Surface structure effects on the electrochemical oxidation of ethanol on platinum single crystal electrodes

Ethanol oxidation has been studied on Pt(111), Pt(100) and Pt(110) electrodes in order to investigate the effect of the surface structure and adsorbing anions using electrochemical and FTIR techniques. The results indicate that the surface structure and anion adsorption affect significantly the reactivity of the electrode. Thus, the main product of the oxidation of ethanol on the Pt(111) electrode is acetic acid, and acetaldehyde is formed as secondary product. Moreover, the amount of CO formed is very small, and probably associated with the defects present on the electrode surface. For that reason, the amount of CO(2) is also small. This electrode has the highest catalytic activity for the formation of acetic acid in perchloric acid. However, the formation of acetic acid is inhibited by the presence of specifically adsorbed anions, such as (bi) sulfate or acetate, which is the result of the formation of acetic acid. On the other hand, CO is readily formed at low potentials on the Pt(100) electrode, blocking completely the surface. Between 0.65 and 0.80 V, the CO layer is oxidized and the production of acetaldehyde and acetic acid is detected. The Pt(110) electrode displays the highest catalytic activity for the splitting of the C-C bond. Reactions giving rise to CO formation, from either ethanol or acetaldehyde, occur at high rate at any potential. On the other hand, the oxidation of acetaldehyde to acetic acid has probably the lower reaction rate of the three basal planes.

Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: electrochemical and spectroscopic studies

Oxidation of ethanol on ruthenium-modified Pt(775) and Pt(332) stepped electrodes has been studied using electrochemical and FTIR techniques. It has been found that the oxidation of ethanol on these electrodes takes place preferentially on the step sites yielding CO(2) as the major final product. The cleavage of the C-C bond, which is the required step to yield CO(2), occurs only on this type of site. The presence of low ruthenium coverages on the step sites promotes the complete oxidation of ethanol since it facilitates the oxidation of CO formed on the step from the cleavage of the C-C bond. However, high ruthenium coverages have an important inhibiting effect since the adatoms block the step sites, which are required for the cleavage of the C-C bond. Under these conditions, the oxidation current diminishes and the major product in the oxidation process is acetic acid, which is the product formed preferentially on the (111) terrace sites.

CHEMICAL AND PHYSICO-CHEMICAL CHARACTERIZATION OF LIGNINS OBTAINED FROM ETHANOL-WATER FRACTIONATION OF BAGASSE

Organosolv lignins can replace petroleum chemicals such as phenol either partially or totally in various applications. Eight lignins, seven of which corresponded to the ethanol-water fractionation of bagasse and the other to a reference lignin (Alcell (R)) were analyzed with the aim to evaluate their chemical and physicochemical characteristics. The purity of the lignin fractions was determined by high pressure liquid chromatography (HPLC) and by ash content. Fourier Transform-Infrared Spectroscopy (FTIR) techniques and differential UV spectroscopy were applied to identify the chemical groups in the lignin samples. The molecular weight distribution was determined by size exclusion chromatography (HPSEC). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to determine the mass loss due to the high temperature treatment. The lignins studied showed the presence of p-hydroxyphenyl (H unit) and a greater proportion of guaiacyl (G unit) moieties, lower purity, similar or greater amount of phenolic hydroxyl groups, and higher degradation temperatures, than the Alcell (R) lignin.

Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms

Ethanol oxidation on platinum stepped surfaces vicinal to the (111) pole modified by tin has been studied to determine the role of this adatom in the oxidation mechanism. Tin has been slowly deposited so that the initial stages of the deposition take place on the step, and deposition on the terrace only occurs when the step has been completely decorated. Voltammetric and chronoamperometric experiments demonstrate that tin on the step catalyzes the oxidation. The maximum enhancement is found when the step is completely decorated by tin. FTIR experiments using normal and isotopically labeled ethanol have been used to elucidate the effect of the tin adatoms in the mechanism. The obtained results indicate that the role of tin is double: (i) when the surface has sites capable of breaking the C-C bond of the molecule, that is, when the step sites are not completely covered by tin, it promotes the oxidation of CO formed from the molecular fragments to CO(2) through a bifunctional mechanism and (ii) it catalyzes the oxidation of ethanol to acetic acid.

Net greenhouse gas fluxes in Brazilian ethanol production systems

Biofuels are both a promising solution to global warming mitigation and a potential contributor to the problem. Several life cycle assessments of bioethanol have been conducted to address these questions. We performed a synthesis of the available data on Brazilian ethanol production focusing on greenhouse gas (GHG) emissions and carbon (C) sinks in the agricultural and industrial phases. Emissions of carbon dioxide (CO(2)) from fossil fuels, methane (CH(4)) and nitrous oxide (N(2)O) from sources commonly included in C footprints, such as fossil fuel usage, biomass burning, nitrogen fertilizer application, liming and litter decomposition were accounted for. In addition, black carbon (BC) emissions from burning biomass and soil C sequestration were included in the balance. Most of the annual emissions per hectare are in the agricultural phase, both in the burned system (2209 out of a total of 2398 kg C(eq)), and in the unburned system (559 out of 748 kg C(eq)). Although nitrogen fertilizer emissions are large, 111 kg C(eq) ha-1 yr-1, the largest single source of emissions is biomass burning in the manual harvest system, with a large amount of both GHG (196 kg C(eq) ha-1 yr-1). and BC (1536 kg C(eq) ha-1 yr-1). Besides avoiding emissions from biomass burning, harvesting sugarcane mechanically without burning tends to increase soil C stocks, providing a C sink of 1500 kg C ha-1 yr-1 in the 30 cm layer. The data show a C output: input ratio of 1.4 for ethanol produced under the conventionally burned and manual harvest compared with 6.5 for the mechanized harvest without burning, signifying the importance of conservation agricultural systems in bioethanol feedstock production.

Quality of sugarcane in productive process of ethanol evaluated by INAA

Soil as an impurity in sugarcane is a serious problem for the ethanol industry, increasing production and maintenance costs and reducing the productivity. Fe, Hf, Sc and Th determined by INAA were used as tracers to assess the amount of soil in sugarcane from truckloads as well as in the juice extraction process. Quality control tools were applied to results identifying the need for stratification according to soil type and moisture. Soil levels of truckloads had high variability indicating potential for improving cut and loading operations. Samples from the juice extraction process allowed tracking the soil in the mill tandem.

Monitoring stress tolerance and occurrences of upper respiratory illness in basketball players by means of psychometric tools and salivary biomarkers

The aim of the study was to evaluate the possible relationships between stress tolerance, training load, banal infections and salivary parameters during 4 weeks of regular training in fifteen basketball players. The Daily Analysis of Life Demands for Athletes` questionnaire (sources and symptoms of stress) and the Wisconsin Upper Respiratory Symptom Survey were used on a weekly basis. Salivary cortisol and salivary immunoglobulin A (SIgA) were collected at the beginning (before) and after the study, and measured by enzyme-linked immunosorbent assay (ELISA). Ratings of perceived exertion (training load) were also obtained. The results from ANOVA with repeated measures showed greater training loads, number of upper respiratory tract infection episodes and negative sensation to both symptoms and sources of stress, at week 2 (p < 0.05). Significant increases in cortisol levels and decreases in SIgA secretion rate were noted (before to after). Negative sensations to symptoms of stress at week 4 were inversely and significantly correlated with SIgA secretion rate. A positive and significant relationship between sources and symptoms of stress at week 4 and cortisol levels were verified. In summary, an approach incorporating in conjunction psychometric tools and salivary biomarkers could be an efficient means of monitoring reaction to stress in sport. Copyright (C) 2010 John Wiley & Sons, Ltd.

Strength training increases walking tolerance in intermittent claudication patients: randomized trial

Objective: To analyse the effects of strength training (ST) in walking capacity in patients with intermittent claudication (IC) compared with walking training (WT) effects. Methods. Thirty patients with IC were randomized into ST and WT. Both groups trained twice a week for 12 weeks at the same rate of perceived exertion. ST consisted of three sets of 10 repetitions of whole body exercises. WT consisted of 15 bouts of 2-minute walking. Before and after the training program walking capacity, peak VO(2), VO(2) at the first stage of treadmill test, ankle brachial index, ischemic window, and knee extension strength were measured. Results: ST improved initial claudication distance (358 +/- 224 vs 504 +/- 276 meters; P < .01), total walking distance (618 +/- 282 to 775 +/- 334 meters; P < .01), VO(2), at the first stage of treadmill test (9.7 +/- 2.6 vs 8.1 +/- 1.7 mL . kg(-1) . minute; P < .01), ischemic window (0.81 +/- 1.16 vs 0.43 +/- 0.47 mm Hg minute meters(-1); P = .04), and knee extension strength (19 +/- 9 vs 21 +/- 8 kg and 21 +/- 9 vs 23 +/- 9; P < .01). Strength increases correlated with the increase in initial claudication distance (r = 0.64; P = .01.) and with the decrease ill VO(2) measured at the first stage of the treadmill test (r = -0.52; P = .04 and r = -0.55; P = .03). Adaptations following ST were similar to the ones observed after WT; however, patients reported lower pain during ST than WT (P < .01). Conclusion: ST improves functional limitation similarly to WT but it produces lower pain, suggesting that this type of exercise could be useful and should be considered in patients with IC. (J Vase Surg 2010;51:89-95.)

Effects of creatine supplementation on glucose tolerance and insulin sensitivity in sedentary healthy males undergoing aerobic training

Recent findings have indicated that creatine supplementation may affect glucose metabolism. This study aimed to examine the effects of creatine supplementation, combined with aerobic training, on glucose tolerance in sedentary healthy male. Subjects (n = 22) were randomly divided in two groups and were allocated to receive treatment with either creatine (CT) (similar to 10g .day over three months) or placebo (PT) (dextrose). Administration of treatments was double blind. Both groups underwent moderate aerobic training. An oral glucose tolerance test (OGTT) was performed and both fasting plasma insulin and the homeostasis model assessment (HOMA) index were assessed at the start, and after four, eight and twelve weeks. CT demonstrated significant decrease in OGTT area under the curve compared to PT (P = 0.034). There were no differences between groups or over time in fasting insulin or HOMA. The results suggest that creatine supplementation, combined with aerobic training, can improve glucose tolerance but does not affect insulin sensitivity, and may warrant further investigation with diabetic subjects.

Ethanol production by a new pentose-fermenting yeast strain, Scheffersomyces stipitis UFMG-IMH 43.2, isolated from the Brazilian forest

The ability of a recently isolated Scheffersomyces stipitis strain (UFMG-IMH 43.2) to produce ethanol from xylose was evaluated. For the assays, a hemicellulosic hydrolysate produced by dilute acid hydrolysis of sugarcane bagasse was used as the fermentation medium. Initially, the necessity of adding nutrients (MgSO(4).7H(2)O, yeast extract and/or urea) to this medium was verified, and the yeast extract supplementation favoured ethanol production by the yeast. Then, in a second stage, assays under different initial xylose and cell concentrations, supplemented or not with yeast extract, were performed. All these three variables showed significant (p < 0.05) influence on ethanol production. The best results (ethanol yield and productivity of 0.19 g/g and 0.13 g/l/h, respectively) were obtained using the hydrolysate containing an initial xylose concentration of 30 g/l, supplemented with 5.0 g/l yeast extract and inoculated with an initial cell concentration of 2.0 g/l. S. stipitis UFMG-IMH 43.2 was demonstrated to be a yeast strain with potential for use in xylose conversion to ethanol. The establishment of the best fermentation conditions was also proved to be of great importance to increasing the product formation by this yeast strain. These findings open up new perspectives for the establishment of a feasible technology for ethanol production from hemicellulosic hydrolysates. Copyright (C) 2011 John Wiley & Sons, Ltd.

Optimal fermentation conditions for maximizing the ethanol production by Kluyveromyces fragilis from cheese whey powder

Cheese whey powder (CWP) is an attractive raw material for ethanol production since it is a dried and concentrated form of CW and contains lactose in addition to nitrogen, phosphate and other essential nutrients. In the present work, deproteinized CWP was utilized as fermentation medium for ethanol production by Kluyveromyces fragilis. The individual and combined effects of initial lactose concentration (50-150 kg m(-3)), temperature (25-35 degrees C) and inoculum concentration (1-3 kg m(-3)) were investigated through a 2(3) full-factorial central composite design, and the optimal conditions for maximizing the ethanol production were determined. According to the statistical analysis, in the studied range of values, only the initial lactose concentration had a significant effect on ethanol production, resulting in higher product formation as the initial substrate concentration was increased. Assays with initial lactose concentration varying from 150 to 250 kg m(-3) were thus performed and revealed that the use of 200 kg m(-3) initial lactose concentration, inoculum concentration of 1 kg m(-3) and temperature of 35 degrees C were the best conditions for maximizing the ethanol production from CWP solution. Under these conditions, 80.95 kg m(-3) of ethanol was obtained after 44 h of fermentation. (C) 2011 Elsevier Ltd. All rights reserved.

ETHANOL PRODUCTION FROM XYLOSE BY Pichia stipitis NRRL Y-7124 IN A STIRRED TANK BIOREACTOR

The ethanol production by Pichia stipitis was evaluated in a stirred tank bioreactor using semi-defined medium containing xylose (90.0 g/l) as the main carbon source. Experimental assays were performed according to a 2(2) full factorial design to evaluate the influence of aeration (0.25 to 0.75 vvm) and agitation (150 to 250 rpm) conditions on ethanol production. In the studied range of values, the agitation increase and aeration decrease favored ethanol production, which was maximum (26.7 g/l) using 250 rpm and 0.25 vvm, conditions that gave a volumetric oxygen transfer coefficient (k(L)a value) of 4.9 h(-1). Under these conditions, the ethanol yield factor, ethanol productivity, and the process efficiency were 0.32 g/g, 0.32 g/l.h, and 63%, respectively. These results are promising and contribute to the development of a suitable process for ethanol production from xylose by Pichia stipitis.

The Influence of Initial Xylose Concentration, Agitation, and Aeration on Ethanol Production by Pichia stipitis from Rice Straw Hemicellulosic Hydrolysate

Rice straw hemicellulosic hydrolysate was used as fermentation medium for ethanol production by Pichia stipitis NRRL Y-7124. Shaking bath experiments were initially performed aiming to establish the best initial xylose concentration to be used in this bioconversion process. In the sequence, assays were carried out under different agitation (100 to 200 rpm) and aeration ((V) under bar (flask)/V(medium) ratio varying from 2.5 to 5.0) conditions, and the influence of these variables on the fermentative parameters values (ethanol yield factor, Y(P/S); cell yield factor, Y(X/S); and ethanol volumetric productivity, Q(P)) was investigated through a 2(2) full-factorial design. Initial xylose concentration of about 50 g/l was the most suitable for the development of this process, since the yeast was able to convert substrate in product with high efficiency. The factorial design assays showed a strong influence of both process variables in all the evaluated responses. The agitation and aeration increase caused a deviation in the yeast metabolism from ethanol to biomass production. The best results (Y(P/S) = 0.37 g/g and Q(P) = 0.39 g/l. h) were found when the lowest aeration (2.5 V(flask)/V(medium) ratio) and highest agitation (200 rpm) levels were employed. Under this condition, a process efficiency of 72.5% was achieved. These results demonstrated that the establishment of adequate conditions of aeration is of great relevance to improve the ethanol production from xylose by Pichia stipitis, using rice straw hemicellulosic hydrolysate as fermentation medium.

The roles of xylan and lignin in oxalic acid pretreated corncob during separate enzymatic hydrolysis and ethanol fermentation

High yields of hemicellulosic and cellulosic sugars are critical in obtaining economical conversion of agricultural residues to ethanol. To optimize pretreatment conditions, we evaluated oxalic acid loading rates, treatment temperatures and times in a 2(3) full factorial design. Response-surface analysis revealed an optimal oxalic acid pretreatment condition to release sugar from the cob of Zea mays L ssp. and for Pichia stipitis CBS 6054. To ferment the residual cellulosic sugars to ethanol following enzymatic hydrolysis, highest saccharification and fermentation yields were obtained following pretreatment at 180 degrees C for 50 min with 0.024 g oxalic acid/g substrate. Under these conditions, only 7.5% hemicellulose remained in the pretreated substrate. The rate of cellulose degradation was significantly less than that of hemicellulose and its hydrolysis was not as extensive. Subsequent enzymatic saccharification of the residual cellulose was strongly affected by the pretreatment condition with cellulose hydrolysis ranging between 26.0% and 76.2%. The residual xylan/lignin ratio ranged from 0.31 to 1.85 depending on the pretreatment condition. Fermentable sugar and ethanol were maximal at the lowest ratio of xylan/lignin and at high glucan contents. The model predicts optimal condition of oxalic acid pretreatment at 168 degrees C, 74 min and 0.027 g/g of oxalic acid. From these findings, we surmised that low residual xylan was critical in obtaining maximal glucose yields from saccharification. Published by Elsevier Ltd.

Ethanol Production from Sugarcane Bagasse Hydrolysate Using Pichia stipitis

The objective of this study was to evaluate the ethanol production from the sugars contained in the sugarcane bagasse hemicellulosic hydrolysate with the yeast Pichia stipitis DSM 3651. The fermentations were carried out in 250-mL Erlenmeyers with 100 mL of medium incubated at 200 rpm and 30 A degrees C for 120 h. The medium was composed by raw (non-detoxified) hydrolysate or by hydrolysates detoxified by pH alteration followed by active charcoal adsorption or by adsorption into ion-exchange resins, all of them supplemented with yeast extract (3 g/L), malt extract (3 g/L), and peptone (5 g/L). The initial concentration of cells was 3 g/L. According to the results, the detoxification procedures removed inhibitory compounds from the hemicellulosic hydrolysate and, thus, improved the bioconversion of the sugars into ethanol. The fermentation using the non-detoxified hydrolysate led to 4.9 g/L ethanol in 120 h, with a yield of 0.20 g/g and a productivity of 0.04 g L(-1) h(-1). The detoxification by pH alteration and active charcoal adsorption led to 6.1 g/L ethanol in 48 h, with a yield of 0.30 g/g and a productivity of 0.13 g L(-1) h(-1). The detoxification by adsorption into ion-exchange resins, in turn, provided 7.5 g/L ethanol in 48 h, with a yield of 0.30 g/g and a productivity of 0.16 g L(-1) h(-1).