CSI step, and from 0.23-1.2mgL(-1) to 2.4-5.0mugL(-1) for the other three analytes by the optimal REPSM step. Tableware made of melamine and samples of flour were used as test samples, and the results indicated that the proposed MEKC methods can successfully determine contaminations from melamine. The study also indicated that when the plastic made of melamine was exposed only once to an acidic solution (acetic or phosphoric acid) at 80 degrees C for 30min, melamine continuously leached out from the test sample even without any further treatment with an acidic solution.

Abstract  A thermal desorption-gas chromatography (GC) system was developed for use with commercial adhesive plasters used for monitoring exposure of hands to common solvents. The efficiency of solvent adsorption on the activated carbon pads located on the plasters was determined for acetone, trichloroethylene, D-limonene, methanol, ethyl methyl ketone, toluene, tetrachloroethylene and m-xylene. The degree of solvent recovery for the system was also investigated for each solvent, as was its sensitivity and reproducibility. All solvents exhibited > 90% adsorption on the pads at spiking levels of 100-200 ng for each solvent, except for m-xylene and d-limonene. Solvent recovery was dependent on the volatility of the solvent at spiking volumes of about 1 microliter per pad with solvents with boiling points above 110 degrees C showing recoveries of < 75%. Increasing primary desorption times and temperatures increased these values. The precision was good with RSD < 5% for all solvents over the range 0.5-5.0 microliters of applied solvent. It was possible to detect 15-60 ng of each solvent component within solvent mixtures on the pads with the exception of D-limonene. It is concluded that all solvents tested except D-limonene can be determined on the pads under the conditions for thermal desorption-GC analysis described. The pads were used under protective gloves with six workers using xylene isomers as solvent in the workplace, when apparent solvent breakthrough through their gloves was observed.

Abstract  BACKGROUND: Salicylic acid (SA) is present in the serum of people who have not taken salicylate drugs. Now we have examined the urine of these subjects and found that it contains SA and salicyluric acid (SU). We have established the identities of these phenolic acids and determined their concentrations. METHODS AND RESULTS: The acidic hydrophobic compounds of urine were separated using high-performance liquid chromatography (HPLC) and were detected and quantified electrochemically. Two approaches were used to establish the identity of SA and SU. First, the retention times (Rt) of the substances extracted and those of SA and SU were compared under two sets of chromatographic conditions; the Rt of the compounds suspected to be SA and SU and those of the authentic substances were very similar under both sets of conditions. Second, the unknown substances, isolated by HPLC, were treated with acetyl chloride in methanol and compared with the methyl esters of SA and SU by using gas chromatography-mass spectrometry; the unknown compounds after esterification had very similar mass spectra and gas chromatographic R, to those of methyl salicylate and methyl salicylurate. The median (n = 10) urinary concentration of SA was 0.56 micromol/L (range 0.07-0.89 micromol/L) and that of SU was 3.20 micromol/L (range 1.32-6.54 micromol/L). SA and its major urinary metabolite, SU, were found in the urine of all of the 10 people examined

Abstract  A variety of indoles underwent enantioselective Friedel-Crafts alkylation with alpha,beta-unsaturated acyl phosphonates in the presence of 10 mol% chiral BINOL-based phosphoric acid and subsequent treatment with methanol and DBU to give methyl 3-(indol-3-yl)propanoates in good yields and with high enantioselectivities.

Abstract  Measurement of fine particulate and gas-phase species during the New Year's fireworks 2005 in Mainz, Germany is investigated. The chemical composition and chemically resolved size distribution of fine aerosol particles are measured at high time resolution with a time-of-flight aerosol mass spectrometer (TOF-AMS). In addition, particle number concentrations and trace gas concentrations are measured using a condensation particle counter (CPC) and a proton transfer reaction mass spectrometer (PTR-MS). The main non-refractory components of the firework aerosol are potassium, sulfate, total organics, and chloride. Increased trace gas mixing ratios of methanol, acetonitrile, acetone and acetaldehyde are observed. It is found that aerosol nitrate and the fireworks as well as the measured aromatic trace gases do not significantly affect ammonium concentrations.

Abstract  BACKGROUND: Formic acid is a toxic metabolite responsible for the metabolic acidosis in methanol poisoning. Formate dehydrogenase (EC 1.2.1.2) converts formate into CO2 in the presence of NAD. We examined the in vitro and in vivo efficiency of formate dehydrogenase-loaded carrier erythrocytes along with carbicarb in eliminating the formate in methanol-intoxicated folate-deficient rats. METHOD: Formate dehydrogenase-loaded erythrocytes were prepared by hypotonic dialysis method. Carbicarb (carb) (equimolar solution of sodium carbonate and sodium bicarbonate) was used to treat metabolic acidosis. Folate depletion was induced by methotrexate (MTX) treatment. Experimental design consisted of 8 groups: saline control, methanol control, MTX control, ELE control, MTX-methanol control, MTX-methanol-carb, MTX-methanol-carb-ELE, and MTX-MeOH-ELE group. Male Wistar rats treated with MTX (0.3 mg/kg) for a week were injected (i.p.) with methanol (4 g/kg). Twelve hours later, the carbicarb solution was infused, and then a formate dehydrogenase-loaded erythrocytes suspension (40% hematocrit) was infused (i.v.) in bolus. Blood samples were collected every hour for 4 h from the cannulated left jugular vein. Blood methanol and formate were estimated respectively with HPLC and fluorimetric assay. Blood pH, blood pO2, pCO2 and bicarbonate were also measured. RESULTS: There was marked elimination of formate in selected groups. CONCLUSION: Formate dehydrogenase-loaded erythrocytes, along with carbicarb, facilitates removal of formate, in methanol poisoning.

Abstract  #With a world production ca. 30 million tons per year, methanol is a solvent, is used to produce formaldehyde, MTBE, and acetic acid, is a component of aspartame, and has been proposed as an alternate vehicle fuel. Methanol occurs naturally in plants and animals. It is sequentially oxidized to formaldehyde, formate and carbon dioxide, but the enzymology differs among species. In primates, oxidation of formate to carbon dioxide is rate-limiting. Formate accumulates above saturating dosages and is the proximate toxicant for blindness and death from acute methanol poisonings. Oxidation of formate in rodents is rapid and it does not accumulate. Further, in primates, methanol oxidation is primarily catalyzed by alcohol dehydrogenase (ADH), while in rodents catalase is the primary enzyme. The developmental toxicity of inhaled methanol has been studied in monkeys, rats and mice. Methanol causes visceral and skeletal malformations in rats and mice, including cervical ribs. In CD-1 mice, methanol causes cleft palate and exencephaly, while in C57BL/6J mice exposed intraperitoneally, methanol causes holoprosencephaly similar to that produced by ethanol. We reported a NOAEL of 1000 ppm methanol for 7 hr/d in CD-1 mice, with increased incidence of cervical rib at 2000 ppm. Cervical ribs and other malformations of the cervical vertebrae indicated posteriorization; e.g., tuberculae anterior normally found on C6 were observed on C5. The mouse model for human developmental toxicity of methanol is contentious because of the differences in formate oxidation. However, human exposures to environmental methanol are unlikely to produce blood levels saturating this pathway, so formate buildup would be unlikely; indeed, monkeys exposed to 2000 ppm showed no formate accumulation. Thus, methanol rather than formate may be the proximate toxicant in humans, and in the mouse higher exposures of methanol can be studied without formate accumulation. Oxidation of methanol by catalase in mice vs. ADH in humans may also be important. These studies will be discussed in the context of a risk assessment of developmental toxicity of methanol in humans. This abstract does not reflect EPA policy.

Abstract  #The effect of methanol on the levels of endogenous carnitine and its derivatives was studied in male Sprague-Dawley rats aged three months. In addition, the effect of L-carnitine supplementation on metabolic disturbances caused by methanol intoxication was studied. The rats were randomized into six groups, including two control groups. Methanol was given at 1/4 LD50 and 1/2 LD50/kg b.w. (or water in control) through an intragastric tube, and L-carnitine (or 0.9% NaCl in the control) was injected intraperitoneally. The levels of plasma L-carnitine and its derivatives were measured at selected time points for four days. Following methanol administration, the rats exhibited dose-dependent increases in L-carnitine levels and altered ratios of L-carnitine and its derivatives. L-carnitine supplementation accelerated the normalization of metabolic disturbances, as indicated by the acylcarnitine to free carnitine ratio (AC/FC). The protective effect of L-carnitine is supported by the fact that 100% of the methanol-treated rats supplemented with carnitine survived, while 8/60 rats and 27/101 rats died at methanol doses of 1/4 LD50 and 1/2 LD50, respectively, in groups without L-carnitine supplementation.

Abstract  When methyl tertiary-butyl ether (MTBE) in gasoline was first introduced to reduce vehicle exhaust emissions and comply with the Clean Air Act, in the United States, a pattern of complaints emerged characterised by seven "key symptoms." Later, carefully controlled volunteer studies did not confirm the existence of the specific key symptoms, although one study of self-reported sensitive (SRS) people did suggest that a threshold at about 11-15% MTBE in gasoline may exist for SRSs in total symptom scores. Neurobehavioral and psychophysiological studies on volunteers, including SRSs, found no adverse responses associated with MTBE at likely exposure levels. MTBE is well and rapidly absorbed following oral and inhalation exposures. Cmax values for MTBE are achieved almost immediately after oral dosing and within 2 h of continuous inhalation. It is rapidly eliminated, either by exhalation as unchanged MTBE or by urinary excretion of its less volatile metabolites. Metabolism is more rapid humans than in rats, for both MTBE and tert-butyl alcohol (TBA), its more persistent primary metabolite. The other primary metabolite, formaldehyde, is detoxified at a rate very much greater than its formation from MTBE. MTBE has no specific effects on reproduction or development, or on genetic material. Neurological effects were observed only at very high concentrations. In carcinogenicity studies of MTBE, TBA, and methanol (included as an endogenous precursor of formaldehyde, without the presence of TBA), some increases in tumor incidence have been observed, but consistency of outcome was lacking and even some degree of replication was observed in only three cases, none of which had human relevance: alpha(2u)-globulin nephropathy-related renal tubule cell adenoma in male rats; Leydig-cell adenoma in male rats, but not in mice, which provide the better model of the human disease; and B-cell-derived lymphoma/leukemia of doubtful pathogenesis that arose mainly in lungs of orally dosed female rats. In addition, hepatocellular adenomas were significantly higher in female CD-1 mice and thyroid follicular-cell adenomas were increased in female B6C3F1 mice treated with TBA, but these results lack any independent confirmation, which would have been possible from a number of other studies.