The rise in global demand for ethanol and poverty in Brazil

Incluye Bibliografía

The rise in global demand for ethanol and poverty in Brazil

Includes bibliography

Determination of saturates, aromatics and ethanol in Brazilian commercial gasoline with low olefin content using 1 H NMR spectroscopy

In this work, a Hydrogen Nuclear Magnetic Resonance (1H NMR) method has been developed to determine aromatics and ethanol in Brazilian commercial gasoline with low olefin content. The proposed method involves subdividing an 1H NMR spectrum into regions, each of which is assumed to be associated with a specific type of structural group (OH, CH, CH2 and CH3). The method is based on the assignment of overlapping regions of 1H NMR spectra due to the signals of naphthene (N), iso and normal paraffins (P) and ethanol (E). Each 1H NMR spectrum was divided into 8 regions and the integration was correlated to the percentage of the substances to be determined. The results of the analysis by 1H NMR were compared with analysis of GC-FID obtained with the PONA system. The proposed technique of 1H NMR was shown to be an appropriate method for this sample type.

New methodology for pH measurements in fuel ethanol using glass electrode

Studies carried out with glass electrode in anhydrous ethanol and ethanol-water solutions for measuring pH values have shown that this parameter depends on the solution composition, the contact time with the solution, the utilized temperature, and the type of electrolyte used. It was also observed that the glass electrode behavior in an acid medium differs from an alkaline medium. These studies provided correction factors for pH values from 2 to 12, allowing the realization of proper measurements of the hydrogen ionic activity in the ethanol-water and anhydrous ethanol solutions. However, these correction factors could not be applied to the fuel ethanol. Alternatively, a new method was developed for the correction of the pH values, which can be applied in hydrous and anhydrous fuel ethanol samples. Copyright © 2011 by ASTM International.

Long-term ethanol consumption promotes hepatic tumorigenesis but impairs normal hepatocyte proliferation in rats

Chronic and excessive alcohol consumption has been related to an increased risk of several cancers, including that of the liver; however, studies in animal models have yet to conclusively determine whether ethanol acts as a tumor promoter in hepatic tumorigenesis. We examined whether prolonged alcohol consumption could act as a hepatic tumor promoter after initiation by diethylnitrosamine (DEN) in a rat model. Male Sprague-Dawley rats were injected with 20 mg DEN/kg body weight 1 wk before introduction of either an ethanol liquid diet or an isoenergic control liquid diet. Hepatic pathological lesions, hepatocyte proliferation, apoptosis, PPARα and PPARγ, and plasma insulin-like growth factor 1 (IGF-1) levels were assessed after 6 and 10 mo. Mean body and liver weights, plasma IGF-1 concentration, hepatic expressions of proliferating cellular nuclear antigen and Ki-67, and cyclin D1 in ethanol-fed rats were all significantly lower after 10 mo of treatment compared with control rats. In addition, levels of hepatic PPARγ protein, not PPARα, were significantly higher in the ethanol-fed rats after prolonged treatment. Although ethanol feeding also resulted in significantly fewer altered hepatic foci, hepatocellular adenoma was detected in ethanol-fed rats at 10 mo, but not in control rats given the same dose of DEN. Together, these results indicate that chronic, excessive ethanol consumption impairs normal hepatocyte proliferation, which is associated with reduced IGF-1 levels, but promotes hepatic carcinogenesis. © 2011 American Society for Nutrition.

Evaluation of water amount in hydrated ethanol fuel by gamma-ray attenuation technique

In this work, is presented an alternative and non conventional technique for evaluate the water amount present in the hydrated ethanol used as automotive fuel. The standard technique used in this kind of measure is the use of densimeter. The proposal of this work is based on the measure of the linear attenuation coefficient of hydrated ethanol, using the gamma-ray attenuation technique. The water amount, in volume, can be determined knowing the linear attenuation coefficient of hydrated ethanol. Samples of hydrated ethanol, collected at fuel stations, located in Sorocaba, SP, Brazil, were analyzed and the results showed the feasibility of the technique. © 2011 American Institute of Physics.

The expression of aquaporins 1 and 9 in adult rat epididymis is perturbed by chronic exposure to ethanol

Aquaporins (AQPs), notably AQP-1 and AQP-9, may contribute to reabsorption of fluid and solute across the epididymis. Ethanol is related to be a toxicant affecting directly or indirectly the epididymis and the sperm motility. This study examined the expression of AQP-1 and AQP-9 in adult epididymis of the UChA and UChB 10% (v/v) ethanol-preferring rats, focusing the ethanol-induced hormonal disturbances upon the regulation of these AQPs. Chronic ethanol intake significantly decreased body weight, while UChA and UChB rats displayed a marked loss of epididymal weights. Both ethanol-consuming animals had a severe reduction of testosterone levels, whereas LH and 17β-estradiol were unchanged. Throughout the epididymis, a strong reaction to AQP-1 was observed in myoid and endothelial cells of the UChB ethanol-preferring rats, differently from a moderate intensity in the initial segment of the UChA rats. In addition, AQP-9 showed a strong immunoreaction in the apical membrane of principal cells at initial segment. In cauda epididymis, the level of AQP-9 was reduced along the microvillus projections in both UChA and UChB rats compared to controls. We conclude that chronic ethanol consumption modulates the androgen levels, thereby modifying the expression pattern of AQP-1 and 9 in the epididymis. © 2011 Elsevier Ltd.

PtSnIr/C anode electrocatalysts: Promoting effect in direct ethanol fuel cells

This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH 2, PtO 2, SnO 2 and IrO 2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded. © 2012 Sociedade Brasileira de Química.

Determination of Sudan II dye in ethanol fuel by chromatographic and electroanalytical methods

Chromatographic and electroanalytical methods were developed to detect and quantify Sudan II (SD-II) dye in fuel ethanol samples. Sudan II is reduced at +0.50 V vs. Ag/AgCl on a glassy carbon electrode using Britton-Robinson buffer (pH 4.0) and N,N-dimethylformamide (70:30, v/v) + sodium dioctyl sulfosuccinate surfactant as supporting electrolyte, due to the azo group. This is the basis for its determination by square-wave voltammetry (SWV). Using the optimized conditions, it is possible to get a linear calibration curve from 3.00×10-6 to 1.80×10-5 mol L-1 (r = 0.998) with limits of detection (LOD) and quantification (LOQ) of 2.05×10-6 and 6.76×10-6 mol L-1, respectively. In addition, the hydroxyl substituent in the SD-II dye is also oxidized at +0.85 V vs. Ag/AgCl, which was conveniently used for its determination by high-performance liquid chromatography coupled to electrochemical detection (HPLC-ED). Under the optimized condition, the SD-II dye was eluted and separated using a reversed-phase column (cyanopropyl, CN) using isocratic elution with the mobile phase containing acetonitrile and aqueous lithium chloride (5.00×10-4 mol L-1) at 70:30 (v/v) and a flow rate of 1.2 mL min-1. Linear calibration curves were obtained from 3.00×10-7 to 2.00×10-6 mol L-1 (r = 0.999) with LOD and LOQ of 3.10×10-8 and 1.05×10-7 mol L-1, respectively. Both methods were simple, fast and suitable to detect and quantify the dye in fuel ethanol samples at recovery values between 83.0 to 102% (SWV) and 88.0 to 112% (HPLC-ED) with satisfactory precision and accuracy.

Chronic Ethanol Consumption Alters All-Trans-Retinoic Acid Concentration and Expression of Their Receptors on the Prostate: A Possible Link Between Alcoholism and Prostate Damage

Background: Ethanol (EtOH) alters the all-trans-retinoic acid (ATRA) levels in some tissues. Retinol and ATRA are essential for cell proliferation, differentiation, and maintenance of prostate homeostasis. It has been suggested that disturbances in retinol/ATRA concentration as well as in the expression of retinoic acid receptors (RARs) contribute to benign prostate hyperplasia and prostate cancer. This study aimed to evaluate whether EtOH consumption is able to alter retinol and ATRA levels in the plasma and prostate tissue as well as the expression of RARs, cell proliferation, and apoptosis index. Methods: All animals were divided into 4 groups (n = 10/group). UChA: rats fed 10% (v/v) EtOH ad libitum; UChACo: EtOH-naïve rats without access to EtOH; UChB: rats fed 10% (v/v) EtOH ad libitum; UChBCo: EtOH-naïve rats without access to EtOH. Animals were euthanized by decapitation after 60 days of EtOH consumption for high-performance liquid chromatography and light microscopy analysis. Results: EtOH reduced plasma retinol concentration in both UChA and UChB groups, while the retinol concentration was not significantly different in prostate tissue. Conversely, plasma and prostate ATRA levels increased in UChB group compared with controls, beyond the up-regulation of RARβ and -γ in dorsal prostate lobe. Additionally, no alteration was found in cell proliferation and apoptosis index involving dorsal and lateral prostate lobe. Conclusions: We conclude that EtOH alters the plasma retinol concentrations proportionally to the amount of EtOH consumed. Moreover, high EtOH consumption increases the concentration of ATRA in plasma/prostate tissue and especially induces the RARβ and RARγ in the dorsal prostate lobe. EtOH consumption and increased ATRA levels were not associated with cell proliferation and apoptosis in the prostate. © 2012 by the Research Society on Alcoholism.

Voltammetric determination of ethyl acetate in ethanol fuel using a Fe 3+/Nafion®-coated glassy carbon electrode

A voltammetric method for the determination of ethyl acetate in ethanol fuel using a Fe3+/Nafion®-coated glassy carbon electrode (GCE) is proposed. The ethyl acetate present in the ethanol fuel was previously converted to acetohydroxamic acid via pretreatment with hydroxylamine chloride. The acetohydroxamic acid promptly reacted with the iron (III) present in the film, producing iron (III) acetohydroxamate, which presents a well-defined voltammetric peak current at -0.02 V. Optimization of the voltammetric parameters for the cyclic, linear sweep, square wave, and differential pulse modalities was carried out for this chemically-modified electrode. Square wave voltammetry afforded the best response for acetohydroxamic acid detection. The analytical curve for this species was linear from 9 to 100 μmol L 1 according to the following equation: ip (μA) = 0.27 + 2.55Cacetohydroxamic acid (μmol L 1), with linear correlation coefficient equal to 0.993. The technique presented limit of detection equal to 5.3 μmol L 1 and quantification limit of 17.6 μmol L 1. The proposed method was compared to the official method of ethyl acetate analysis (Gas Chromatography), and a satisfactory correlation was found between these techniques. © 2012 Elsevier Ltd. All rights reserved.

Ultra-structural mapping of sugarcane bagasse after oxalic acid fiber expansion (OAFEX) and ethanol production by Candida shehatae and Saccharomyces cerevisiae

Background: Diminishing supplies of fossil fuels and oil spills are rousing to explore the alternative sources of energy that can be produced from non-food/feed-based substrates. Due to its abundance, sugarcane bagasse (SB) could be a model substrate for the second-generation biofuel cellulosic ethanol. However, the efficient bioconversion of SB remains a challenge for the commercial production of cellulosic ethanol. We hypothesized that oxalic-acid-mediated thermochemical pretreatment (OAFEX) would overcome the native recalcitrance of SB by enhancing the cellulase amenability toward the embedded cellulosic microfibrils. Results: OAFEX treatment revealed the solubilization of hemicellulose releasing sugars (12.56 g/l xylose and 1.85 g/l glucose), leaving cellulignin in an accessible form for enzymatic hydrolysis. The highest hydrolytic efficiency (66.51%) of cellulignin was achieved by enzymatic hydrolysis (Celluclast 1.5 L and Novozym 188). The ultrastructure characterization of SB using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy, Fourier transform-near infrared spectroscopy (FT-NIR), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) revealed structural differences before and after OAFEX treatment with enzymatic hydrolysis. Furthermore, fermentation mediated by C. shehatae UFMG HM52.2 and S. cerevisiae 174 showed fuel ethanol production from detoxified acid (3.2 g/l, yield 0.353 g/g; 0.52 g/l, yield, 0.246 g/g) and enzymatic hydrolysates (4.83 g/l, yield, 0.28 g/g; 6.6 g/l, yield 0.46 g/g). Conclusions: OAFEX treatment revealed marked hemicellulose degradation, improving the cellulases ability to access the cellulignin and release fermentable sugars from the pretreated substrate. The ultrastructure of SB after OAFEX and enzymatic hydrolysis of cellulignin established thorough insights at the molecular level. © 2013 Chandel et al; licensee BioMed Central Ltd.

Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica

A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and 13C and 29Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmolg -1) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol. © 2012 Elsevier Inc.

Quantification of water in ethanol using a photothermal transparent transducer

Ethanol with added water may be found during the process of assessing its physical and chemical properties. This addition can damage automotive vehicle engines and also may contribute to tax evasion. The present contribution describes a method based on a photothermal transparent transducer to determine the water content in ethanol. A chamber with a window of lithium tantalate coated with a thin layer of indium tin oxide was used, and a 1450-nm laser diode was employed as the excitation source. The results indicated a nearly linear response of the apparatus, as a function of the water content in water/ethanol solutions ranging from 0 to 100 (vol.%). The results for the dependency of the photothermal signal on the laser power and chopping frequency suggested that reliable results can be obtained using laser power and chopping rates above 100 mW and 10 Hz, respectively. The results reported here may be useful in the development of an alternative method that can provide real-time data on the water concentration in ethanol in a rapid, portable and unambiguous way, and that can be easily used in laboratory analyses or in gas stations. © 2013 Elsevier B.V.

Development and validation of an environmentally friendly attenuated total reflectance in the mid-infrared region method for the determination of ethanol content in used engine lubrication oil

Lubricating oils are crucial in the operation of automotive engines because they both reduce friction between moving parts and protect against corrosion. However, the performance of lubricant oil may be affected by contaminants, such as gasoline, diesel, ethanol, water and ethylene glycol. Although there are many standard methods and studies related to the quantification of contaminants in lubricant oil, such as gasoline and diesel oil, to the best of our knowledge, no methods have been reported for the quantification of ethanol in used Otto cycle engine lubrication oils. Therefore, this work aimed at the development and validation of a routine method based on partial least-squares multivariate analysis combined with attenuated total reflectance in the mid-infrared region to quantify ethanol content in used lubrication oil. The method was validated based on its figures of merit (using the net analyte signal) as follows: limit of detection (0.049%), limit of quantification (0.16%), accuracy (root mean square error of prediction=0.089% w/w), repeatability (0.05% w/w), fit (R 2 =0.9997), mean selectivity (0.047), sensitivity (0.011), inverse analytical sensitivity (0.016% w/w-1) and signal-to-noise ratio (max: 812.4 and min: 200.9). The results show that the proposed method can be routinely implemented for the quality control of lubricant oils. © 2013 Elsevier B.V. All rights reserved.