Sample records for alkaline h2o2 pretreatment

  1. [Effect of Residual Hydrogen Peroxide on Hydrolysis Acidification of Sludge Pretreated by Microwave -H2O2-Alkaline Process].

    PubMed

    Jia, Rui-lai; Liu, Ji-bao; Wei, Yuan-song; Cai, Xing

    2015-10-01

    Previous studies have found that in the hydrolysis acidification process, sludge after microwave -H2O2-alkaline (MW-H2O2-OH, pH = 10) pretreatment had an acid production lag due to the residual hydrogen peroxide. In this study, effects of residual hydrogen peroxide after MW-H2O2-OH (pH = 10 or pH = 11) pretreatment on the sludge hydrolysis acidification were investigated through batch experiments. Our results showed that catalase had a higher catalytic efficiency than manganese dioxide for hydrogen peroxide, which could completely degraded hydrogen peroxide within 10 min. During the 8 d of hydrolysis acidification time, both SCOD concentrations and the total VFAs concentrations of four groups were firstly increased and then decreased. The optimized hydrolysis times were 0.5 d for four groups, and the optimized hydrolysis acidification times were 3 d for MW-H2O2-OH (pH = 10) group, MW-H2O2-OH (pH = 10) + catalase group and MW-H2O2-OH (pH = 11) + catalase group. The optimized hydrolysis acidification time for MW-H2O2-OH (pH = 11) group was 4 d. Residual hydrogen peroxide inhibited acid production for sludge after MW-H2O2-OH (pH = 10) pretreatment, resulting in a lag in acidification stage. Compared with MW-H2O2-OH ( pH = 10) pretreatment, MW-H2O2-OH (pH = 11 ) pretreatment released more SCOD by 19.29% and more organic matters, which resulted in the increase of total VFAs production significantly by 84.80% at 5 d of hydrolysis acidification time and MW-H2O2-OH (pH = 11) group could shorten the lag time slightly. Dosing catalase (100 mg x -L(-1)) after the MW-H2O2-OH (pH = 10 or pH = 11) pretreatment not only significantly shortened the lag time (0.5 d) in acidification stage, but also produced more total VFAs by 23.61% and 50.12% in the MW-H2O2-OH (pH = 10) + catalase group and MW-H2O2-OH (pH = 11) + catalase group, compared with MW-H2O2-OH (pH = 10) group at 3d of hydrolysis acidification time. For MW-H2O2-OH (pH = 10) group, MW-H2O2-OH (pH = 10) + catalase group and

  2. Enhancement of sludge anaerobic biodegradability by combined microwave-H2O2 pretreatment in acidic conditions.

    PubMed

    Eswari, Parvathy; Kavitha, S; Kaliappan, S; Yeom, Ick-Tae; Banu, J Rajesh

    2016-07-01

    The aim of this study was to increase the sludge disintegration and reduce the cost of microwave (MW) pretreatment. Thermodynamic analysis of MW hydrolysis revealed the best fit with a first-order kinetic model at a specific energy of 18,600 kJ/kg total solids (TS). Combining H2O2 with MW resulted in a significant increment in solubilization from 30 to 50 % at 18,600 kJ/kg TS. The pH of H2O2-assisted MW-pretreated sludge (MW + H2O2) was in the alkaline range (pH 9-10), and it made the sludge unfavorable for subsequent anaerobic digestion and inhibits methane production. In order to nullify the alkaline effect caused by the MW + H2O2 combination, the addition of acid was considered for pH adjustment. H2O2-assisted MW-pretreated sludge in acidic conditions (MW + H2O2 + acid) showed a maximum methane production of 323 mL/g volatile solids (VS) than others during anaerobic biodegradability. A cost analysis of this study reveals that MW + H2O2 + acid was the most economical method with a net profit of 59.90 €/t of sludge.

  3. Innovative pretreatment of sugarcane bagasse using supercritical CO2 followed by alkaline hydrogen peroxide.

    PubMed

    Phan, Duy The; Tan, Chung-Sung

    2014-09-01

    An innovative method for pretreatment of sugarcane bagasse using sequential combination of supercritical CO2 (scCO2) and alkaline hydrogen peroxide (H2O2) at mild conditions is proposed. This method was found to be superior to the individual pretreatment with scCO2, ultrasound, or H2O2 and the sequential combination of scCO2 and ultrasound regarding the yield of cellulose and hemicellulose, almost twice the yield was observed. Pretreatment with scCO2 could obtain higher amount of cellulose and hemicellulose but also acid-insoluble lignin. Pretreatment with ultrasound or H2O2 could partly depolymerize lignin, however, could not separate cellulose from lignin. The analysis of liquid products via enzymatic hydrolysis by HPLC and the characterization of the solid residues by SEM revealed strong synergetic effects in the sequential combination of scCO2 and H2O2. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. CO2-H2O based pretreatment and enzyme hydrolysis of soybean hulls.

    PubMed

    Islam, S M Mahfuzul; Li, Qian; Loman, Abdullah Al; Ju, Lu-Kwang

    2017-11-01

    The high carbohydrate content of soybean hull makes it an attractive biorefinery resource. But hydrolyzing its complex structure requires concerted enzyme activities, at least cellulase, xylanase, pectinase and α-galactosidase. Effective pretreatment that generates minimal inhibitory products is important to facilitate enzymatic hydrolysis. Combined CO 2 -H 2 O pretreatment and enzymatic hydrolysis by Aspergillus niger and Trichoderma reesei enzyme broths was studied here. The pretreatment was evaluated at 80°C-180°C temperature and 750psi-1800psi pressure, with fixed moisture content (66.7%) and pretreatment time (30min). Ground hulls without and with different pretreatments were hydrolyzed by enzyme at 50°C and pH 4.8 and compared for glucose, xylose, galactose, arabinose, mannose and total reducing sugar release. CO 2 -H 2 O pretreatment at 1250psi and 130°C was found to be optimal. Compared to the unpretreated hulls hydrolyzed with 2.5-fold more enzyme, this pretreatment improved glucose, xylose, galactose, arabinose and mannose releases by 55%, 35%, 105%, 683% and 52%, respectively. Conversions of 97% for glucose, 98% for xylose, 41% for galactose, 59% for arabinose, 87% for mannose and 89% for total reducing sugar were achieved with Spezyme CP at 18FPU/g hull. Monomerization of all carbohydrate types was demonstrated. At the optimum pretreatment condition, generation of inhibitors acetic acid, furfural and hydroxymethylfurfural (HMF) was negligible, 1.5mg/g hull in total. The results confirmed the effective CO 2 -H 2 O pretreatment of soybean hulls at much lower pressure and temperature than those reported for biomass of higher lignin contents. The lower pressure requirement reduces the reactor cost and makes this new pretreatment method more practical and economical. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Electrooxidation as the anaerobic pre-treatment of fats: oleate conversion using RuO2 and IrO2 based anodes.

    PubMed

    Gonçalves, M; Alves, M M; Correia, J P; Marques, I P

    2008-11-01

    Electrochemical treatment of oleate using RuO2 and IrO2 type dimensionally stable anodes in alkaline medium was performed to develop a feasible anaerobic pre-treatment of fatty effluents. The results showed that the pre-treated solutions over RuO2 were faster degraded by anaerobic consortium than the raw oleate solutions or the electrolysed solutions using IrO2. In batch experiments carried out with pre-treated solutions over RuO2 (100-500mg/L), no lag phases were observed before the methane production onset. On the other hand, raw oleate and pre-treated oleate over IrO2 had originated lag phases of 0-140 and 0-210h, respectively. This study demonstrated that it is advantageous to apply the electrochemical treatment carried out on the RuO2 type DSA in order to achieve a faster biodegradation of lipid-containing effluent and consequently to obtain a faster methane production.

  6. Ethanol production from bamboo using mild alkaline pre-extraction followed by alkaline hydrogen peroxide pretreatment.

    PubMed

    Yuan, Zhaoyang; Wen, Yangbing; Kapu, Nuwan Sella

    2018-01-01

    A sequential two-stage pretreatment process comprising alkaline pre-extraction and alkaline hydrogen peroxide pretreatment (AHP) was investigated to convert bamboo carbohydrates into bioethanol. The results showed that mild alkaline pre-extraction using 8% (w/w) sodium hydroxide (NaOH) at 100°C for 180min followed by AHP pretreatment with 4% (w/w) hydrogen peroxide (H 2 O 2 ) was sufficient to generate a substrate that could be efficiently digested with low enzyme loadings. Moreover, alkali pre-extraction enabled the use of lower H 2 O 2 charges in AHP treatment. Two-stage pretreatment followed by enzymatic hydrolysis with only 9FPU/g cellulose led to the recovery of 87% of the original sugars in the raw feedstock. The use of the pentose-hexose fermenting Saccharomyces cerevisiae SR8u strain enabled the utilization of 95.7% sugars in the hydrolysate to reach 4.6%w/v ethanol titer. The overall process also enabled the recovery of 62.9% lignin and 93.8% silica at high levels of purity. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Enhanced Nitrobenzene reduction by zero valent iron pretreated with H2O2/HCl.

    PubMed

    Yang, Zhe; Ma, Xiaowen; Shan, Chao; Fang, Zhuoyao; Pan, Bingcai

    2018-04-01

    In this study a novel iron-based reducing agent of highly effective reduction toward nitrobenzene (NB) was obtained by pretreating zero valent iron (ZVI) with H 2 O 2 /HCl. During the H 2 O 2 /HCl pretreatment, ZVI undergoes an intensive corrosion process with formation of various reducing corrosion products (e.g., Fe 2+ , ferrous oxides/hydroxides, Fe 3 O 4 ), yielding a synergetic system (prtZVI) including liquid, suspensions and solid phase. The pretreatment process remarkably enhances the reductive performance of ZVI, where a rapid reduction of NB (200 mg L -1 ) in the prtZVI suspension was accomplished in a broad pH range (3-9) and at low dosage. Nitrosobenzene and phenylhydroxylamine are identified as the intermediates for NB reduction with the end-product of aniline. Compared with the virgin ZVI as well as another nanosized ZVI, the prtZVI system exhibits much higher electron efficiency for NB reduction as well as higher utilization ratio of Fe 0 . A rapid reduction of various nitroaromatics in an actual pharmaceutical wastewater further demonstrated the feasibility of the prtZVI system in real wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Evaluation of High Solids Alkaline Pretreatment of Rice Straw

    PubMed Central

    Cheng, Yu-Shen; Zheng, Yi; Yu, Chao Wei; Dooley, Todd M.; Jenkins, Bryan M.

    2010-01-01

    Fresh-harvested, air-dried rice straw was pretreated at a water content of 5 g H2O/g straw using sodium hydroxide (NaOH) and compared to pretreatment at 10 g H2O/g straw by hydrated lime (Ca(OH)2). Full factorial experiments including parallel wash-only treatments were completed with both sources of alkali. The experiments were designed to measure the effects of alkaline loading and pretreatment time on delignification and sugar yield upon enzymatic hydrolysis. Reaction temperature was held constant at 95°C for lime pretreatment and 55°C for NaOH pretreatment. The range of delignification was 13.1% to 27.0% for lime pretreatments and was 8.6% to 23.1% for NaOH pretreatments. Both alkaline loading and reaction time had significant positive effects (p < 0.001) on delignification under the design conditions, but only alkaline loading had a significant positive effect on enzymatic hydrolysis. Treatment at higher temperature also improved delignification; delignification with water alone ranged from 9.9% to 14.5% for pretreatment at 95°C, but there was little effect observed at 55°C. Post-pretreatment washing of biomass was not necessary for subsequent enzymatic hydrolysis. Maximum glucose yields were 176.3 mg/g dried biomass (48.5% conversion efficiency of total glucose) in lime-pretreated and unwashed biomass and were 142.3 mg/g dried biomass (39.2% conversion efficiency of total glucose) in NaOH-pretreated and unwashed biomass. PMID:20440580

  9. Effects of Aging on PuO2∙xH2O Particle Size in Alkaline Solution

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Delegard, Calvin H.

    Between 1944 and 1989, 54.5 metric tons of the United States’ weapons-grade plutonium and an additional 12.9 metric tons of fuel-grade plutonium were produced and separated from irradiated fuel at the Hanford Site. Acidic high-activity wastes containing around 600 kg of plutonium were made alkaline and discharged to underground storage tanks from separations, isolation, and recycle processes to yield average plutonium concentration of about 0.003 grams per liter (or ~0.0002 wt%) in the ~200 million liter tank waste volume. The plutonium is largely associated with low-solubility metal hydroxide/oxide sludges where its low concentration and intimate mixture with neutron-absorbing elements (e.g.,more » iron) are credited in nuclear criticality safety. However, concerns have been expressed that plutonium, in the form of plutonium hydrous oxide, PuO2∙xH2O, could undergo sufficient crystal growth through dissolution and reprecipitation in the alkaline tank waste to potentially become separable from neutron absorbing constituents by settling or sedimentation. Thermodynamic considerations and laboratory studies of systems chemically analogous to tank waste show that the plutonium formed in the alkaline tank waste by precipitation through neutralization from acid solution probably entered as 2–4-nm PuO2∙xH2O crystallite particles that, because of their low solubility and opposition from radiolytic processes, grow from that point at exceedingly slow rates, thus posing no risk of physical segregation.« less

  10. Integrated experimental and technoeconomic evaluation of two-stage Cu-catalyzed alkaline-oxidative pretreatment of hybrid poplar.

    PubMed

    Bhalla, Aditya; Fasahati, Peyman; Particka, Chrislyn A; Assad, Aline E; Stoklosa, Ryan J; Bansal, Namita; Semaan, Rachel; Saffron, Christopher M; Hodge, David B; Hegg, Eric L

    2018-01-01

    When applied to recalcitrant lignocellulosic feedstocks, multi-stage pretreatments can provide more processing flexibility to optimize or balance process outcomes such as increasing delignification, preserving hemicellulose, and maximizing enzymatic hydrolysis yields. We previously reported that adding an alkaline pre-extraction step to a copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in improved sugar yields, but the process still utilized relatively high chemical inputs (catalyst and H 2 O 2 ) and enzyme loadings. We hypothesized that by increasing the temperature of the alkaline pre-extraction step in water or ethanol, we could reduce the inputs required during Cu-AHP pretreatment and enzymatic hydrolysis without significant loss in sugar yield. We also performed technoeconomic analysis to determine if ethanol or water was the more cost-effective solvent during alkaline pre-extraction and if the expense associated with increasing the temperature was economically justified. After Cu-AHP pretreatment of 120 °C NaOH-H 2 O pre-extracted and 120 °C NaOH-EtOH pre-extracted biomass, approximately 1.4-fold more total lignin was solubilized (78% and 74%, respectively) compared to the 30 °C NaOH-H 2 O pre-extraction (55%) carried out in a previous study. Consequently, increasing the temperature of the alkaline pre-extraction step to 120 °C in both ethanol and water allowed us to decrease bipyridine and H 2 O 2 during Cu-AHP and enzymes during hydrolysis with only a small reduction in sugar yields compared to 30 °C alkaline pre-extraction. Technoeconomic analysis indicated that 120 °C NaOH-H 2 O pre-extraction has the lowest installed ($246 million) and raw material ($175 million) costs compared to the other process configurations. We found that by increasing the temperature of the alkaline pre-extraction step, we could successfully lower the inputs for pretreatment and enzymatic hydrolysis. Based on sugar yields as well as

  11. Rheological properties of sewage sludge during enhanced anaerobic digestion with microwave-H2O2 pretreatment.

    PubMed

    Liu, Jibao; Yu, Dawei; Zhang, Jian; Yang, Min; Wang, Yawei; Wei, Yuansong; Tong, Juan

    2016-07-01

    The rheological behavior of sludge is of serious concern in anaerobic digestion. This study investigated the rheological properties of sewage sludge during enhanced anaerobic digestion with microwave-H2O2 pretreatment (MW-H2O2). The results showed that MW-H2O2 pretreatment resulted in the improvement of sludge flowability and weakening of its viscoelastic properties. Further positive effects on the rheological properties of digested sludge during anaerobic digestion were observed. The flowability was improved with a low level of apparent viscosity. The decrease of the consistency index and increase of the flow behavior index indicated that the strength of the inner structures and non-Newtonian flow characteristics of digested sludge weakened. Both the storage modulus (G') and loss modulus (G″) decreased, indicating that the viscoelastic behavior became weak. These effects were possibly attributed to the changes of the digested sludge micro-structures, such as extracellular polymeric substances (EPS). This study concluded that anaerobic digestion for treating sewage sludge combined with pretreatment is a more favorable option than single anaerobic digestion from the perspective of rheology. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Comparison of high-titer lactic acid fermentation from NaOH- and NH3-H2O2-pretreated corncob by Bacillus coagulans using simultaneous saccharification and fermentation.

    PubMed

    Zhang, Zhenting; Xie, Yuejiao; He, Xiaolan; Li, Xinli; Hu, Jinlong; Ruan, Zhiyong; Zhao, Shumiao; Peng, Nan; Liang, Yunxiang

    2016-11-17

    Lignocellulose is one of the most abundant renewable feedstocks that has attracted considerable attention as a substrate for biofuel and biochemical production. One such biochemical product, lactic acid, is an important fermentation product because of its great potential for the production of biodegradable and biocompatible polylactic acid. High-titer lactic acid production from lignocellulosic materials has been achieved recently; however, it requires biodetoxification or results in large amounts of waste washing water. In this study, we employed two alkaline pretreatment methods and compared their effects on lactic acid fermentation of pretreated corncob by Bacillus coagulans LA204 using fed-batch simultaneous saccharification and fermentation under non-sterile conditions. The lactic acid titer, yield, and productivity from 16% (w/w) NaOH-pretreated and washed corncob were 122.99 g/L, 0.77 g/g corncob, and 1.37 g/L/h, respectively, and from 16% NH 3 -H 2 O 2 -pretreated and washed corncob were 118.60 g/L, 0.74 g/g corncob, and 1.32 g/L/h, respectively. Importantly, the lactic acid titer, yield, and productivity from 18.4% NH 3 -H 2 O 2 -pretreated and unwashed corncob by using fed-batch simultaneous saccharification and fermentation reached 79.47 g/L, 0.43 g/g corncob, and 1.10 g/L/h, respectively, demonstrating that this method is possible for industrial applications and saves washing water.

  13. Comparison of high-titer lactic acid fermentation from NaOH- and NH3-H2O2-pretreated corncob by Bacillus coagulans using simultaneous saccharification and fermentation

    PubMed Central

    Zhang, Zhenting; Xie, Yuejiao; He, Xiaolan; Li, Xinli; Hu, Jinlong; Ruan, Zhiyong; Zhao, Shumiao; Peng, Nan; Liang, Yunxiang

    2016-01-01

    Lignocellulose is one of the most abundant renewable feedstocks that has attracted considerable attention as a substrate for biofuel and biochemical production. One such biochemical product, lactic acid, is an important fermentation product because of its great potential for the production of biodegradable and biocompatible polylactic acid. High-titer lactic acid production from lignocellulosic materials has been achieved recently; however, it requires biodetoxification or results in large amounts of waste washing water. In this study, we employed two alkaline pretreatment methods and compared their effects on lactic acid fermentation of pretreated corncob by Bacillus coagulans LA204 using fed-batch simultaneous saccharification and fermentation under non-sterile conditions. The lactic acid titer, yield, and productivity from 16% (w/w) NaOH-pretreated and washed corncob were 122.99 g/L, 0.77 g/g corncob, and 1.37 g/L/h, respectively, and from 16% NH3-H2O2-pretreated and washed corncob were 118.60 g/L, 0.74 g/g corncob, and 1.32 g/L/h, respectively. Importantly, the lactic acid titer, yield, and productivity from 18.4% NH3-H2O2-pretreated and unwashed corncob by using fed-batch simultaneous saccharification and fermentation reached 79.47 g/L, 0.43 g/g corncob, and 1.10 g/L/h, respectively, demonstrating that this method is possible for industrial applications and saves washing water. PMID:27853308

  14. Production of bioethanol and value added compounds from wheat straw through combined alkaline/alkaline-peroxide pretreatment.

    PubMed

    Yuan, Zhaoyang; Wen, Yangbing; Li, Guodong

    2018-07-01

    An efficient scheme was developed for the conversion of wheat straw (WS) into bioethanol, silica and lignin. WS was pre-extracted with 0.2 mol/L sodium hydroxide at 30 °C for 5 h to remove about 91% of initial silica. Subsequently, the alkaline-pretreated solids were subjected to alkaline hydrogen peroxide (AHP) pretreatment with 40 mg hydrogen peroxide (H 2 O 2 )/g biomass at 50 °C for 7 h to prepare highly digestible substrate. The results of enzymatic hydrolysis demonstrated that the sequential alkaline-AHP pretreated WS was efficiently hydrolyzed at 10% (w/v) solids loading using an enzyme dosage of 10 mg protein/g glucan. The total sugar conversion of 92.4% was achieved. Simultaneous saccharification and co-fermentation (SSCF) was applied to produce ethanol from the two-stage pretreated substrate using Saccharomyces cerevisiae SR8u strain. Ethanol with concentration of 31.1 g/L was produced. Through the proposed process, about 86.4% and 54.1% of the initial silica and lignin were recovered, respectively. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Improved methane production from waste activated sludge with low organic content by alkaline pretreatment at pH 10.

    PubMed

    Feng, L Y; Yang, L Q; Zhang, L X; Chen, H L; Chen, J

    2013-01-01

    Sludge with low organic content always results in an unsatisfactory performance, even failure of anaerobic digestion. The alkaline pretreatment effect on anaerobic digestion of sludge with low organic content has seldom been studied although it gives many benefits for sludge with high organic content. In this study the influence of alkaline pretreatment (pH 10, an effective alkaline pH) on the solubilization and methane production from waste activated sludge (WAS) with low organic content was investigated. Results from biochemical methane potential (BMP) experiments showed that anaerobic biodegradability of WAS was greatly improved by alkaline pretreatment at pH 10. Methane production from the current WAS under conditions of pretreatment time 4 h and digestion time 15 d was 139.6 mL/g VS (volatile solids), much higher than that from the unpretreated WAS with digestion time of 20 d (75.2 mL/g VS). Also, the solubilization of WAS was significantly accelerated by alkaline pretreatment. Mechanism exploration indicated that the general activities of anaerobic microorganisms, specific activities of key enzymes and the amounts of methanogens were enhanced by alkaline pretreatment at pH 10, showing good agreement with methane production.

  16. The effect of H2O and pretreatment on the activity of a Pt/SnO2 catalyst

    NASA Technical Reports Server (NTRS)

    Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Schryer, David R.; Upchurch, Billy T.; Sidney, Barry D.

    1990-01-01

    CO oxidation catalysts with high activity at 25 C to 100 C are important for long-life, closed-cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 has been shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady-state yield is attained. This dip has been found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

  17. Application of H2O and UV/H2O2 processes for enhancing the biodegradability of reactive black 5 dye.

    PubMed

    Kalpana, S Divya; Kalyanaraman, Chitra; Gandhi, N Nagendra

    2011-07-01

    Leather processing is a traditional activity in India during which many organic and inorganic chemicals are added while part of it is absorbed by the leather, the remaining chemicals are discharged along with the effluent. The effluent contains both easily biodegradable and not easily biodegradable synthetic organics like dyes, syntans. Easily biodegradable organics are removed in the existing biological treatment units whereas synthetic organics present in the wastewater are mostly adsorbed over the microbes. As the tannery effluent contains complex chemicals, it is difficult to ascertain the degradation of specific pollutants. To determine the increase in the biodegradability, one of the complex and synthetic organic chemical like dye used in the tanning operation was selected for Advanced Oxidation Process (AOPs) treatment for cleaving complex organics and its subsequent treatment in aerobic process. In the present study, Reactive Black 5 Dye used in the tanning operation was selected for Hydrogen Peroxide (H2O2) and UV/H2O2 pre-treatment for different operating conditions like pH, contact time and different volume of H2O2. A comparison was made between the untreated, Hydrogen Peroxide (H2O2) and UV/H2O2 treated effluent in order to ascertain the influence of AOP on the improvement of biodegradability of effluent. An increase in the BOD5/COD ratio from 0.21 to 0.435 was achieved in the UV/H2O2 pre-treatment process. This pre-treated effluent was further subjected to aerobic process. Biochemical Oxygen Demand (BOD5) and Chemical Oxygen Demand (COD) removal efficiency of the UV/H2O2 pre-treated dye solution in the aerobic process was found to be 86.39% and 77.82% when compared to 52.43% of BOD5 and 51.55% of COD removal efficiency without any pre-treatment. Hence from these results, to increase the biodegradability of Reactive Black 5 dye pre-treatment methods like H2O2 and UV/H2O2 can be used prior to biological treatment process.

  18. Alkaline hydrogen peroxide pretreatment of cashew apple bagasse for ethanol production: study of parameters.

    PubMed

    Correia, Jessyca Aline da Costa; Júnior, José Edvan Marques; Gonçalves, Luciana Rocha B; Rocha, Maria Valderez Ponte

    2013-07-01

    The alkaline hydrogen peroxide (AHP) pretreatment of cashew apple bagasse (CAB) was evaluated based on the conversion of the resultant cellulose into glucose. The effects of the concentration of hydrogen peroxide at pH 11.5, the biomass loading and the pretreatment duration performed at 35°C and 250 rpm were evaluated after the subsequent enzymatic saccharification of the pretreated biomass using a commercial cellulase enzyme. The CAB used in this study contained 20.56 ± 2.19% cellulose, 10.17 ± 0.89% hemicellulose and 35.26 ± 0.90% lignin. The pretreatment resulted in a reduced lignin content in the residual solids. Increasing the H2O2 concentration (0-4.3% v/v) resulted in a higher rate of enzymatic hydrolysis. Lower biomass loadings gave higher glucose yields. In addition, no measurable furfural and hydroxymethyl furfural were produced in the liquid fraction during the pretreatment. The results show that alkaline hydrogen peroxide is effective for the pretreatment of CAB. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

  19. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

    USGS Publications Warehouse

    Chen, S.G.; Yang, R.T.

    1997-01-01

    From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

  20. Alkaline peroxide pretreatment of corn stover: effects of biomass, peroxide, and enzyme loading and composition on yields of glucose and xylose

    PubMed Central

    2011-01-01

    Background Pretreatment is a critical step in the conversion of lignocellulose to fermentable sugars. Although many pretreatment processes are currently under investigation, none of them are entirely satisfactory in regard to effectiveness, cost, or environmental impact. The use of hydrogen peroxide at pH 11.5 (alkaline hydrogen peroxide (AHP)) was shown by Gould and coworkers to be an effective pretreatment of grass stovers and other plant materials in the context of animal nutrition and ethanol production. Our earlier experiments indicated that AHP performed well when compared against two other alkaline pretreatments. Here, we explored several key parameters to test the potential of AHP for further improvement relevant to lignocellulosic ethanol production. Results The effects of biomass loading, hydrogen peroxide loading, residence time, and pH control were tested in combination with subsequent digestion with a commercial enzyme preparation, optimized mixtures of four commercial enzymes, or optimized synthetic mixtures of pure enzymes. AHP pretreatment was performed at room temperature (23°C) and atmospheric pressure, and after AHP pretreatment the biomass was neutralized with HCl but not washed before enzyme digestion. Standard enzyme digestion conditions were 0.2% glucan loading, 15 mg protein/g glucan, and 48 h digestion at 50°C. Higher pretreatment biomass loadings (10% to 20%) gave higher monomeric glucose (Glc) and xylose (Xyl) yields than the 2% loading used in earlier studies. An H2O2 loading of 0.25 g/g biomass was almost as effective as 0.5 g/g, but 0.125 g/g was significantly less effective. Optimized mixtures of four commercial enzymes substantially increased post-AHP-pretreatment enzymatic hydrolysis yields at all H2O2 concentrations compared to any single commercial enzyme. At a pretreatment biomass loading of 10% and an H2O2 loading of 0.5 g/g biomass, an optimized commercial mixture at total protein loadings of 8 or 15 mg/g glucan gave

  1. Recycling the liquid fraction of alkaline hydrogen peroxide in the pretreatment of corn stover.

    PubMed

    Alencar, Bárbara Ribeiro Alves; Reis, Alexandre Libanio Silva; de Souza, Raquel de Fatima Rodrigues; Morais, Marcos Antônio; Menezes, Rômulo Simões Cezar; Dutra, Emmanuel Damilano

    2017-10-01

    The aim of this study was to evaluate the influence of recycling the liquid fraction of pretreatment with alkaline hydrogen peroxide (AHP) on the hydrolysis of corn stover. Corn stover was pretreated in the traditional condition with 7.5% v/v H 2 O 2 . After pretreatment, the solids were separated from the liquid fraction and five successive reuse cycles of the liquid fraction were tested. The solid fraction from pretreatment in each recycle was submitted to enzymatic hydrolysis. The number of recycles had a linear negative effect (R 2 =0.98) on biomass delignification efficiency and also affected negatively the enzymatic conversion efficiency. Despite the decrease in efficiency after each recycling step, reuse of the liquid fraction leads to reduction in water, H 2 O 2 and NaOH consumption of up to 57.6%, 59.6% and 57.6%, respectively. These findings point to an efficient recycling technology, which may reduce costs and save water. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

    PubMed

    Solbrå, S; Allison, N; Waite, S; Mikhalovsky, S V; Bortun, A I; Bortun, L N; Clearfield, A

    2001-02-01

    The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

  3. Two-stage alkaline-enzymatic pretreatments to enhance biohydrogen production from sunflower stalks.

    PubMed

    Monlau, Florian; Trably, Eric; Barakat, Abdellatif; Hamelin, Jérôme; Steyer, Jean-Philippe; Carrere, Hélène

    2013-01-01

    Because of their rich composition in carbohydrates, lignocellulosic residues represent an interesting source of biomass to produce biohydrogen by dark fermentation. Nevertheless, pretreatments should be applied to enhance the solubilization of holocelluloses and increase their further conversion into biohydrogen. The aim of this study was to investigate the effect of thermo-alkaline pretreatment alone and combined with enzymatic hydrolysis to enhance biohydrogen production from sunflower stalks. A low increase of hydrogen potentials from 2.3 ± 0.9 to 4.4 ± 2.6 and 20.6 ± 5.6 mL of H2 g(-1) of volatile solids (VS) was observed with raw sunflower stalks and after thermo-alkaline pretreatment at 55 °C, 24 h, and 4% NaOH and 170 °C, 1 h, and 4% NaOH, respectively. Enzymatic pretreatment alone showed an enhancement of the biohydrogen yields to 30.4 mL of H2 g(-1) of initial VS, whereas it led to 49 and 59.5 mL of H2 g(-1) of initial VS when combined with alkaline pretreatment at 55 and 170 °C, respectively. Interestingly, a diauxic effect was observed with sequential consumption of sugars by the mixed cultures during dark fermentation. Glucose was first consumed, and once glucose was completely exhausted, xylose was used by the microorganisms, mainly related to Clostridium species.

  4. Controllable synthesis of (NH4)Fe2(PO4)2(OH)·2H2O using two-step route: Ultrasonic-intensified impinging stream pre-treatment followed by hydrothermal treatment.

    PubMed

    Dong, Bin; Li, Guang; Yang, Xiaogang; Chen, Luming; Chen, George Z

    2018-04-01

    (NH 4 )Fe 2 (PO 4 ) 2 (OH)·2H 2 O samples with different morphology are successfully synthesized via two-step synthesis route - ultrasonic-intensified impinging stream pre-treatment followed by hydrothermal treatment (UIHT) method. The effects of the adoption of ultrasonic-intensified impinging stream pre-treatment, reagent concentration (C), pH value of solution and hydrothermal reaction time (T) on the physical and chemical properties of the synthesised (NH 4 )Fe 2 (PO 4 ) 2 (OH)·2H 2 O composites and FePO 4 particles were systematically investigated. Nano-seeds were firstly synthesized using the ultrasonic-intensified T-mixer and these nano-seeds were then transferred into a hydrothermal reactor, heated at 170 °C for 4 h. The obtained samples were characterized by utilising XRD, BET, TG-DTA, SEM, TEM, Mastersizer 3000 and FTIR, respectively. The experimental results have indicated that the particle size and morphology of the obtained samples are remarkably affected by the use of ultrasonic-intensified impinging stream pre-treatment, hydrothermal reaction time, reagent concentration, and pH value of solution. When such (NH 4 )Fe 2 (PO 4 ) 2 (OH)·2H 2 O precursor samples were transformed to FePO 4 products after sintering at 650 °C for 10 h, the SEM images have clearly shown that both the precursor and the final product still retain their monodispersed spherical microstructures with similar particle size of about 3 μm when the samples are synthesised at the optimised condition. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Impact of ozonation, anion exchange resin and UV/H2O2 pre-treatments to control fouling of ultrafiltration membrane for drinking water treatment.

    PubMed

    Pramanik, Biplob Kumar; Pramanik, Sagor Kumar; Sarker, Dipok Chandra; Suja, Fatihah

    2017-06-01

    The effects of ozonation, anion exchange resin (AER) and UV/H 2 O 2 were investigated as a pre-treatment to control organic fouling (OF) of ultrafiltration membrane in the treatment of drinking water. It was found that high molecular weight (MW) organics such as protein and polysaccharide substances were majorly responsible for reversible fouling which contributed to 90% of total fouling. The decline rate increased with successive filtration cycles due to deposition of protein content over time. All pre-treatment could reduce the foulants of a Ultrafiltration membrane which contributed to the improvement in flux, and there was a greater improvement of flux by UV/H 2 O 2 (61%) than ozonation (43%) which in turn was greater than AER (23%) treatment. This was likely due to the effective removal/breakdown of high MW organic content. AER gave greater removal of biofouling potential components (such as biodegradable dissolved organic carbon and assimilable organic carbon contents) compared to UV/H 2 O 2 and ozonation treatment. Overall, this study demonstrated the potential of pre-treatments for reducing OF of ultrafiltration for the treatment of drinking water.

  6. A fuel-cell reactor for the direct synthesis of hydrogen peroxide alkaline solutions from H(2) and O(2).

    PubMed

    Yamanaka, Ichiro; Onisawa, Takeshi; Hashimoto, Toshikazu; Murayama, Toru

    2011-04-18

    The effects of the type of fuel-cell reactors (undivided or divided by cation- and anion-exchange membranes), alkaline electrolytes (LiOH, NaOH, KOH), vapor-grown carbon fiber (VGCF) cathode components (additives: none, activated carbon, Valcan XC72, Black Pearls 2000, Seast-6, and Ketjen Black), and the flow rates of anolyte (0, 1.5, 12 mL h(-1)) and catholyte (0, 12 mL h(-1)) on the formation of hydrogen peroxide were studied. A divided fuel-cell system, O(2) (g)|VGCF-XC72 cathode|2 M NaOH catholyte|cation-exchange membrane (Nafion-117)|Pt/XC72-VGCF anode|2 M NaOH anolyte at 12 mL h(-1) flow|H(2) (g), was effective for the selective formation of hydrogen peroxide, with 130 mA cm(-2) , a 2 M aqueous solution of H(2)O(2)/NaOH, and a current efficiency of 95 % at atmospheric pressure and 298 K. The current and formation rate gradually decreased over a long period of time. The cause of the slow decrease in electrocatalytic performance was revealed and the decrease was stopped by a flow of catholyte. Cyclic voltammetry studies at the VGCF-XC72 electrode indicated that fast diffusion of O(2) from the gas phase to the electrode, and quick desorption of hydrogen peroxide from the electrode to the electrolyte were essential for the efficient formation of solutions of H(2)O(2)/NaOH. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Combined (alkaline+ultrasonic) pretreatment effect on sewage sludge disintegration.

    PubMed

    Kim, Dong-Hoon; Jeong, Emma; Oh, Sae-Eun; Shin, Hang-Sik

    2010-05-01

    The individual effects of alkaline (pH 8-13) and ultrasonic (3750-45,000kJ/kg TS) pretreatments on the disintegration of sewage sludge were separately tested, and then the effect of combining these two methods at different intensity levels was investigated using response surface methodology (RSM). In the combined pretreatment, ultrasonic treatment was applied to the alkali-pretreated sludge. While the solubilization (SCOD/TCOD) increase was limited to 50% in individual pretreatments, it reached 70% in combined pretreatment, and the results clearly showed that preconditioning of sludge at high pH levels played a crucial role in enhancing the disintegration efficiency of the subsequent ultrasonic pretreatment. By applying regression analysis, the disintegration degree (DD) was fitted based on the actual value to a second order polynomial equation: Y=-172.44+29.82X(1)+5.30x10(-3)X(2)-7.53x10(-5)X(1)X(2)-1.10X(1)(2)-1.043x10(-7)X(2)(2), where X(1), X(2), and Y are pH, specific energy input (kJ/kg TS), and DD, respectively. In a 2D contour plot describing the tendency of DD with respect to pH and specific energy input, it was clear that DD increased as pH increased, but it seemed that DD decreased when the specific energy input exceeded about 20,000kJ/kg TS. This phenomenon tells us that there exists a certain point where additional energy input is ineffective in achieving further disintegration. A synergetic disintegration effect was also found in the combined pretreatment, with lower specific energy input in ultrasonic pretreatment yielding higher synergetic effect. Finally, in order to see the combined pretreatment effect in continuous operation, the sludge pretreated with low intensity alkaline (pH 9)/ultrasonic (7500kJ/kg TS) treatment was fed to a 3 L of anaerobic sequencing batch reactor after 70 days of control operation. CH(4) production yield significantly increased from 81.9+/-4.5mL CH(4)/g COD(added) to 127.3+/-5.0mL CH(4)/g COD(added) by pretreatment, and

  8. Alkaline-Acid Zn-H2 O Fuel Cell for the Simultaneous Generation of Hydrogen and Electricity.

    PubMed

    Cai, Pingwei; Li, Yan; Wang, Genxiang; Wen, Zhenhai

    2018-04-03

    An alkaline-acid Zn-H 2 O fuel cell is proposed for the simultaneous generation of electricity with an open circuit voltage of about 1.25 V and production of H 2 with almost 100 % Faradic efficiency. We demonstrate that, as a result of harvesting energy from both electrochemical neutralization and electrochemical Zn oxidation, the as-developed hybrid cell can deliver a power density of up to 80 mW cm -2 and an energy density of 934 Wh kg -1 and maintain long-term stability for H 2 production with an output voltage of 1.16 V at a current density of 10 mA cm -2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Solar light (hv) and H2O2/hv photo-disinfection of natural alkaline water (pH 8.6) in a compound parabolic collector at different day periods in Sahelian region.

    PubMed

    Ndounla, J; Pulgarin, C

    2015-11-01

    The photo-disinfection of natural alkaline surface water (pH 8.6 ± 0.3) for drinking purposes was carried out under solar radiation treatments. The enteric bacteria studied were the wild total coliforms/Escherichia coli (10(4) CFU/ml) and Salmonella spp. (10(4) CFU/ml) naturally present in the water. The photo-disinfection of a 25-l water sample was carried out in a solar compound parabolic collector (CPC) in the absence and in the presence of hydrogen peroxide (H2O2). The addition of H2O2 (10 mg/L) to the sample water was sufficient to enhance the photo-disinfection and ensure an irreversible lethal action on the wild enteric bacteria contents of the sample. The inactivation kinetic of the system was significantly enhanced compared to the one carried out without H2O2 addition. The effect of the solar radiation parameters on the efficiency of the photo-disinfection were assessed. The pH has increased during the treatment in all the photo-disinfection processes (hv and H2O2/hv). The Salmonella spp strain has shown the best effective inactivate time in alkaline water than the one recorded under acidic or near-neutral conditions. The evolution of some physico-chemical parameters of the water (turbidity, NO2(-), NO3(-), NH4(+), HPO4(2-), and bicarbonate (HCO3(-))) was monitored during the treatment. Finally, the possible mechanistic process involved during the enteric bacteria inactivation was suggested.

  10. Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

    1992-01-01

    Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

  11. Alkaline-assisted screw press pretreatment affecting enzymatic hydrolysis of wheat straw.

    PubMed

    Yan, Qingqi; Wang, Yumei; Rodiahwati, Wawat; Spiess, Antje; Modigell, Michael

    2017-02-01

    Screw press processing of biomass can be considered as a suitable mechanically based pretreatment for biofuel production since it disrupts the structure of lignocellulosic biomass with high shear and pressure forces. The combination with chemical treatment has been suggested to increase the conversion of lignocellulosic biomass to fermentable sugars. Within the study, the synergetic effect of alkaline (sodium hydroxide, NaOH) soaking and screw press pretreatment on wheat straw was evaluated based on, e.g., sugar recovery and energy efficiency. After alkaline soaking (at 0.1 M for 30 min) and sequential screw press pretreatment with various screw press configurations and modified screw barrel, the lignin content of pretreated wheat straw was quantified. In addition, the structure of pretreated wheat straw was investigated by scanning electron microscopy and measurement of specific surface area. It could be shown that removal of lignin is more important than increase of surface area of the biomass to reach a high sugar recovery. The rate constant of the enzymatic hydrolysis increased from 1.1 × 10 -3  1/h for the non-treated material over 2.3 × 10 -3  1/h for the alkaline-soaked material to 26.9 × 10 -3  1/h for alkaline-assisted screw press pretreated material, indicating a nearly 25-fold improvement of the digestibility by the combined chemo-mechanical pretreatment. Finally, the screw configuration was found to be an important factor for improving the sugar recovery and for reducing the specific energy consumption of the screw press pretreatment.

  12. Combined acid/alkaline-peroxide pretreatment of olive tree biomass for bioethanol production.

    PubMed

    Martínez-Patiño, José Carlos; Ruiz, Encarnación; Romero, Inmaculada; Cara, Cristóbal; López-Linares, Juan Carlos; Castro, Eulogio

    2017-09-01

    Olive tree biomass (OTB) can be used for producing second generation bioethanol. In this work, extracted OTB was subjected to fractionation using a sequential acid/alkaline oxidative pretreatment. In the first acid stage, the effects of sulfuric acid concentration and reaction times at 130°C were investigated. Up to 71% solubilization of hemicellulosic sugars was achieved under optimized conditions (2.4% H 2 SO 4 , 84min). In the second stage, the influence of hydrogen peroxide concentration and process time were evaluated at 80°C. Approximately 80% delignification was achieved under the best operational conditions (7% H 2 O 2 , 90min) within the experimental range studied. This pretreatment produced a substrate with 72% cellulose that was highly accessible to enzymatic attack, yielding 82g glucose/100g glucose in delignified OTB. Ethanol production from both hemicellulosic sugars solubilized in the acid pretreatment and glucose from enzymatic hydrolysis of delignified OTB yielded 15g ethanol/100g OTB. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

    2013-01-01

    We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

  14. Mega-solubility of quartz resulting from highly alkaline fluids produced by dissolved albite in H2O at deep crustal conditions

    NASA Astrophysics Data System (ADS)

    Makhluf, A. R.; Manning, C. E.

    2017-12-01

    Models of H2O-rich fluids equilibrated with rocks at high P and T fail to predict the high solubilities observed experimentally, chiefly because thermodynamic data for the most abundant solutes is lacking. We investigated the effects of dissolved albite (Ab) on the solubility of quartz (Qz) at 1.0 GPa and 675-900 °C using a piston-cylinder apparatus to quantify possible mineral buffering or enhancement effects. We found a very large enhancement effect on the solubility of Qz when dissolved in dilute aqueous Ab solutions. SiO2 concentrations are similar to Qz solubility in strongly alkaline KOH solutions. At the highest temperature of 900 °C, we found that the solubility of Qz in 1.0 molal Ab solution increases by of factor of 4.5 over that in pure H2O, which corresponds to 10.7 molal SiO2. The nearly identical solubility of Qz in KOH(aq) and Ab solutions of the same concentration, P, and T, strongly suggest that NaOH(aq) liberated from NaAlSi3O8 in H2O fluids effects SiO2 solubility in a similar manner to that of KOH(aq). The deprotonated silica dimer was found to be a key species responsible for the high solubility of Qz in KOH(aq) and is likely responsible for the high solubility of Qz in Ab solutions. While the binaries Qz-H2O, Ab-H2O, and Qz-Ab are well known at 1.0 GPa, little data exists on the ternary system. The new results help quantify the ternary relations in the Ab-Qz-H2O system, which can be used as a simple model for liquid-vapor immiscibility granitic magmas. In addition, these highly alkaline solute-rich aqueous fluids suggest a mechanism for Ab-Qz metasomatism in subduction zones, such as in the Catalina schist (Bebout and Barton 1993), which provides an alternative to high P-T magmas. Our results show that subduction zone and metasomatic fluids may be much more alkaline and have significantly higher dissolving power than previously thought.

  15. Enhanced enzymatic saccharification of sugarcane bagasse pretreated by combining O2 and NaOH.

    PubMed

    Bi, Shuaizhu; Peng, Lincai; Chen, Keli; Zhu, Zhengliang

    2016-08-01

    Sugarcane bagasse pretreated by combining O2 and NaOH with different variables was conducted to improve its enzymatic digestibility and sugar recovery, and the results were compared with sole NaOH pretreatment. Lignin removal for O2-NaOH pretreatment was around 10% higher than that for sole NaOH pretreatment under the same conditions, and O2-NaOH pretreatment resulted in higher glucan recovery in the solid remain. Subsequently, O2-NaOH pretreated sugarcane bagasse presented more efficient enzymatic digestibility than sole NaOH pretreatment. Under the moderate pretreatment conditions of combining 1% NaOH and 0.5MPa O2 at 80°C for 120min, a high glucan conversion of 95% was achieved after 48h enzymatic hydrolysis. Coupled with the operations of pretreatment and enzymatic hydrolysis, an admirable total sugar recovery of 89% (glucose recovery of 93% and xylose recovery of 84%) was obtained. The susceptibility of the substrates to enzymatic digestibility was explained by their physical and chemical characteristics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Protective effect of Dendrobium officinale polysaccharides on H2O2-induced injury in H9c2 cardiomyocytes.

    PubMed

    Zhao, Xiaoyan; Dou, Mengmeng; Zhang, Zhihao; Zhang, Duoduo; Huang, Chengzhi

    2017-10-01

    The preliminary studies have shown that Dendrobium officinale possessed therapeutic effects on hypertension and atherosclerosis. Studies also reported that Dendrobium officinale polysaccharides showed antioxidant capabilities. However, little is known about its effects on myocardial cells under oxidative stress. The present study was designed to study the protective effect of Dendrobium officinale polysaccharides against H 2 O 2 -induced oxidative stress in H9c2 cells. MTT assay was carried out to determine the cell viability of H9c2 cells when pretreated with Dendrobium officinale polysaccharides. Fluorescent microscopy measurements were performed for evaluating the apoptosis in H9c2 cells. Furthermore, effects of Dendrobium officinale polysaccharides on the activities of antioxidative indicators (malondialdehyde, superoxide dismutase), reactive oxygen species (ROS) production and mitochondrial membrane potential (MMP) levels were analyzed. Dendrobium officinale polysaccharides attenuated H 2 O 2 -induced cell death, as determined by the MTT assay. Dendrobium officinale polysaccharides decreased malondialdehyde levels, increased superoxide dismutase activities, and inhibited the generation of intracellular ROS. Moreover, pretreatment with Dendrobium officinale polysaccharides also inhibited apoptosis and increased the MMP levels in H9c2 cells. These results suggested the protective effects of Dendrobium officinale polysaccharides against H 2 O 2 -induced injury in H9c2 cells. The results also indicated the anti-oxidative capability of Dendrobium officinale polysaccharides. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  17. Chlorogenic acid analogues from Gynura nepalensis protect H9c2 cardiomyoblasts against H2O2-induced apoptosis

    PubMed Central

    Yu, Bang-wei; Li, Jin-long; Guo, Bin-bin; Fan, Hui-min; Zhao, Wei-min; Wang, He-yao

    2016-01-01

    Aim: Chlorogenic acid has shown protective effect on cardiomyocytes against oxidative stress-induced damage. Herein, we evaluated nine caffeoylquinic acid analogues (1–9) isolated from the leaves of Gynura nepalensis for their protective effect against H2O2-induced H9c2 cardiomyoblast damage and explored the underlying mechanisms. Methods: H9c2 cardiomyoblasts were exposed to H2O2 (0.3 mmol/L) for 3 h, and cell viability was detected with MTT assay. Hoechst 33342 staining was performed to evaluate cell apoptosis. MMPs (mitochondrial membrane potentials) were measured using a JC-1 assay kit, and ROS (reactive oxygen species) generation was measured using CM-H2 DCFDA. The expression levels of relevant proteins were detected using Western blot analysis. Results: Exposure to H2O2 markedly decreased the viability of H9c2 cells and catalase activity, and increased LDH release and intracellular ROS production; accompanied by a loss of MMP and increased apoptotic rate. Among the 9 chlorogenic acid analogues as well as the positive control drug epigallocatechin gallate (EGCG) tested, compound 6 (3,5-dicaffeoylquinic acid ethyl ester) was the most effective in protecting H9c2 cells from H2O2-induced cell death. Pretreatment with compound 6 (1.56–100 μmol/L) dose-dependently alleviated all the H2O2-induced detrimental effects. Moreover, exposure to H2O2 significantly increased the levels of Bax, p53, cleaved caspase-8, and cleaved caspase-9, and decreased the level of Bcl-2, resulting in cell apoptosis. Exposure to H2O2 also significantly increased the phosphorylation of p38, JNK and ERK in the H9c2 cells. Pretreatment with compound 6 (12.5 and 25 μmol/L) dose-dependently inhibited the H2O2-induced increase in the level of cleaved caspase-9 but not of cleaved caspase-8. It also dose-dependently suppressed the H2O2-induced phosphorylation of JNK and ERK but not that of p38. Conclusion: Compound 6 isolated from the leaves of Gynura nepalensis potently protects H9c2

  18. Epigallocatechin gallate (EGCG) prevents H2O2-induced oxidative stress in primary rat retinal pigment epithelial cells.

    PubMed

    Cia, David; Vergnaud-Gauduchon, Juliette; Jacquemot, Nathalie; Doly, Michel

    2014-09-01

    To determine whether the green tea polyphenol epigallocatechin gallate (EGCG) could prevent H(2)O(2)-induced oxidative stress in primary rat retinal pigment epithelial cells. Primary cultures of retinal pigment epithelium (RPE) cells were established from Long-Evans newborn rats. RPE cells were pretreated with various concentrations of EGCG for 24 h before being exposed to hydrogen peroxide (H(2)O(2)) for 2h to induce oxidative stress. Cell metabolic activity was measured using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Cell death was quantified by flow cytometry using propidium iodide (PI). Treatment of RPE cells with EGCG alone does not affect the cell viability up to 50 µM. Exposure of RPE cells to 600 µM H(2)O(2) caused a significant decrease in cell viability; whereas pretreatment with 10, 25, and 50 µM EGCG significantly reduced this decrease in a dose-dependent manner. The proportion of PI-positive cells increased significantly in cultures treated with H(2)O(2) alone; whereas pretreatment of RPE cells with 50 µM EGCG significantly reduced H(2)O(2)-induced RPE cell death. Our study shows that EGCG pretreatment can protect primary rat RPE cells from H(2)O(2)-induced death. This suggests potential effect of EGCG in the prevention of retinal diseases associated with H(2)O(2)-induced oxidative stress.

  19. Effect of H2O2 and nonionic surfactant in alkaline copper slurry

    NASA Astrophysics Data System (ADS)

    Haobo, Yuan; Yuling, Liu; Mengting, Jiang; Guodong, Chen; Weijuan, Liu; Shengli, Wang

    2015-01-01

    For improving the polishing performance, in this article, the roles of a nonionic surfactant (Fatty alcohol polyoxyethylene ether) and H2O2 were investigated in the chemical mechanical planarization process, respectively. Firstly, the effects of the nonionic surfactant on the within-wafer non-uniformity (WIWNU) and the surface roughness were mainly analyzed. In addition, the passivation ability of the slurry, which had no addition of BTA, was also discussed from the viewpoint of the static etch rate, electrochemical curve and residual step height under different concentrations of H2O2. The experimental results distinctly revealed that the nonionic surfactant introduced in the slurry improved the WIWNU and surface roughness, and that a 2 vol% was considered as an appropriate concentration relatively. When the concentration of H2O2 surpasses 3 vol%, the slurry will possess a relatively preferable passivation ability, which can effectively decrease the step height and contribute to acquiring a flat and smooth surface. Hence, based on the result of these experiments, the influences of the nonionic surfactant and H2O2 are further understood, which means the properties of slurry can be improved.

  20. Micropore Formation of [Zn2(Oxac) (Taz)2]·(H2O)2.5 via CO2 Adsorption.

    PubMed

    Zubir, Moondra; Hamasaki, Atom; Iiyama, Taku; Ohta, Akira; Ohki, Hiroshi; Ozeki, Sumio

    2017-01-24

    As-synthesized [Zn 2 (Oxac) (Taz) 2 ]·(H 2 O) 2.5 , referred to as ZOTW 2.5 , was prepared from aqueous methanol solutions of Zn 5 (CO 3 ) 2 (OH) 6 and two kinds of ligands of 1,2,4-triazole (Taz) and oxalic acid (Oxac) at 453 K for 12 h. The crystal structure was determined by the Rietveld method. As-synthesized ZOTW 2.5 was pretreated at 383 K and 1 mPa for t pt h, ZOTW x (t pt h). ZOTW x (≥3h) showed a type I adsorption isotherm for N 2 at 77 K having a saturation amount (V s ) of 180 mg/g, but that pretreated shortly showed only 1/10 in V s . CO 2 was adsorbed at 303 K in sigmoid on nonporous ZOTW x (≤2h) and in Langmuir-type on ZOTW x (≥3h) to reach the adsorption amount of 120 mg/g at 700 Torr. N 2 adsorption on ZOTW x (≤2h)deCO 2 , degassed after CO 2 adsorption on ZOTW x (≤2h), was promoted 5-fold from 180 mg/g on ZOTW x (t pt h) and ZOTW x (≥3h)deCO 2 up to ca. 1000 mg/g. The interaction of CO 2 and H 2 O molecules in micropores may lead to a new route for micropore formation.

  1. Effective alkaline metal-catalyzed oxidative delignification of hybrid poplar

    DOE PAGES

    Bhalla, Aditya; Bansal, Namita; Stoklosa, Ryan J.; ...

    2016-02-09

    Background: Strategies to improve copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment of hybrid poplar were investigated. These improvements included a combination of increasing hydrolysis yields, while simultaneously decreasing process inputs through (i) more efficient utilization of H 2O 2 and (ii) the addition of an alkaline extraction step prior to the metal-catalyzed AHP pretreatment. We hypothesized that utilizing this improved process could substantially lower the chemical inputs needed during pretreatment. Results: Hybrid poplar was pretreated utilizing a modified process in which an alkaline extraction step was incorporated prior to the Cu-AHP treatment step and H 2O 2 was added batch-wise overmore » the course of 10 h. Our results revealed that the alkaline pre-extraction step improved both lignin and xylan solubilization, which ultimately led to improved glucose (86 %) and xylose (95 %) yields following enzymatic hydrolysis. An increase in the lignin solubilization was also observed with fed-batch H 2O 2 addition relative to batch-only addition, which again resulted in increased glucose and xylose yields (77 and 93 % versus 63 and 74 %, respectively). Importantly, combining these strategies led to significantly improved sugar yields (96 % glucose and 94 % xylose) following enzymatic hydrolysis. In addition, we found that we could substantially lower the chemical inputs (enzyme, H 2O 2, and catalyst), while still maintaining high product yields utilizing the improved Cu-AHP process. This pretreatment also provided a relatively pure lignin stream consisting of ≥90 % Klason lignin and only 3 % xylan and 2 % ash following precipitation. Two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR and size-exclusion chromatography demonstrated that the solubilized lignin was high molecular weight (Mw ≈ 22,000 Da) and only slightly oxidized relative to lignin from untreated poplar. In conclusion: This study demonstrated that the fed

  2. Cutin monomers and surface wax constituents elicit H2O2 in conditioned cucumber hypocotyl segments and enhance the activity of other H2O2 elicitors

    PubMed

    Fauth; Schweizer; Buchala; Markstadter; Riederer; Kato; Kauss

    1998-08-01

    Hypocotyls from etiolated cucumber (Cucumis sativus L.) seedlings were gently abraded at their epidermal surface and cut segments were conditioned to develop competence for H2O2 elicitation. Alkaline hydrolysates of cutin from cucumber, tomato, and apple elicited H2O2 in such conditioned segments. The most active constituent of cucumber cutin was identified as dodecan-1-ol, a novel cutin monomer capable of forming hydrophobic terminal chains. Additionally, the cutin hydrolysates enhanced the activity of a fungal H2O2 elicitor, similar to cucumber surface wax, which contained newly identified alkan-1,3-diols. The specificity of elicitor and enhancement activity was further elaborated using some pure model compounds. Certain saturated hydroxy fatty acids were potent H2O2 elicitors as well as enhancers. Some unsaturated epoxy and hydroxy fatty acids were also excellent H2O2 elicitors but inhibited the fungal elicitor activity. Short-chain alkanols exhibited good elicitor and enhancer activity, whereas longer-chain alkan-1-ols were barely active. The enhancement effect was also observed for H2O2 elicitation by ergosterol and chitosan. The physiological significance of these observations might be that once the cuticle is degraded by fungal cutinase, the cutin monomers may act as H2O2 elicitors. Corrosion of cutin may also bring surface wax constituents in contact with protoplasts and enhance elicitation.

  3. Effect of coagulation on treatment of municipal wastewater reverse osmosis concentrate by UVC/H2O2.

    PubMed

    Umar, Muhammad; Roddick, Felicity; Fan, Linhua

    2014-02-15

    Disposal of reverse osmosis concentrate (ROC) is a growing concern due to potential health and ecological risks. Alum coagulation was investigated as pre-treatment for the UVC/H2O2 treatment of two high salinity ROC samples (ROC A and B) of comparable organic and inorganic content. Coagulation removed a greater fraction of the organic content for ROC B (29%) than ROC A (16%) which correlated well with the reductions of colour and A254. Although the total reductions after 60 min UVC/H2O2 treatment with and without coagulation were comparable, large differences in the trends of reduction were observed which were attributed to the different nature of the organic content (humic-like) of the samples as indicated by the LC-OCD analyses and different initial (5% and 16%) biodegradability. Coagulation and UVC/H2O2 treatment preferentially removed humic-like compounds which resulted in low reaction rates after UVC/H2O2 treatment of the coagulated samples. The improvement in biodegradability was greater (2-3-fold) during UVC/H2O2 treatment of the pre-treated samples than without pre-treatment. The target DOC residual (≤ 15 mg/L) was obtained after 30 and 20 min irradiation of pre-treated ROC A and ROC B with downstream biological treatment, corresponding to reductions of 55% and 62%, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.

    PubMed

    Little, Brian K; Lockhart, PaviElle; Slaten, B L; Mills, G

    2013-05-23

    Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.

  5. H2O2 dynamics in the malaria parasite Plasmodium falciparum

    PubMed Central

    Rahbari, Mahsa; Bogeski, Ivan

    2017-01-01

    Hydrogen peroxide is an important antimicrobial agent but is also crucially involved in redox signaling and pathogen-host cell interactions. As a basis for systematically investigating intracellular H2O2 dynamics and regulation in living malaria parasites, we established the genetically encoded fluorescent H2O2 sensors roGFP2-Orp1 and HyPer-3 in Plasmodium falciparum. Both ratiometric redox probes as well as the pH control SypHer were expressed in the cytosol of blood-stage parasites. Both redox sensors showed reproducible sensitivity towards H2O2 in the lower micromolar range in vitro and in the parasites. Due to the pH sensitivity of HyPer-3, we used parasites expressing roGFP2-Orp1 for evaluation of short-, medium-, and long-term effects of antimalarial drugs on H2O2 levels and detoxification in Plasmodium. None of the quinolines or artemisinins tested had detectable direct effects on the H2O2 homeostasis at pharmacologically relevant concentrations. However, pre-treatment of the cells with antimalarial drugs or heat shock led to a higher tolerance towards exogenous H2O2. The systematic evaluation and comparison of the two genetically encoded cytosolic H2O2 probes in malaria parasites provides a basis for studying parasite-host cell interactions or drug effects with spatio-temporal resolution while preserving cell integrity. PMID:28369083

  6. Hydrothermal and alkaline hydrothermal pretreatments plus anaerobic digestion of sewage sludge for dewatering and biogas production: Bench-scale research and pilot-scale verification.

    PubMed

    Li, Chunxing; Wang, Xingdong; Zhang, Guangyi; Yu, Guangwei; Lin, Jingjiang; Wang, Yin

    2017-06-15

    To test the feasibility and practicability of the process combing hydrothermal pretreatment for dewatering with biogas production for full utilization of sewage sludge, hydrothermal/alkaline hydrothermal pretreatments and in turn anaerobic digestion of the filtrates obtained after dewatering the pretreated sludge were performed at bench- and pilot-scales. The hydrothermal temperature fell within the range of 140 °C-220 °C and the pretreatment time varied from 30 min to 120 min. For the alkaline hydrothermal pretreatment the pH value of the sludge was adjusted to 9.0-11.0 by adding Ca(OH) 2 . The results showed that the dewaterability of the sewage sludge was improved with increasing pretreatment temperature but the impact of the pretreatment time was not significant. The addition of Ca(OH) 2 gave better performance on the subsequent mechanical dewatering of the pretreated sludge compared to pure hydrothermal pretreatment, and the higher the pH value was, the better the dewaterability of the pretreated sludge was. The conditions of 180 °C/30 min and 160 °C/60 min/pH = 10.0 (for hydrothermal and alkaline hydrothermal pretreatments, respectively) resulted in relatively good results in the theoretical energy balance, which were verified in the pilot-scale tests. Based on the data from the pilot tests, the alkaline hydrothermal process realized self-sufficiency in energy at the cost of a proper amount of CaO. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Coupling UV-H2O2 to accelerate dimethyl phthalate (DMP) biodegradation and oxidation.

    PubMed

    Chen, Bin; Song, Jiaxiu; Yang, Lihui; Bai, Qi; Li, Rongjie; Zhang, Yongming; Rittmann, Bruce E

    2015-11-01

    Dimethyl phthalate (DMP), an important industrial raw material, is an endocrine disruptor of concern for human and environmental health. DMP exhibits slow biodegradation, and its coupled treatment by means of advanced oxidation may enhance its biotransformation and mineralization. We evaluated two ways of coupling UV-H2O2 advanced oxidation to biodegradation: sequential coupling and intimate coupling in an internal circulation baffled biofilm reactor (ICBBR). During sequential coupling, UV-H2O2 pretreatment generated carboxylic acids that depressed the pH, and subsequent biodegradation generated phthalic acid; both factors inhibited DMP biodegradation. During intimately coupled UV-H2O2 with biodegradation, carboxylic acids and phthalic acid (PA) did not accumulate, and the biodegradation rate was 13 % faster than with biodegradation alone and 78 % faster than with biodegradation after UV-H2O2 pretreatment. Similarly, DMP oxidation with intimate coupling increased by 5 and 39 %, respectively, compared with biodegradation alone and sequential coupling. The enhancement effects during intimate coupling can be attributed to the rapid catabolism of carboxylic acids, which generated intracellular electron carriers that directly accelerated di-oxygenation of PA and relieved the inhibition effect of PA and low pH. Thus, intimate coupling optimized the impacts of energy input from UV irradiation used together with biodegradation.

  8. Removing polysaccharides-and saccharides-related coloring impurities in alkyl polyglycosides by bleaching with the H2O2/TAED/NaHCO3 system.

    PubMed

    Yanmei, Liu; Jinliang, Tao; Jiao, Sun; Wenyi, Chen

    2014-11-04

    The effect of H2O2/TAED/NaHCO3 system, namely NaHCO3 as alkaline agent with the (tetra acetyl ethylene diamine (TAED)) TAED-activated peroxide system, bleaching of alkyl polyglycosides solution was studied by spectrophotometry. The results showed that the optimal bleaching conditions about H2O2/TAED/NaHCO3 system bleaching of alkyl polyglycosides solution were as follows: molar ratio of TAED to H2O2 was 0.06, addition of H2O2 was 8.6%, addition of NaHCO3 was 3.2%, bleaching temperature of 50-65 °C, addition of MgO was 0.13%, and bleaching time was 8h. If too much amount of NaHCO3 was added to the system and maintained alkaline pH, the bleaching effect would be greatly reduced. Fixing molar ratio of TAED to H2O2 and increasing the amount of H2O2 were beneficial to improve the whiteness of alkyl polyglycosides, but adding too much amount of H2O2 would reduce the transparency. In the TAED-activated peroxide system, NaHCO3 as alkaline agent and buffer agent, could overcome the disadvantage of producing black precipitates when NaOH as alkaline agent. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Molecular identification for epigallocatechin-3-gallate-mediated antioxidant intervention on the H2O2-induced oxidative stress in H9c2 rat cardiomyoblasts.

    PubMed

    Chen, Wei-Cheng; Hsieh, Shih-Rong; Chiu, Chun-Hwei; Hsu, Ban-Dar; Liou, Ying-Ming

    2014-06-09

    Epigallocatechin-3-gallate (EGCG) has been documented for its beneficial effects protecting oxidative stress to cardiac cells. Previously, we have shown the EGCG-mediated cardiac protection by attenuating reactive oxygen species and cytosolic Ca2+ in cardiac cells during oxidative stress and myocardial ischemia. Here, we aimed to seek a deeper elucidation of the molecular anti-oxidative capabilities of EGCG in an H2O2-induced oxidative stress model of myocardial ischemia injury using H9c2 rat cardiomyoblasts. Proteomics analysis was used to determine the differential expression of proteins in H9c2 cells cultured in the conditions of control, 400 μM H2O2 exposure for 30 min with and/or without 10 to 20 μM EGCG pre-treatment. In this model, eight proteins associated with energy metabolism, mitochondrial electron transfer, redox regulation, signal transduction, and RNA binding were identified to take part in EGCG-ameliorating H2O2-induced injury in H9c2 cells. H2O2 exposure increased oxidative stress evidenced by increases in reactive oxygen species and cytosolic Ca2+ overload, increases in glycolytic protein, α-enolase, decreases in antioxidant protein, peroxiredoxin-4, as well as decreases in mitochondrial proteins, including aldehyde dehydrogenase-2, ornithine aminotransferase, and succinate dehydrogenase ubiquinone flavoprotein subunit. All of these effects were reversed by EGCG pre-treatment. In addition, EGCG attenuated the H2O2-induced increases of Type II inositol 3, 4-bisphosphate 4-phosphatase and relieved its subsequent inhibition of the downstream signalling for Akt and glycogen synthase kinase-3β (GSK-3β)/cyclin D1 in H9c2 cells. Pre-treatment with EGCG or GSK-3β inhibitor (SB 216763) significantly improved the H2O2-induced suppression on cell viability, phosphorylation of pAkt (S473) and pGSK-3β (S9), and level of cyclin D1 in cells. Collectively, these findings suggest that EGCG blunts the H2O2-induced oxidative effect on the Akt activity

  10. Molecular identification for epigallocatechin-3-gallate-mediated antioxidant intervention on the H2O2-induced oxidative stress in H9c2 rat cardiomyoblasts

    PubMed Central

    2014-01-01

    Background Epigallocatechin-3-gallate (EGCG) has been documented for its beneficial effects protecting oxidative stress to cardiac cells. Previously, we have shown the EGCG-mediated cardiac protection by attenuating reactive oxygen species and cytosolic Ca2+ in cardiac cells during oxidative stress and myocardial ischemia. Here, we aimed to seek a deeper elucidation of the molecular anti-oxidative capabilities of EGCG in an H2O2-induced oxidative stress model of myocardial ischemia injury using H9c2 rat cardiomyoblasts. Results Proteomics analysis was used to determine the differential expression of proteins in H9c2 cells cultured in the conditions of control, 400 μM H2O2 exposure for 30 min with and/or without 10 to 20 μM EGCG pre-treatment. In this model, eight proteins associated with energy metabolism, mitochondrial electron transfer, redox regulation, signal transduction, and RNA binding were identified to take part in EGCG-ameliorating H2O2-induced injury in H9c2 cells. H2O2 exposure increased oxidative stress evidenced by increases in reactive oxygen species and cytosolic Ca2+ overload, increases in glycolytic protein, α-enolase, decreases in antioxidant protein, peroxiredoxin-4, as well as decreases in mitochondrial proteins, including aldehyde dehydrogenase-2, ornithine aminotransferase, and succinate dehydrogenase ubiquinone flavoprotein subunit. All of these effects were reversed by EGCG pre-treatment. In addition, EGCG attenuated the H2O2-induced increases of Type II inositol 3, 4-bisphosphate 4-phosphatase and relieved its subsequent inhibition of the downstream signalling for Akt and glycogen synthase kinase-3β (GSK-3β)/cyclin D1 in H9c2 cells. Pre-treatment with EGCG or GSK-3β inhibitor (SB 216763) significantly improved the H2O2-induced suppression on cell viability, phosphorylation of pAkt (S473) and pGSK-3β (S9), and level of cyclin D1 in cells. Conclusions Collectively, these findings suggest that EGCG blunts the H2O2-induced oxidative

  11. Formation of iodo-trihalomethanes (I-THMs) during disinfection with chlorine or chloramine: Impact of UV/H2O2 pre-oxidation.

    PubMed

    Zhang, Jie; Liu, Jing; He, Chuan-Shu; Qian, Chen; Mu, Yang

    2018-06-04

    Ultraviolet/hydrogen peroxide (UV/H 2 O 2 ) pre-oxidation has the potential to induce reactions with dissolved organic matter (DOM) and alter the generation of disinfection byproducts (DBPs). This study evaluated the influence of UV/H 2 O 2 pretreatment on the formation of iodo-trihalomethanes (I-THMs) during disinfection with chlorine or chloramine. The changes of precursors, I - and Br - , after UV/H 2 O 2 pretreatment were investigated, and then, the formation and speciation of I-THMs during chlorination or chloramination after pre-oxidation were explored. Additionally, the effects of UV doses and H 2 O 2 concentrations on the formation and speciation of I-THMs were studied. It was found that UV/H 2 O 2 pretreatment could change larger molecular weight (MW) DOM to smaller MW species, which had less aromatic organic compounds and fluorescence substances. Additionally, insignificant transformations of I - and Br - were observed after UV/H 2 O 2 treatment. Compared to direct disinfection, UV/H 2 O 2 pretreatment resulted in 23.0 ± 3.5% reduction in I-THMs formation during post-chlorination while an enhancement was observed during post-chloramination at a UV dose of 460 mJ/cm 2 and 20 mg/L H 2 O 2 . Moreover, total I-THM concentration increased from 43.7 ± 2.4 to 97.6 ± 14.9 nM with the increase of UV doses from 0 to 1400 mJ/cm 2 during the post-chlorination process, while reduced when the UV fluence was >460 mJ/cm 2 during the post-chloramination. Additionally, the generation of I-THMs during both post-chlorination and post-chloramination was positively related to the H 2 O 2 levels from 0 to 20 mg/L in the UV/H 2 O 2 pretreatment. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. Treatment of Salmonella enterica serovar Enteritidis with a sublethal concentration of trisodium phosphate or alkaline pH induces thermotolerance.

    PubMed

    Sampathkumar, Balamurugan; Khachatourians, George G; Korber, Darren R

    2004-08-01

    The responses of Salmonella enterica serovar Enteritidis to a sublethal dose of trisodium phosphate (TSP) and its equivalent alkaline pH made with NaOH were examined. Pretreatment of S. enterica serovar Enteritidis cells with 1.5% TSP or pH 10.0 solutions resulted in a significant increase in thermotolerance, resistance to 2.5% TSP, resistance to high pH, and sensitivity to acid and H(2)O(2). Protein inhibition studies with chloramphenicol revealed that thermotolerance, unlike resistance to high pH, was dependent on de novo protein synthesis. Two-dimensional polyacrylamide gel electrophoresis (PAGE) of total cellular proteins from untreated control cells resolved as many as 232 proteins, of which 22 and 15% were absent in TSP- or alkaline pH-pretreated cells, respectively. More than 50% of the proteins that were either up- or down-regulated by TSP pretreatment were also up- or down-regulated by alkaline pH pretreatment. Sodium dodecyl sulfate-PAGE analysis of detergent-insoluble outer membrane proteins revealed the up-regulation of at least four proteins. Mass spectrometric analysis showed the up-regulated proteins to include those involved in the transport of small hydrophilic molecules across the cytoplasmic membrane and those that act as chaperones and aid in the export of newly synthesized proteins by keeping them in open conformation. Other up-regulated proteins included common housekeeping proteins like those involved in amino acid biosynthesis, nucleotide metabolism, and aminoacyl-tRNA biosynthesis. In addition to the differential expression of proteins following TSP or alkaline pH treatment, changes in membrane fatty acid composition were also observed. Alkaline pH- or TSP-pretreated cells showed a higher saturated and cyclic to unsaturated fatty acid ratio than did the untreated control cells. These results suggest that the cytoplasmic membrane could play a significant role in the induction of thermotolerance and resistance to other stresses following TSP

  13. Osmopriming-induced salt tolerance during seed germination of alfalfa most likely mediates through H2O2 signaling and upregulation of heme oxygenase.

    PubMed

    Amooaghaie, Rayhaneh; Tabatabaie, Fatemeh

    2017-07-01

    The present study showed that osmopriming or pretreatment with low H 2 O 2 doses (2 mM) for 6 h alleviated salt-reduced seed germination. The NADPH oxidase activity was the main source, and superoxide dismutase (SOD) activity might be a secondary source of H 2 O 2 generation during osmopriming or H 2 O 2 pretreatment. Hematin pretreatment similar to osmopriming improved salt-reduced seed germination that was coincident with the enhancement of heme oxygenase (HO) activity. The semi-quantitative RT-PCR confirmed that osmopriming or H 2 O 2 pretreatment was able to upregulate heme oxygenase HO-1 transcription, while the application of N,N-dimethyl thiourea (DMTU as trap of endogenous H 2 O 2 ) and diphenyleneiodonium (DPI as inhibitor of NADPHox) not only blocked the upregulation of HO but also reversed the osmopriming-induced salt attenuation. The addition of CO-saturated aqueous rescued the inhibitory effect of DMTU and DPI on seed germination and α-amylase activity during osmopriming or H 2 O 2 pretreatment, but H 2 O 2 could not reverse the inhibitory effect of ZnPPIX (as HO inhibitor) or Hb (as CO scavenger) that indicates that the CO acts downstream of H 2 O 2 in priming-driven salt acclimation. The antioxidant enzymes and proline synthesis were upregulated in roots of seedlings grown from primed seeds, and these responses were reversed by adding DMTU, ZnPPIX, and Hb during osmopriming. These findings for the first time suggest that H 2 O 2 signaling and upregulation of heme oxygenase play a crucial role in priming-driven salt tolerance.

  14. The H2O2 scavenger ebselen decreases ethanol-induced locomotor stimulation in mice.

    PubMed

    Ledesma, Juan Carlos; Font, Laura; Aragon, Carlos M G

    2012-07-01

    In the brain, the enzyme catalase by reacting with H(2)O(2) forms Compound I (catalase-H(2)O(2) system), which is the main system of central ethanol metabolism to acetaldehyde. Previous research has demonstrated that acetaldehyde derived from central-ethanol metabolism mediates some of the psychopharmacological effects produced by ethanol. Manipulations that modulate central catalase activity or sequester acetaldehyde after ethanol administration modify the stimulant effects induced by ethanol in mice. However, the role of H(2)O(2) in the behavioral effects caused by ethanol has not been clearly addressed. The present study investigated the effects of ebselen, an H(2)O(2) scavenger, on ethanol-induced locomotion. Swiss RjOrl mice were pre-treated with ebselen (0-50mg/kg) intraperitoneally (IP) prior to administration of ethanol (0-3.75g/kg; IP). In another experiment, animals were pre-treated with ebselen (0 or 25mg/kg; IP) before caffeine (15mg/kg; IP), amphetamine (2mg/kg; IP) or cocaine (10mg/kg; IP) administration. Following these treatments, animals were placed in an open field to measure their locomotor activity. Additionally, we evaluated the effect of ebselen on the H(2)O(2)-mediated inactivation of brain catalase activity by 3-amino-1,2,4-triazole (AT). Ebselen selectively prevented ethanol-induced locomotor stimulation without altering the baseline activity or the locomotor stimulating effects caused by caffeine, amphetamine and cocaine. Ebselen reduced the ability of AT to inhibit brain catalase activity. Taken together, these data suggest that a decline in H(2)O(2) levels might result in a reduction of the ethanol locomotor-stimulating effects, indicating a possible role for H(2)O(2) in some of the psychopharmacological effects produced by ethanol. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  15. Comparison of liquid hot water and alkaline pretreatments of giant reed for improved enzymatic digestibility and biogas energy production.

    PubMed

    Jiang, Danping; Ge, Xumeng; Zhang, Quanguo; Li, Yebo

    2016-09-01

    Liquid hot water (LHW) and alkaline pretreatments of giant reed biomass were compared in terms of digestibility, methane production, and cost-benefit efficiency for electricity generation via anaerobic digestion with a combined heat and power system. Compared to LHW pretreatment, alkaline pretreatment retained more of the dry matter in giant reed biomass solids due to less severe conditions. Under their optimal conditions, LHW pretreatment (190°C, 15min) and alkaline pretreatment (20g/L of NaOH, 24h) improved glucose yield from giant reed by more than 2-fold, while only the alkaline pretreatment significantly (p<0.05) increased cumulative methane yield (by 63%) over that of untreated biomass (217L/kgVS). LHW pretreatment obtained negative net electrical energy production due to high energy input. Alkaline pretreatment achieved 27% higher net electrical energy production than that of non-pretreatment (3859kJ/kg initial total solids), but alkaline liquor reuse is needed for improved net benefit. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Alkaline hydrolysis of dimethyl terephthalate in the presence of [LiAl{sub 2}(OH){sub 6}]Cl.2H{sub 2}O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lei Lixu; Zhang Weifeng; Hu Meng

    2006-11-15

    The alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl has been investigated to demonstrate a possible application of anion exchange facility of layered double hydroxides (LDHs) to control chemical reactions. The results show that (i) in the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl, most of the interlayer Cl{sup -} of [LiAl{sub 2}(OH){sub 6}]Cl is quickly replaced by OH{sup -} in the alkaline solution because the LDH host favors OH{sup -} more; (ii) the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl is faster than the reaction ofmore » DMT and [LiAl{sub 2}(OH){sub 6}]OH; (iii) The hydrolysis of DMT in a buffer solution of pH{approx}8 takes longer time to reach equilibrium than the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl. It is believed that the selective anion exchange chemistry of the LDH plays a key role in storage and controlled release of active reactant, that is, OH{sup -}, thus make the hydrolysis proceeds in a controlled way. - Graphical abstract: XRD patterns of the solid products of the alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl at 70 deg. C halted at different time, which shows that [LiAl{sub 2}(OH){sub 6}]Cl turns out to be [LiAl{sub 2}(OH){sub 6}]OH, and [LiAl{sub 2}(OH){sub 6}]{sub 2}TP forms gradually. In this reaction, the alkaline hydrolysis of DMT is controlled by replacement of Cl{sup -} in [LiAl{sub 2}(OH){sub 6}]Cl by OH{sup -}, and subsequent replacement of OH{sup -} in [LiAl{sub 2}(OH){sub 6}]OH by terephthalate anion.« less

  17. Efficient bioconversion of rice straw to ethanol with TiO2/UV pretreatment.

    PubMed

    Kang, Hee-Kyoung; Kim, Doman

    2012-01-01

    Rice straw is a lignocellulosic biomass that constitutes a renewable organic substance and alternative source of energy; however, its structure confounds the liberation of monosaccharides. Pretreating rice straw using a TiO(2)/UV system facilitated its hydrolysis with Accellerase 1000(™), suggesting that hydroxyl radicals (OH·) from the TiO(2)/UV system could degrade lignin and carbohydrates. TiO(2)/UV pretreatment was an essential step for conversion of hemicellulose to xylose; optimal conditions for this conversion were a TiO(2) concentration of 0.1% (w/v) and an irradiation time of 2 h with a UV-C lamp at 254 nm. After enzymatic hydrolysis, the sugar yields from rice straw pretreated with these parameters were 59.8 ± 0.7% of the theoretical for glucose (339 ± 13 mg/g rice straw) and 50.3 ± 2.8% for xylose (64 ± 3 mg/g rice straw). The fermentation of enzymatic hydrolysates containing 10.5 g glucose/L and 3.2 g xylose/L with Pichia stipitis produced 3.9 g ethanol/L with a corresponding yield of 0.39 g/g rice straw. The maximum possible ethanol conversion rate is 76.47%. TiO(2)/UV pretreatment can be performed at room temperature and atmospheric pressure and demonstrates potential in large-scale production of fermentable sugars.

  18. Hydrolysis of alkaline pretreated banana peel

    NASA Astrophysics Data System (ADS)

    Fatmawati, A.; Gunawan, K. Y.; Hadiwijaya, F. A.

    2017-11-01

    Banana peel is one of food wastes that are rich in carbohydrate. This shows its potential as fermentation substrate including bio-ethanol. This paper presented banana peel alkaline pretreatment and enzymatic hydrolysis. The pretreatment was intended to prepare banana peel in order to increase hydrolysis performance. The alkaline pretreatment used 10, 20, and 30% w/v NaOH solution and was done at 60, 70 and 80°C for 1 hour. The hydrolysis reaction was conducted using two commercial cellulose enzymes. The reaction time was varied for 3, 5, and 7 days. The best condition for pretreatment process was one conducted using 30% NaOH solution and at 80°C. This condition resulted in cellulose content of 90.27% and acid insoluble lignin content of 2.88%. Seven-day hydrolysis time had exhibited the highest reducing sugar concentration, which was7.2869 g/L.

  19. A Comparison between Lime and Alkaline Hydrogen Peroxide Pretreatments of Sugarcane Bagasse for Ethanol Production

    NASA Astrophysics Data System (ADS)

    Rabelo, Sarita C.; Filho, Rubens Maciel; Costa, Aline C.

    Pretreatment procedures of sugarcane bagasse with lime (calcium hydroxide) or alkaline hydrogen peroxide were evaluated and compared. Analyses were performed using 2 × 2 × 2 factorial designs, with pretreatment time, temperature, and lime loading and hydrogen peroxide concentration as factors. The responses evaluated were the yield of total reducing sugars (TRS) and glucose released from pretreated bagasse after enzymatic hydrolysis. Experiments were performed using the bagasse as it comes from an alcohol/ sugar factory and bagasse in the size range of 0.248 to 1.397 mm (12-60 mesh). The results show that when hexoses and pentoses are of interest, lime should be the pretreatment agent chosen, as high TRS yields are obtained for nonscreened bagasse using 0.40 g lime/g dry biomass at 70 °C for 36 h. When the product of interest is glucose, the best results were obtained with lime pretreatment of screened bagasse. However, the results for alkaline peroxide and lime pretreatments of nonscreened bagasse are not very different.

  20. A comparison between lime and alkaline hydrogen peroxide pretreatments of sugarcane bagasse for ethanol production.

    PubMed

    Rabelo, Sarita C; Maciel Filho, Rubens; Costa, Aline C

    2008-03-01

    Pretreatment procedures of sugarcane bagasse with lime (calcium hydroxide) or alkaline hydrogen peroxide were evaluated and compared. Analyses were performed using 2 x 2 x 2 factorial designs, with pretreatment time, temperature, and lime loading and hydrogen peroxide concentration as factors. The responses evaluated were the yield of total reducing sugars (TRS) and glucose released from pretreated bagasse after enzymatic hydrolysis. Experiments were performed using the bagasse as it comes from an alcohol/sugar factory and bagasse in the size range of 0.248 to 1.397 mm (12-60 mesh). The results show that when hexoses and pentoses are of interest, lime should be the pretreatment agent chosen, as high TRS yields are obtained for nonscreened bagasse using 0.40 g lime/g dry biomass at 70 degrees C for 36 h. When the product of interest is glucose, the best results were obtained with lime pretreatment of screened bagasse. However, the results for alkaline peroxide and lime pretreatments of nonscreened bagasse are not very different.

  1. Analysis of by-product formation and sugar monomerization in sugarcane bagasse pretreated at pilot plant scale: differences between autohydrolysis, alkaline and acid pretreatment.

    PubMed

    van der Pol, Edwin; Bakker, Rob; van Zeeland, Alniek; Sanchez Garcia, David; Punt, Arjen; Eggink, Gerrit

    2015-04-01

    Sugarcane bagasse is an interesting feedstock for the biobased economy since a large fraction is polymerized sugars. Autohydrolysis, alkaline and acid pretreatment conditions combined with enzyme hydrolysis were used on lignocellulose rich bagasse to acquire monomeric. By-products found after pretreatment included acetic, glycolic and coumaric acid in concentrations up to 40, 21 and 2.5 g/kg dry weight bagasse respectively. Alkaline pretreated material contained up to 45 g/kg bagasse DW of sodium. Acid and autohydrolysis pretreatment results in a furan formation of 14 g/kg and 25 g/kg DW bagasse respectively. Enzyme monomerization efficiencies of pretreated solid material after 72 h were 81% for acid pretreatment, 77% for autohydrolysis and 57% for alkaline pretreatment. Solid material was washed with superheated water to decrease the amount of by-products. Washing decreased organic acid, phenol and furan concentrations in solid material by at least 60%, without a major sugar loss. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Optimization and evaluation of alkaline potassium permanganate pretreatment of corncob.

    PubMed

    Ma, Lijuan; Cui, Youzhi; Cai, Rui; Liu, Xueqiang; Zhang, Cuiying; Xiao, Dongguang

    2015-03-01

    Alkaline potassium permanganate solution (APP) was applied to the pretreatment of corncob with a simple and effective optimization of APP concentration, reaction time, temperature and solid to liquid ratio (SLR). The optimized pretreatment conditions were at 2% (w/v) potassium permanganate with SLR of 1:10 treating for 6h at 50°C. This simple one-step treatment resulted in significant 94.56% of the cellulose and 81.47% of the hemicellulose recoveries and 46.79% of the lignin removal of corncob. The reducing sugar in the hydrolysate from APP-pretreated corncob was 8.39g/L after 12h enzymatic hydrolysis, which was 1.44 and 1.29 folds higher than those from raw and acid pretreated corncobs. Physical characteristics, crystallinity and structure of the pretreated corncob were analyzed and assessed by SEM, XRD and FTIR. The APP pretreatment process was novel and enhanced enzymatic hydrolysis of lignocellulose by affecting composition and structural features. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Preparation and characterization of activated carbon from acorn shell by physical activation with H2O-CO2 in two-step pretreatment.

    PubMed

    Şahin, Ömer; Saka, Cafer

    2013-05-01

    Activated carbons have been prepared by physical activation with H2O-CO2 in two-step pre-treatment including ZnCl2-HCl from acorn shell at 850 °C. The active carbons were characterized by N2 adsorption at 77 K. Adsorption capacity was demonstrated by the iodine numbers. The surface chemical characteristics of activated carbons were determined by FTIR spectroscopic method. The microstructure of the activated carbons prepared was examined by scanning electron microscopy. The maximum BET surface area of the obtained activated carbon was found to be around 1779 m(2)/g. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Comparison of Seven Chemical Pretreatments of Corn Straw for Improving Methane Yield by Anaerobic Digestion

    PubMed Central

    Song, Zilin; GaiheYang; Liu, Xiaofeng; Yan, Zhiying; Yuan, Yuexiang; Liao, Yinzhang

    2014-01-01

    Agriculture straw is considered a renewable resource that has the potential to contribute greatly to bioenergy supplies. Chemical pretreatment prior to anaerobic digestion can increase the anaerobic digestibility of agriculture straw. The present study investigated the effects of seven chemical pretreatments on the composition and methane yield of corn straw to assess their effectiveness of digestibility. Four acid reagents (H2SO4, HCl, H2O2, and CH3COOH) at concentrations of 1%, 2%, 3%, and 4% (w/w) and three alkaline reagents (NaOH, Ca(OH)2, and NH3·H2O) at concentrations of 4%, 6%, 8%, and 10% (w/w) were used for the pretreatments. All pretreatments were effective in the biodegradation of the lignocellulosic straw structure. The straw, pretreated with 3% H2O2 and 8% Ca(OH)2, acquired the highest methane yield of 216.7 and 206.6 mL CH4 g VS −1 in the acid and alkaline pretreatments, which are 115.4% and 105.3% greater than the untreated straw. H2O2 and Ca(OH)2 can be considered as the most favorable pretreatment methods for improving the methane yield of straw because of their effectiveness and low cost. PMID:24695485

  5. Comparison of seven chemical pretreatments of corn straw for improving methane yield by anaerobic digestion.

    PubMed

    Song, Zilin; GaiheYang; Liu, Xiaofeng; Yan, Zhiying; Yuan, Yuexiang; Liao, Yinzhang

    2014-01-01

    Agriculture straw is considered a renewable resource that has the potential to contribute greatly to bioenergy supplies. Chemical pretreatment prior to anaerobic digestion can increase the anaerobic digestibility of agriculture straw. The present study investigated the effects of seven chemical pretreatments on the composition and methane yield of corn straw to assess their effectiveness of digestibility. Four acid reagents (H2SO4, HCl, H2O2, and CH3COOH) at concentrations of 1%, 2%, 3%, and 4% (w/w) and three alkaline reagents (NaOH, Ca(OH)2, and NH3·H2O) at concentrations of 4%, 6%, 8%, and 10% (w/w) were used for the pretreatments. All pretreatments were effective in the biodegradation of the lignocellulosic straw structure. The straw, pretreated with 3% H2O2 and 8% Ca(OH)2, acquired the highest methane yield of 216.7 and 206.6 mL CH4 g VS(-1) in the acid and alkaline pretreatments, which are 115.4% and 105.3% greater than the untreated straw. H2O2 and Ca(OH)2 can be considered as the most favorable pretreatment methods for improving the methane yield of straw because of their effectiveness and low cost.

  6. Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

    NASA Astrophysics Data System (ADS)

    Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

    1996-11-01

    The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

  7. Integrated experimental and technoeconomic evaluation of two-stage Cu-catalyzed alkaline–oxidative pretreatment of hybrid poplar

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bhalla, Aditya; Fasahati, Peyman; Particka, Chrislyn A.

    When applied to recalcitrant lignocellulosic feedstocks, multi-stage pretreatments can provide more processing flexibility to optimize or balance process outcomes such as increasing delignification, preserving hemicellulose, and maximizing enzymatic hydrolysis yields. We previously reported that adding an alkaline pre-extraction step to a copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in improved sugar yields, but the process still utilized relatively high chemical inputs (catalyst and H 2O 2) and enzyme loadings. We hypothesized that by increasing the temperature of the alkaline pre-extraction step in water or ethanol, we could reduce the inputs required during Cu-AHP pretreatment and enzymatic hydrolysis without significantmore » loss in sugar yield. We also performed technoeconomic analysis to determine if ethanol or water was the more cost-effective solvent during alkaline pre-extraction and if the expense associated with increasing the temperature was economically justified. After Cu-AHP pretreatment of 120 °C NaOH-H 2O pre-extracted and 120 °C NaOH-EtOH pre-extracted biomass, approximately 1.4-fold more total lignin was solubilized (78% and 74%, respectively) compared to the 30 °C NaOH-H 2O pre-extraction (55%) carried out in a previous study. Consequently, increasing the temperature of the alkaline pre-extraction step to 120 °C in both ethanol and water allowed us to decrease bipyridine and H 2O 2 during Cu-AHP and enzymes during hydrolysis with only a small reduction in sugar yields compared to 30 °C alkaline pre-extraction. Technoeconomic analysis indicated that 120 °C NaOH-H 2O pre-extraction has the lowest installed ($246 million) and raw material (175 million) costs compared to the other process configurations. We found that by increasing the temperature of the alkaline pre-extraction step, we could successfully lower the inputs for pretreatment and enzymatic hydrolysis. Based on sugar yields as well as

  8. Integrated experimental and technoeconomic evaluation of two-stage Cu-catalyzed alkaline–oxidative pretreatment of hybrid poplar

    DOE PAGES

    Bhalla, Aditya; Fasahati, Peyman; Particka, Chrislyn A.; ...

    2018-05-17

    When applied to recalcitrant lignocellulosic feedstocks, multi-stage pretreatments can provide more processing flexibility to optimize or balance process outcomes such as increasing delignification, preserving hemicellulose, and maximizing enzymatic hydrolysis yields. We previously reported that adding an alkaline pre-extraction step to a copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in improved sugar yields, but the process still utilized relatively high chemical inputs (catalyst and H 2O 2) and enzyme loadings. We hypothesized that by increasing the temperature of the alkaline pre-extraction step in water or ethanol, we could reduce the inputs required during Cu-AHP pretreatment and enzymatic hydrolysis without significantmore » loss in sugar yield. We also performed technoeconomic analysis to determine if ethanol or water was the more cost-effective solvent during alkaline pre-extraction and if the expense associated with increasing the temperature was economically justified. After Cu-AHP pretreatment of 120 °C NaOH-H 2O pre-extracted and 120 °C NaOH-EtOH pre-extracted biomass, approximately 1.4-fold more total lignin was solubilized (78% and 74%, respectively) compared to the 30 °C NaOH-H 2O pre-extraction (55%) carried out in a previous study. Consequently, increasing the temperature of the alkaline pre-extraction step to 120 °C in both ethanol and water allowed us to decrease bipyridine and H 2O 2 during Cu-AHP and enzymes during hydrolysis with only a small reduction in sugar yields compared to 30 °C alkaline pre-extraction. Technoeconomic analysis indicated that 120 °C NaOH-H 2O pre-extraction has the lowest installed ($246 million) and raw material (175 million) costs compared to the other process configurations. We found that by increasing the temperature of the alkaline pre-extraction step, we could successfully lower the inputs for pretreatment and enzymatic hydrolysis. Based on sugar yields as well as

  9. Protective effect of pomegranate seed oil against H2O2 -induced oxidative stress in cardiomyocytes

    PubMed Central

    Bihamta, Mehdi; Hosseini, Azar; Ghorbani, Ahmad; Boroushaki, Mohammad Taher

    2017-01-01

    Objective: It has been well documented that oxidative stress is involved in the pathogenesis of cardiac diseases. Previous studies have shown that pomegranate seed oil (PSO) has antioxidant properties. This study was designed to investigate probable protective effects of PSO against hydrogen peroxide (H2O2)-induced damage in H9c2 cardiomyocytes. Materials and Methods: The cells were pretreated 24 hr with PSO 1 hr before exposure to 200 µM H2O2. Cell viability was evaluated using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium (MTT) assay. The level of reactive oxygen species (ROS) and lipid peroxidation were measured by fluorimetric methods. Results: H2O2 significantly decreased cell viability which was accompanied by an increase in ROS production and lipid peroxidation and a decline in superoxide dismutase activity. Pretreatment with PSO increased viability of cardiomyocytes and decrease the elevated ROS production and lipid peroxidation. Also, PSO was able to restore superoxide dismutase activity. Conclusion: PSO has protective effect against oxidative stress-induced damage in cardiomyocytes and can be considered as a natural cardioprotective agent to prevent cardiovascular diseases. PMID:28265546

  10. Baicalin Ameliorates H2O2 Induced Cytotoxicity in HK-2 Cells through the Inhibition of ER Stress and the Activation of Nrf2 Signaling

    PubMed Central

    Lin, Miao; Li, Long; Zhang, Yi; Zheng, Long; Xu, Ming; Rong, Ruiming; Zhu, Tongyu

    2014-01-01

    Renal ischemia-reperfusion injury plays a key role in renal transplantation and greatly affects the outcome of allograft. Our previous study proved that Baicalin, a flavonoid glycoside isolated from Scutellaria baicalensis, protects kidney from ischemia-reperfusion injury. This study aimed to study the underlying mechanism in vitro. Human renal proximal tubular epithelial cell line HK-2 cells were stimulated by H2O2 with and without Baicalin pretreatment. The cell viability, apoptosis and oxidative stress level were measured. The expression of endoplasmic reticulum (ER) stress hallmarks, such as binding immunoglobulin protein (BiP) and C/EBP homologous protein (CHOP), were analyzed by western blot and real-time PCR. NF-E2-related factor 2 (Nrf2) expression was also measured. In the H2O2 group, cell viability decreased and cell apoptosis increased. Reactive Oxygen Species (ROS) and Glutathione/Oxidized Glutathione (GSH/GSSG) analysis revealed increased oxidative stress. ER stress and Nrf2 signaling also increased. Baicalin pretreatment ameliorated H2O2-induced cytotoxicity, reduced oxidative stress and ER stress and further activated the anti-oxidative Nrf2 signaling pathway. The inducer of ER stress and the inhibitor of Nrf2 abrogated the protective effects, while the inhibitor of ER stress and the inducer of Nrf2 did not improve the outcome. This study revealed that Baicalin pretreatment serves a protective role against H2O2-induced cytotoxicity in HK-2 cells, where the inhibition of ER stress and the activation of downstream Nrf2 signaling are involved. PMID:25029541

  11. Comparative study of alkaline hydrogen peroxide and organosolv pretreatments of sugarcane bagasse to improve the overall sugar yield.

    PubMed

    Yu, Hailong; You, Yanzhi; Lei, Fuhou; Liu, Zuguang; Zhang, Weiming; Jiang, Jianxin

    2015-01-01

    Green liquor (GL) combined with H2O2 (GL-H2O2) and green liquor (GL) combined with ethanol (GL-ethanol) were chosen for treating sugarcane bagasse. Results showed that the glucose yield (calculated from the glucose content as a percentage of the theoretical glucose available in the substrates)of sugarcane bagasse from GL-ethanol pretreatment (97.7%) was higher than that from GL-H2O2 pretreatment (41.7%) after 72h hydrolysis with 18 filter paper unit (FPU)/g-cellulose for cellulase, 27,175 cellobiase units (CBU)/g-cellulose for β-glucosidase. Furthermore, about 94.1% of xylan was converted to xylose after GL-ethanol pretreatment without additional xylanase, while the xylose yield was only 29.2% after GL-H2O2 pretreatment. Scanning electron microscopy showed that GL-ethanol pretreatment could break up the fiber severely. Moreover, GL-ethanol pretreated substrate was more accessible to cellulase and more hydrophilic than that of GL-H2O2 pretreated. Therefore, GL-ethanol pretreatment is a promising method for improving the overall sugar (glucose and xylan) yield of sugarcane bagasse. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Removal of petroleum hydrocarbons from contaminated groundwater by the combined technique of adsorption onto perlite followed by the O3/H2O2 process.

    PubMed

    Moussavi, Gholamreza; Bagheri, Amir

    2012-09-01

    Groundwater contaminated with petroleum hydrocarbons was treated using a combined system of adsorption onto powdered expanded perlite (PEP) followed by the O3/H2O2 process. The pretreatment investigations indicated a high capacity for PEP to remove petroleum hydrocarbons from the contaminated water. An experimental total petroleum hydrocarbon (TPH) adsorption capacity of 275 mg/g PEP was obtained at the natural pH of water. The experimental data fit best with the Freundlich isotherm model and pseudo-second-order adsorption model. The second phase of the experiment evaluated the performance of the O3/H2O2 process in the removal of residual TPH from pretreated water and compared the results with that of raw water. The O3/H202 process attained a maximum TPH removal rate for the pretreated water after 70 min, when 93% of the residual TPH in the effluent of the adsorption system was removed. Overall, the combination of adsorption onto PEP for 100 min and the subsequent treatment with the O3/H2O2 process for 70min eliminated over 99% of the TPH of highly petroleum-contaminated groundwater, with initial values of 162 mg/L. Therefore, we can conclude that the developed treatment system is an appropriate method of remediation for petroleum-contaminated waters.

  13. Scale-up and integration of alkaline hydrogen peroxide pretreatment, enzymatic hydrolysis, and ethanolic fermentation.

    PubMed

    Banerjee, Goutami; Car, Suzana; Liu, Tongjun; Williams, Daniel L; Meza, Sarynna López; Walton, Jonathan D; Hodge, David B

    2012-04-01

    Alkaline hydrogen peroxide (AHP) has several attractive features as a pretreatment in the lignocellulosic biomass-to-ethanol pipeline. Here, the feasibility of scaling-up the AHP process and integrating it with enzymatic hydrolysis and fermentation was studied. Corn stover (1 kg) was subjected to AHP pretreatment, hydrolyzed enzymatically, and the resulting sugars fermented to ethanol. The AHP pretreatment was performed at 0.125 g H(2) O(2) /g biomass, 22°C, and atmospheric pressure for 48 h with periodic pH readjustment. The enzymatic hydrolysis was performed in the same reactor following pH neutralization of the biomass slurry and without washing. After 48 h, glucose and xylose yields were 75% and 71% of the theoretical maximum. Sterility was maintained during pretreatment and enzymatic hydrolysis without the use of antibiotics. During fermentation using a glucose- and xylose-utilizing strain of Saccharomyces cerevisiae, all of the Glc and 67% of the Xyl were consumed in 120 h. The final ethanol titer was 13.7 g/L. Treatment of the enzymatic hydrolysate with activated carbon prior to fermentation had little effect on Glc fermentation but markedly improved utilization of Xyl, presumably due to the removal of soluble aromatic inhibitors. The results indicate that AHP is readily scalable and can be integrated with enzyme hydrolysis and fermentation. Compared to other leading pretreatments for lignocellulosic biomass, AHP has potential advantages with regard to capital costs, process simplicity, feedstock handling, and compatibility with enzymatic deconstruction and fermentation. Biotechnol. Bioeng. 2012; 109:922-931. © 2011 Wiley Periodicals, Inc. Copyright © 2011 Wiley Periodicals, Inc.

  14. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    NASA Astrophysics Data System (ADS)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  15. Effect of alkaline microwaving pretreatment on anaerobic digestion and biogas production of swine manure.

    PubMed

    Yu, Tao; Deng, Yihuan; Liu, Hongyu; Yang, Chunping; Wu, Bingwen; Zeng, Guangming; Lu, Li; Nishimura, Fumitake

    2017-05-10

    Microwave assisted with alkaline (MW-A) condition was applied in the pretreatment of swine manure, and the effect of the pretreatment on anaerobic treatment and biogas production was evaluated in this study. The two main microwaving (MW) parameters, microwaving power and reaction time, were optimized for the pretreatment. Response surface methodology (RSM) was used to investigate the effect of alkaline microwaving process for manure pretreatment at various values of pH and energy input. Results showed that the manure disintegration degree was maximized of 63.91% at energy input of 54 J/g and pH of 12.0, and variance analysis indicated that pH value played a more important role in the pretreatment than in energy input. Anaerobic digestion results demonstrated that MW-A pretreatment not only significantly increased cumulative biogas production, but also shortened the duration for a stable biogas production rate. Therefore, the alkaline microwaving pretreatment could become an alternative process for effective treatment of swine manure.

  16. Vigrishinite, Zn2Ti4 - x Si4O14(OH,H2O,□)8, a new mineral from the Lovozero alkaline complex, Kola Peninsula, Russia

    NASA Astrophysics Data System (ADS)

    Pekov, I. V.; Britvin, S. N.; Zubkova, N. V.; Chukanov, N. V.; Bryzgalov, I. A.; Lykova, I. S.; Belakovskiy, D. I.; Pushcharovsky, D. Yu.

    2013-12-01

    A new mineral vigrishinite, epistolite-group member and first layer titanosilicate with species-defining Zn, was found at Mt. Malyi Punkaruaiv, in the Lovozero alkaline complex, Kola Peninsula, Russia. It occurs in a hydrothermally altered peralkaline pegmatite and is associated with microcline, ussingite, aegirine, analcime, gmelinite-Na, and chabazite-Ca. Vigrishinite forms rectangular or irregularly shaped lamellae up to 0.05 × 2 × 3 cm flattened on [001]. They are typically slightly split and show blocky character. The mineral is translucent to transparent and pale pink, yellowish-pinkish or colorless. The luster is vitreous. The Mohs' hardness is 2.5-3. Vigrishinite is brittle. Cleavage is {001} perfect. D meas = 3.03(2), D calc = 2.97 g/cm3. The mineral is optically biaxial (-), α = 1.755(5), β = 1.82(1), γ = 1.835(8), 2 V meas = 45(10)°, 2 V calc = 50°. IR spectrum is given. The chemical composition (wt %; average of 9 point analyses, H2O is determined by modified Penfield method) is as follows: 0.98 Na2O, 0.30 K2O, 0.56 CaO, 0.05 SrO, 0.44 BaO, 0.36 MgO, 2.09 MnO, 14.39 ZnO, 2.00 Fe2O3, 0.36 Al2O3, 32.29 SiO2, 29.14 TiO2, 2.08 ZrO2, 7.34 Nb2O5, 0.46 F, 9.1 H2O, -0.19 O=F2, total is 101.75. The empirical formula calculated on the basis of Si + Al = 4 is: H7.42(Zn1.30Na0.23Mn0.22Ca0.07Mg0.07K0.05Ba0.02)Σ1.96(Ti2.68Nb0.41Fe{0.18/3+}Zr0.12)Σ3.39(Si3.95Al0.05)Σ4 20.31F0.18. The simplified formula is: Zn2Ti4- x Si4O14(OH,H2O,□)8 ( x < 1). Vigrishinite is triclinic, space group P , a = 8.743(9), b = 8.698(9), c = 11.581(11)Å, α = 91.54(8)°, β = 98.29(8)°, γ = 105.65(8)°, V = 837.2(1.5) Å3, Z = 2. The strongest reflections in the X-ray powder pattern ( d, Å, - I[ hkl]) are: 11.7-67[001], 8.27-50[100], 6.94-43[01, 10], 5.73-54[11, 002], 4.17-65[020, 2, 200], and 2.861-100[30, 22, 004, 11]. The crystal structure model was obtained on a single crystal, R = 0.171. Vigrishinite and murmanite are close in the structure of the TiSiO motif, but

  17. Decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H2O2 and UV/TiO2 oxidation processes.

    PubMed

    Yan, Yingjie; Liao, Qi-Nan; Ji, Feng; Wang, Wei; Yuan, Shoujun; Hu, Zhen-Hu

    2017-02-01

    3,5-Dinitrobenzamide has been widely used as a feed additive to control coccidiosis in poultry, and part of the added 3,5-dinitrobenzamide is excreted into wastewater and surface water. The removal of 3,5-dinitrobenzamide from wastewater and surface water has not been reported in previous studies. Highly reactive hydroxyl radicals from UV/hydrogen peroxide (H 2 O 2 ) and UV/titanium dioxide (TiO 2 ) advanced oxidation processes (AOPs) can decompose organic contaminants efficiently. In this study, the decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H 2 O 2 and UV/TiO 2 oxidation processes was investigated. The decomposition of 3,5-dinitrobenzamide fits well with a fluence-based pseudo-first-order kinetics model. The decomposition in both two oxidation processes was affected by solution pH, and was inhibited under alkaline conditions. Inorganic anions such as NO 3 - , Cl - , SO 4 2- , HCO 3 - , and CO 3 2- inhibited the degradation of 3,5-dinitrobenzamide during the UV/H 2 O 2 and UV/TiO 2 oxidation processes. After complete decomposition in both oxidation processes, approximately 50% of 3,5-dinitrobenzamide was decomposed into organic intermediates, and the rest was mineralized to CO 2 , H 2 O, and other inorganic anions. Ions such as NH 4 + , NO 3 - , and NO 2 - were released into aqueous solution during the degradation. The primary decomposition products of 3,5-dinitrobenzamide were identified using time-of-flight mass spectrometry (LCMS-IT-TOF). Based on these products and ions release, a possible decomposition pathway of 3,5-dinitrobenzamide in both UV/H 2 O 2 and UV/TiO 2 processes was proposed.

  18. Formation and removal of genotoxic activity during UV/H(2)O(2)-GAC treatment of drinking water.

    PubMed

    Heringa, M B; Harmsen, D J H; Beerendonk, E F; Reus, A A; Krul, C A M; Metz, D H; Ijpelaar, G F

    2011-01-01

    The objective of this study was to determine the genotoxic activity of water after UV/H(2)O(2) oxidation and GAC filtration. Pre-treated surface water from three locations was treated with UV/H(2)O(2) with medium pressure (MP) lamps and passed through granulated activated carbon (GAC). Samples taken before and after each treatment step were extracted and concentrated by solid phase extraction (SPE) and analyzed for genotoxicity using the Comet assay with HepG2 cells and the Ames II assay. The Comet assay showed no genotoxic response in any of the samples. In the Ames II, no genotoxic response was obtained with the TAMix (a mix of six strains), but the TA98 strain showed an increase in genotoxic activity after MP-UV/H(2)O(2) for all three locations. GAC post treatment effectively reduced the activities to control levels at two of the three locations and to below the level of the pre-treated water at one site. The results indicate that UV/H(2)O(2) treatment may lead to the formation of genotoxic by-products, which can be removed by subsequent GAC filtration. Copyright © 2010 Elsevier Ltd. All rights reserved.

  19. New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

    NASA Astrophysics Data System (ADS)

    Weng, Sheng-Feng; Wang, Yun-Hsin; Lee, Chi-Shen

    2012-04-01

    Two novel materials, [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La(1a), Ce(1b)) and [Ce2(C2O4)(C6H6O7)2] . 4H2O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1¯ (No. 2); compound 2 crystallized in monoclinic space group P21/c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of CuII ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d1 excited state and two levels of the 4f1 ground state (2F5/2 and 2F7/2). Compounds 1b and 2 containing CeIII ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers.

  20. Enhancement of Pt/SnO2 Catalysts by Addition of H2O

    NASA Technical Reports Server (NTRS)

    Schryer, David R.; Sidney, Barry D.; Van Norman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Upchurch, Billy T.

    1990-01-01

    Water vapor in pretreatment gas restores essential hydroxyl groups. Platinum on tin oxide (Pt/SnO2) is good catalyst for oxidation of carbon monoxide (CO) at temperatures from about 25 degrees C to 100 degress C. Activity of Pt/SnO2 for CO oxidation significantly enhanced by pretreating it at approximately 225 degrees C with reducing gas such as CO. Technique useful in manufacture of high-power CO2 lasers for industrial and scientific uses.

  1. Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

    NASA Astrophysics Data System (ADS)

    Roggensack, K.; Allison, C. M.; Clarke, A. B.

    2017-12-01

    A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that

  2. Effect of mild-temperature H2O2 oxidation on solubilization and anaerobic digestion of waste activated sludge.

    PubMed

    Junga, Heejung; Kim, Jaai; Lee, Seungyong; Lee, Changsoo

    2014-08-01

    Efficient sludge management is among the most challenging issues in wastewater treatment today, and anaerobic digestion is regarded as a viable solution. Mild-temperature H202 oxidation was examined for enhanced solubilization and biogas production of waste activated sludge (WAS). The effects of pretreatment factors (i.e. temperature and H202 concentration) on the degree of WAS disintegration (DD) and biogas yield (BY) were assessed by response surface analysis within the design space of 60-90 degrees C and 0-200mM H202. Significant sludge disintegration (up to 23.0% DD) and visibly enhanced BY (up to 26.9%) were shown in the pretreatment trials. Two response surface models to describe how DD and BY respond to changes in the pretreatment conditions were successfully constructed (R2 > 0.95, p < 0.05). The models showed totally different response surface shapes, indicating the DD and BY were influenced by pretreatment conditions in very different ways. DD was dominantly affected by temperature and showed higher model responses at the high-temperature region, while the BY response peaked in the low-temperature and mid-level H2O2 region. This observation implies that the enhanced solubilization of WAS was not directly translated into an increase in biogas production. Our results showed that WAS can be efficiently disintegrated by H202 oxidation under mild-temperature conditions for enhanced anaerobic digestibility. Within the explored region of pretreatment conditions, the maximum BY was estimated to be 82.1 mL/gCODadded (32.8% greater than the untreated control) at (60.0 degrees C, 74.2 mM H2O2).

  3. A polysaccharide of Dendrobium officinale ameliorates H2O2-induced apoptosis in H9c2 cardiomyocytes via PI3K/AKT and MAPK pathways.

    PubMed

    Zhang, Jing-Yi; Guo, Ying; Si, Jin-Ping; Sun, Xiao-Bo; Sun, Gui-Bo; Liu, Jing-Jing

    2017-11-01

    Dendrobium officinale is one valuable traditional Chinese medicine, which has skyscraping medicinal value. Polysaccharide is the main active ingredient in D. officinale; its antioxidant activity is a hot research topic nowadays. Oxidative stress plays an important role in the pathological progress of a variety of cardiovascular disease, as one of key factors of cardiomyocyte apoptosis. This research adopts a model of H 2 O 2 induction-H9c2 cardiomyocytes apoptosis, aiming to study the effect of Dendrobium officinale Polysaccharide (DOP-GY) for cardiomyocyte apoptosis caused by oxidative stress and its possible mechanism. Our results showed that pretreatment of DOP-GY (low dose: 6.25μg/mL, medium dose: 12.5μg/mL, high dose: 25μg/mL) followed by a 2h incubation with 200μM H 2 O 2 elevated the survival rate, cutted the LDH leakage, reduced lipid peroxidation damage, improved the activity of the endogenous antioxidant enzymes. In addition, the pretreatment of DOP-GY significantly inhibited the production of ROS, declined of the mitochondrial membrane potential, down-regulated pro-apoptosis protein and up-regulated anti-apoptosis protein. The protective effect was correlated with the PI3K/Akt and MAPK signal pathway. Collectively, these observations suggest that DOY-GY has the potential to exert cardioprotective effects against H 2 O 2 -induced H9c2 cardiomyocyte apoptosis. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Effect of hydrogen peroxide pretreatment on the structural features and the enzymatic hydrolysis of rice straw.

    PubMed

    Wei, C J; Cheng, C Y

    1985-10-01

    Assessment was made to evaluate the effect of hydrogen peroxide pretreatment on the change of the structural features and the enzymatic hydrolysis of rice straw. Changes in the lignin content, weight loss, accessibility for Cadoxen, water holding capacity, and crystallinity of straw were measured during pretreatment to express the modification of the lignocellulosic structure of straw. The rates and the extents of enzymatic hydrolysis, cellulase adsorption, and cellobiose accumulation in the initial stage of hydrolysis were determined to study the pretreatment effect on hydrolysis. Pretreatment at 60 degrees C for 5 h in a solution with 1% (w/w) H(2)O(2) and NaOH resulted in 60% delignification, 40% weight loss, a fivefold increase in the accessibility for Cadoxen, an one times increase in the water-holding capacity, and only a slight decrease in crystallinity as compared with that of the untreated straw. Improvement on the pretreatment effect could be made by increasing the initial alkalinity and the pretreatment temperature of hydrogen peroxide solution. A saturated improvement on the structural features was found when the weight ratio of hydrogen peroxide to straw was above 0.25 g H(2)O(2)/g straw in an alkaline H(2)O(2) solution with 1% (w/w) NaOH at 32 degrees C. The initial rates and extents of hydrolysis, cellulase adsorption, and cellobiose accumulation in hydrolysis were enhanced in accordance with the improved structural features of straw pretreated. A four times increase in the extent of the enzymatic hydrolysis of straw for 24 h was attributed to the alkaline hydrogen peroxide pretreatment.

  5. Comparative evaluation of acid and alkaline sulfite pretreatments for enzymatic saccharification of bagasses from three different sugarcane hybrids.

    PubMed

    Monte, Joseana R; Laurito-Friend, Debora F; Ferraz, André; Milagres, Adriane M F

    2018-04-26

    Sugarcane bagasses from three experimental sugarcane hybrids and a mill-reference sample were used to compare the efficiency and mode of action of acid and alkaline sulfite pretreatment processes. Varied chemical loads and reaction temperatures were used to prepare samples with distinguished characteristics regarding xylan and lignin removals, as well as sulfonation levels of residual lignins. The pretreatment with low sulfite loads (5%) under acidic conditions (pH 2) provided maximum glucose yield of 70% during enzymatic hydrolysis with cellulases (10 FPU/g) and β-glucosidases (20 UI/g bagasse). In this case, glucan enzymatic conversion from pretreated materials was mostly associated with extensive xylan removal (70-100%) and partial delignification occurred during the pretreatment. The use of low sulfite loads under acidic conditions required pretreatment temperatures of 160°C. In contrast, at a lower pretreatment temperature (120°C), alkaline sulfite process achieved similar glucan digestibility, but required a higher sulfite load (7.5%). Residual xylans from acid pretreated materials were almost completely hydrolysed by commercial enzymes, contrasting with relatively lower xylan to xylose conversions observed in alkaline pretreated samples. Efficient xylan removal during acid sulfite pretreatment and also during enzymatic digestion can be useful to enhance glucan accessibility and digestibility by cellulases. Alkaline sulfite process also provided substrates with high glucan digestibility, mainly associated with delignification and sulfonation of residual lignins. The results demonstrate that temperature, pH and sulfite can be combined for reducing lignocellulose recalcitrance and achieve similar glucan conversion rates in the alkaline and acid sulfite pretreated bagasses. This article is protected by copyright. All rights reserved. © 2018 American Institute of Chemical Engineers.

  6. A comparison between lime and alkaline hydrogen peroxide pretreatments of sugarcane bagasse for ethanol production.

    PubMed

    Rabelo, Sarita C; Filho, Rubens Maciel; Costa, Aline C

    2008-01-01

    Pretreatment procedures of sugarcane bagasse with lime (calcium hydroxide) or alkaline hydrogen peroxide were evaluated and compared. Analyses were performed using 2(3) factorial designs, with pretreatment time, temperature, and lime loading and hydrogen peroxide concentration as factors. The responses evaluated were the yield of total reducing sugars (TRS) and glucose released from pretreated bagasse after enzymatic hydrolysis. Experiments were performed using the bagasse, as it comes from an alcohol/sugar factory and bagasse, in the size, range from 0.248 to 1.397 mm (12-60 mesh). The results show that, when hexoses and pentoses are of interest, lime should be the pretreatment agent chosen, as high TRS yields are obtained for non-screened bagasse using 0.40 g lime/g dry biomass at 70 degrees C for 36 h. When the product of interest is glucose, the best results were obtained with lime pretreatment of screened bagasse. However, the results for alkaline peroxide and lime pretreatments of non-screened bagasse are not very different.

  7. Neuroprotective and antioxidant activities of bamboo salt soy sauce against H2O2-induced oxidative stress in rat cortical neurons.

    PubMed

    Jeong, Jong Hee; Noh, Min-Young; Choi, Jae-Hyeok; Lee, Haiwon; Kim, Seung Hyun

    2016-04-01

    Bamboo salt (BS) and soy sauce (SS) are traditional foods in Asia, which contain antioxidants that have cytoprotective effects on the body. The majority of SS products contain high levels of common salt, consumption of which has been associated with numerous detrimental effects on the body. However, BS may be considered a healthier substitute to common salt. The present study hypothesized that SS made from BS, known as bamboo salt soy sauce (BSSS), may possess enhanced cytoprotective properties; this was evaluated using a hydrogen peroxide (H 2 O 2 )-induced neuronal cell death rat model. Rat neuronal cells were pretreated with various concentrations (0.001, 0.01, 0.1, 1 and 10%) of BSSS, traditional soy sauce (TRSS) and brewed soy sauce (BRSS), and were subsequently exposed to H 2 O 2 (100 µM). The viability of neuronal cells, and the occurrence of DNA fragmentation, was subsequently examined. Pretreatment of neuronal cells with TRSS and BRSS reduced cell viability in a concentration-dependent manner, whereas neuronal cells pretreated with BSSS exhibited increased cell viability, as compared with non-treated neuronal cells. Furthermore, neuronal cells pretreated with 0.01% BSSS exhibited the greatest increase in viability. Exposure of neuronal cells to H 2 O 2 significantly increased the levels of reactive oxygen species (ROS), B-cell lymphoma 2-associated X protein, poly (ADP-ribose), cleaved poly (ADP-ribose) polymerase, cytochrome c , apoptosis-inducing factor, cleaved caspase-9 and cleaved caspase-3, in all cases. Pretreatment of neuronal cells with BSSS significantly reduced the levels of ROS generated by H 2 O 2 , and increased the levels of phosphorylated AKT and phosphorylated glycogen synthase kinase-3β. Furthermore, the observed effects of BSSS could be blocked by administration of 10 µM LY294002, a phosphatidylinositol 3-kinase inhibitor. The results of the present study suggested that BSSS may exert positive neuroprotective effects against H 2 O 2

  8. Saccharification of microalgae biomass obtained from wastewater treatment by enzymatic hydrolysis. Effect of alkaline-peroxide pretreatment.

    PubMed

    Martín Juárez, Judit; Lorenzo Hernando, Ana; Muñoz Torre, Raúl; Blanco Lanza, Saúl; Bolado Rodríguez, Silvia

    2016-10-01

    An enzymatic method for the carbohydrate hydrolysis of different microalgae biomass cultivated in domestic (DWB) and pig manure (PMWB) wastewaters, at different storage conditions (fresh, freeze-dried and reconstituted), was evaluated. The DWB provided sugars yields between 40 and 63%, although low xylose yields (< 23.5%). Approximately 2% of this biomass was converted to byproducts as succinic, acetic and formic acids. For PMWB, a high fraction of the sugars (up to 87%) was extracted, but mainly converted into acetic, butyric and formic acids, which was attributed to the bacterial action. In addition, the performance of an alkaline-peroxide pretreatment, conducted for 1h, 50°C and H2O2 concentrations from 1 to 7.5% (w/w), was essayed. The hydrolysis of pretreated microalgae supported a wide range of sugars extraction for DWB (55-90%), and 100% for PMWB. Nevertheless, a large fraction of these sugars (∼30% for DWB and 100% for PMWB) was transformed to byproducts. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Photocatalytic pretreatment of oily wastewater from the restaurant by a vacuum ultraviolet/TiO2 system.

    PubMed

    Kang, Jian-xiong; Lu, Lu; Zhan, Wei; Li, Bo; Li, Dao-sheng; Ren, Yong-zheng; Liu, Dong-qi

    2011-02-15

    The present study aims at investigating the performance of a vacuum ultraviolet (VUV, 185 nm) and TiO(2) oxidation system for the pretreatment of oily wastewater from restaurant. The influence of irradiation time, pH, dissolved oxygen (DO), the dosage of TiO(2) and the initial chemical oxygen demand (COD) concentration on COD removal efficiency was ascertained and optimum process conditions for stable and effective operation were determined. Under the optimum conditions of irradiation 10 min, initial COD 3981 mg/L, TiO(2) 150 mg/L, pH 7.0 and flow rate of air 40 L/h, the process of VUV and TiO(2)/VUV achieved removal efficiencies of COD, BOD(5) and oil as 50±3%, 37±2%, 86±3%, and 63±3%, 43±2%, 70±3%, respectively. The biodegradability factor f(B) of the wastewater was determined as 1.56 which indicated that the VUV/TiO(2) process improved the biodegradability of the oily wastewater significantly. Results clearly indicate that VUV/TiO(2) photolysis tends to destruct parts of COD, BOD(5), and ammonia, as well as enhances the biodegradability of the oily wastewater simultaneously. Thus, this technique could be used as a pretreatment step for conventional biological treatment of oily wastewater. Copyright © 2010 Elsevier B.V. All rights reserved.

  10. Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

    NASA Astrophysics Data System (ADS)

    Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

    2012-02-01

    We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

  11. Siudaite, Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O: a new eudialyte-group mineral from the Khibiny alkaline massif, Kola Peninsula

    NASA Astrophysics Data System (ADS)

    Chukanov, Nikita V.; Rastsvetaeva, Ramiza K.; Kruszewski, Łukasz; Aksenov, Sergey M.; Rusakov, Vyacheslav S.; Britvin, Sergey N.; Vozchikova, Svetlana A.

    2018-03-01

    The new eudialyte-group mineral siudaite, ideally Na8(Mn2+ 2Na)Ca6Fe3+ 3Zr3NbSi25O74(OH)2Cl·5H2O, was discovered in a peralkaline pegmatite situated at the Eveslogchorr Mt., Khibiny alkaline massif, Kola Peninsula, Russia. The associated minerals are aegirine, albite, microcline, nepheline, astrophyllite, and loparite-(Ce). Siudaite forms yellow to brownish-yellow equant anhedral grains up to 1.5 cm across. Its lustre is vitreous, and the streak is white. Cleavage is none observed. The Mohs' hardness is 4½. Density measured by hydrostatic weighing is 2.96(1) g/cm3. Density calculated using the empirical formula is equal to 2.973 g/cm3. Siudaite is nonpleochroic, optically uniaxial, negative, with ω = 1.635(1) and ɛ = 1.626(1) (λ = 589 nm). The IR spectrum is given. The chemical composition of siudaite is (wt%; electron microprobe, H2O determined by HCN analysis): Na2O 8.40, K2O 0.62, CaO 9.81, La2O3 1.03, Ce2O3 1.62, Pr2O3 0.21, Nd2O3 0.29, MnO 6.45, Fe2O3 4.51. TiO2 0.54, ZrO2 11.67, HfO2 0.29, Nb2O5 2.76, SiO2 47.20, Cl 0.54, H2O 3.5, -O = Cl - 0.12, total 99.32. According to Mössbauer spectroscopy data, all iron is trivalent. The empirical formula (based on 24.5 Si atoms pfu, in accordance with structural data) is [Na7.57(H2O)1.43]Σ9(Mn1.11Na0.88Ce0.31La0.20Nd0.05Pr0.04K0.41)Σ3(H2O)1.8(Ca5.46Mn0.54)Σ6(Fe3+ 1.76Mn2+ 1.19)Σ2.95Nb0.65(Ti0.20Si0.50)Σ0.71(Zr2.95Hf0.04Ti0.01)Σ3Si24.00Cl0.47O70(OH)2Cl0.47·1.82H2O. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is trigonal, space group R3m, with a = 14.1885(26) Å, c = 29.831(7) Å, V = 5200.8(23) Å3 and Z = 3. Siudaite is chemically related to georgbarsanovite and is its analogue with Fe3+-dominant M2 site. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 6.38 (60) (-114), 4.29 (55) (-225), 3.389 (47) (131), 3.191 (63) (-228). 2.963 (100) (4-15), 2.843 (99) (-444), 2.577 (49) (3-39). Siudaite is named after the Polish

  12. Neuroprotective effects of corn silk maysin via inhibition of H2O2-induced apoptotic cell death in SK-N-MC cells.

    PubMed

    Choi, Doo Jin; Kim, Sun-Lim; Choi, Ji Won; Park, Yong Il

    2014-07-25

    Neuroprotective effects of maysin, which is a flavone glycoside that was isolated from the corn silk (CS, Zea mays L.) of a Korean hybrid corn Kwangpyeongok, against oxidative stress (H2O2)-induced apoptotic cell death of human neuroblastoma SK-N-MC cells were investigated. Maysin cytotoxicity was determined by measuring cell viability using MTT and lactate dehydrogenase (LDH) assays. Intracellular reactive oxygen species (ROS) were measured using a 2,7-dichlorofluorescein diacetate (DCF-DA) assay. Apoptotic cell death was monitored by annexin V-FITC/PI double staining and by a TUNEL assay. Antioxidant enzyme mRNA levels were determined by real-time PCR. The cleavage of poly (ADP-ribose) polymerase (PARP) was measured by western blotting. Maysin pretreatment reduced the cytotoxic effect of H2O2 on SK-N-MC cells, as shown by the increase in cell viability and by reduced LDH release. Maysin pretreatment also dose-dependently reduced the intracellular ROS level and inhibited PARP cleavage. In addition, DNA damage and H2O2-induced apoptotic cell death were significantly attenuated by maysin pretreatment. Moreover, maysin pretreatment (5-50 μg/ml) for 2h significantly and dose-dependently increased the mRNA levels of antioxidant enzymes (CAT, GPx-1, SOD-1, SOD-2 and HO-1) in H2O2 (200 μM)-insulted cells. These results suggest that CS maysin has neuroprotective effects against oxidative stress (H2O2)-induced apoptotic death of human brain SK-N-MC cells through its antioxidative action. This report is the first regarding neuroprotective health benefits of corn silk maysin by its anti-apoptotic action and by triggering the expression of intracellular antioxidant enzyme systems in SK-N-MC cells. Copyright © 2014 Elsevier Inc. All rights reserved.

  13. Synthesis of Nanoscale CaO-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O Using the Hydrothermal Method and Their Characterization

    PubMed Central

    Yang, Jingbin; Li, Dongxu; Fang, Yuan

    2017-01-01

    C-A-S-H (CaO-Al2O3-SiO2-H2O) and N-A-S-H (Na2O-Al2O3-SiO2-H2O) have a wide range of chemical compositions and structures and are difficult to separate from alkali-activated materials. Therefore, it is difficult to analyze their microscopic properties directly. This paper reports research on the synthesis of C-A-S-H and N-A-S-H particles with an average particle size smaller than 300 nm by applying the hydrothermal method. The composition and microstructure of the products with different CaO(Na2O)/SiO2 ratios and curing conditions were characterized using XRD, the RIR method, FTIR, SEM, TEM, and laser particle size analysis. The results showed that the C-A-S-H system products with a low CaO/SiO2 ratio were mainly amorphous C-A-S-H gels. With an increase in the CaO/SiO2 ratio, an excess of Ca(OH)2 was observed at room temperature, while in a high-temperature reaction system, katoite, C4AcH11, and other crystallized products were observed. The katoite content was related to the curing temperature and the content of Ca(OH)2 and it tended to form at a high-temperature and high-calcium environment, and an increase in the temperature renders the C-A-S-H gels more compact. The main products of the N-A-S-H system at room temperature were amorphous N-A-S-H gels and a small amount of sodalite. An increase in the curing temperature promoted the formation of the crystalline products faujasite and zeolite-P. The crystallization products consisted of only zeolite-P in the high-temperature N-A-S-H system and its content were stable above 70%. An increase in the Na2O/SiO2 ratio resulted in more non-bridging oxygen and the TO4 was more isolated in the N-A-S-H structure. The composition and microstructure of the C-A-S-H and N-A-S-H system products synthesized by the hydrothermal method were closely related to the ratio of the raw materials and the curing conditions. The results of this study increase our understanding of the hydration products of alkali-activated materials. PMID

  14. Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

    PubMed

    Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

    2012-02-20

    Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

  15. Rhus verniciflua Stokes Extract and Its Flavonoids Protect PC-12 Cells against H2O2-Induced Cytotoxicity.

    PubMed

    Nam, Tae Gyu; Lee, Bong Han; Choi, Hyo-Kyoung; Mansur, Ahmad Rois; Lee, Sang Gil; Kim, Dae-Ok

    2017-06-28

    Rhus verniciflua Stokes (RVS), an herbal medicine found in East Asia, was extracted and further fractionated to investigate its antioxidant capacity and neuroprotective effects. The RVS ethyl acetate (EtOAc) fraction had the highest level of total phenolics and antioxidant capacity among all solvent fractions tested. Pretreatment of PC-12 cells with the EtOAc fraction effectively attenuated H 2 O 2 -induced oxidative damage. Furthermore, the EtOAc fraction significantly attenuated caspase-3 activity, resulting in inhibition of H 2 O 2 -induced apoptosis. We identified and quantified fustin, sulfuretin, and butein in the EtOAc fraction using accurate mass quadrupole time-of-flight mass spectrometry and reversed-phase high-performance liquid chromatography. The intracellular antioxidant capacity and superoxide dismutase (SOD) activity were significantly increased in PC-12 cells treated with the EtOAc fraction and with individual flavonoids. When cells were pretreated with the EtOAc fraction or individual flavonoids and then co-incubated with diethyldithiocarbamic acid (an inhibitor of SOD activity), cell viability against H 2 O 2 -induced oxidative stress was attenuated. These results suggest that the RVS EtOAc fraction and its flavonoid constituents protect PC-12 cells against H 2 O 2 -induced neurotoxicity through their antioxidant properties.

  16. Structural diversity of alkaline-earth 2,5-thiophenedicarboxylates

    NASA Astrophysics Data System (ADS)

    Balendra; Ramanan, Arunachalam

    2017-03-01

    Exploration of the structural landscape of the system containing divalent alkaline-earth metal ion (Mg, Ca and Sr) with the rigid 2,5-thiophenedicarboxylic acid (TDC) under varying solvothermal condition (DMF, DMA and DEF) yielded five new crystals: [Mg(TDC) (DEF)2(H2O)1/2] (1), [Ca(TDC) (DMA)] (2), [Ca(TDC) (DMA) (H2O)] (3), [Sr(TDC) (DMA)] (4) and [Sr(TDC) (DMA) (H2O)] (5) and two known solids. Single crystal structures of all the solids are characteristic of extended coordination interaction between metal and carboxylate ions. While the smaller magnesium ion crystallized into a 2D coordination polymer, the larger calcium and strontium compounds resulted into the growth of 3D metal organic frameworks. All the solids show blue emission arising from intra ligand charge transfer.

  17. 5-AIQ inhibits H2O2-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes.

    PubMed

    Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun; Jang, Yong Chang; Yi, Kyu Yang; Chung, Hun-Jong; Park, Jong Seok; Kim, Bokyung; Feng, Zhong-Ping; Shin, Hwa-Sup

    2013-04-01

    Poly(adenosine 5'-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H2O2-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxide dismutase and catalase accompanied the protective effect of 5-AIQ on H2O2-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H2O2-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H2O2-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. Copyright © 2013 Elsevier Inc. All rights reserved.

  18. Development of a reactor with carbon catalysts for modular-scale, low-cost electrochemical generation of H 2O 2

    DOE PAGES

    Chen, Zhihua; Chen, Shucheng; Siahrostami, Samira; ...

    2017-03-01

    The development of small-scale, decentralized reactors for H 2O 2 production that can couple to renewable energy sources would be of great benefit, particularly for water purification in the developing world. Herein, we describe our efforts to develop electrochemical reactors for H 2O 2 generation with high Faradaic efficiencies of >90%, requiring cell voltages of only ~1.6 V. The reactor employs a carbon-based catalyst that demonstrates excellent performance for H 2O 2 production under alkaline conditions, as demonstrated by fundamental studies involving rotating-ring disk electrode methods. Finally, the low-cost, membrane-free reactor design represents a step towards a continuous, modular-scale, de-centralizedmore » production of H 2O 2.« less

  19. Coupling alkaline pre-extraction with alkaline-oxidative post-treatment of corn stover to enhance enzymatic hydrolysis and fermentability.

    PubMed

    Liu, Tongjun; Williams, Daniel L; Pattathil, Sivakumar; Li, Muyang; Hahn, Michael G; Hodge, David B

    2014-04-03

    A two-stage chemical pretreatment of corn stover is investigated comprising an NaOH pre-extraction followed by an alkaline hydrogen peroxide (AHP) post-treatment. We propose that conventional one-stage AHP pretreatment can be improved using alkaline pre-extraction, which requires significantly less H2O2 and NaOH. To better understand the potential of this approach, this study investigates several components of this process including alkaline pre-extraction, alkaline and alkaline-oxidative post-treatment, fermentation, and the composition of alkali extracts. Mild NaOH pre-extraction of corn stover uses less than 0.1 g NaOH per g corn stover at 80°C. The resulting substrates were highly digestible by cellulolytic enzymes at relatively low enzyme loadings and had a strong susceptibility to drying-induced hydrolysis yield losses. Alkaline pre-extraction was highly selective for lignin removal over xylan removal; xylan removal was relatively minimal (~20%). During alkaline pre-extraction, up to 0.10 g of alkali was consumed per g of corn stover. AHP post-treatment at low oxidant loading (25 mg H2O2 per g pre-extracted biomass) increased glucose hydrolysis yields by 5%, which approached near-theoretical yields. ELISA screening of alkali pre-extraction liquors and the AHP post-treatment liquors demonstrated that xyloglucan and β-glucans likely remained tightly bound in the biomass whereas the majority of the soluble polymeric xylans were glucurono (arabino) xylans and potentially homoxylans. Pectic polysaccharides were depleted in the AHP post-treatment liquor relative to the alkaline pre-extraction liquor. Because the already-low inhibitor content was further decreased in the alkaline pre-extraction, the hydrolysates generated by this two-stage pretreatment were highly fermentable by Saccharomyces cerevisiae strains that were metabolically engineered and evolved for xylose fermentation. This work demonstrates that this two-stage pretreatment process is well suited for

  20. Coupling alkaline pre-extraction with alkaline-oxidative post-treatment of corn stover to enhance enzymatic hydrolysis and fermentability

    PubMed Central

    2014-01-01

    Background A two-stage chemical pretreatment of corn stover is investigated comprising an NaOH pre-extraction followed by an alkaline hydrogen peroxide (AHP) post-treatment. We propose that conventional one-stage AHP pretreatment can be improved using alkaline pre-extraction, which requires significantly less H2O2 and NaOH. To better understand the potential of this approach, this study investigates several components of this process including alkaline pre-extraction, alkaline and alkaline-oxidative post-treatment, fermentation, and the composition of alkali extracts. Results Mild NaOH pre-extraction of corn stover uses less than 0.1 g NaOH per g corn stover at 80°C. The resulting substrates were highly digestible by cellulolytic enzymes at relatively low enzyme loadings and had a strong susceptibility to drying-induced hydrolysis yield losses. Alkaline pre-extraction was highly selective for lignin removal over xylan removal; xylan removal was relatively minimal (~20%). During alkaline pre-extraction, up to 0.10 g of alkali was consumed per g of corn stover. AHP post-treatment at low oxidant loading (25 mg H2O2 per g pre-extracted biomass) increased glucose hydrolysis yields by 5%, which approached near-theoretical yields. ELISA screening of alkali pre-extraction liquors and the AHP post-treatment liquors demonstrated that xyloglucan and β-glucans likely remained tightly bound in the biomass whereas the majority of the soluble polymeric xylans were glucurono (arabino) xylans and potentially homoxylans. Pectic polysaccharides were depleted in the AHP post-treatment liquor relative to the alkaline pre-extraction liquor. Because the already-low inhibitor content was further decreased in the alkaline pre-extraction, the hydrolysates generated by this two-stage pretreatment were highly fermentable by Saccharomyces cerevisiae strains that were metabolically engineered and evolved for xylose fermentation. Conclusions This work demonstrates that this two

  1. First identification and thermodynamic characterization of the ternary U(VI) species, UO2(O2)(CO3)2(4-), in UO2-H2O2-K2CO3 solutions.

    PubMed

    Goff, George S; Brodnax, Lia F; Cisneros, Michael R; Peper, Shane M; Field, Stephanie E; Scott, Brian L; Runde, Wolfgang H

    2008-03-17

    In alkaline carbonate solutions, hydrogen peroxide can selectively replace one of the carbonate ligands in UO2(CO3)3(4-) to form the ternary mixed U(VI) peroxo-carbonato species UO2(O2)(CO3)2(4-). Orange rectangular plates of K4[UO2(CO3)2(O2)].H2O were isolated and characterized by single crystal X-ray diffraction studies. Crystallographic data: monoclinic, space group P2(1)/ n, a = 6.9670(14) A, b = 9.2158(10) A, c = 18.052(4) A, Z = 4. Spectrophotometric titrations with H 2O 2 were performed in 0.5 M K 2CO 3, with UO2(O2)(CO3)2(4-) concentrations ranging from 0.1 to 0.55 mM. The molar absorptivities (M(-1) cm(-1)) for UO2(CO3)3(4-) and UO2(O2)(CO3)2(4-) were determined to be 23.3 +/- 0.3 at 448.5 nm and 1022.7 +/- 19.0 at 347.5 nm, respectively. Stoichiometric analyses coupled with spectroscopic comparisons between solution and solid state indicate that the stable solution species is UO2(O2)(CO3)2(4-), which has an apparent formation constant of log K' = 4.70 +/- 0.02 relative to the tris-carbonato complex.

  2. The effects of pretreatment conditions on a Pt/SnO2 catalyst for the oxidation of CO in CO2 lasers

    NASA Technical Reports Server (NTRS)

    Schryer, David R.; Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline

    1989-01-01

    CO oxidation catalysts with high activity at 25 to 100 C are important for long life, closed cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 was shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment of no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady state yield is attained. This dip was found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

  3. Improving methane production from anaerobic digestion of Pennisetum Hybrid by alkaline pretreatment.

    PubMed

    Kang, Xihui; Sun, Yongming; Li, Lianhua; Kong, Xiaoying; Yuan, Zhenhong

    2018-05-01

    Alkaline pretreatment with NaOH was used to improve methane yield from Pennisetum Hybrid. The pretreatments were carried out with different NaOH solutions (2-8% w/w) at three temperatures (35, 55 and 121 °C) for different periods of time (24, 24 and 1 h). All treated and untreated Pennisetum Hybrid were digested under mesophilic conditions (37 °C) to biogas, significant effects of the pretreatments on the yield of methane were observed. Results showed the modified Gompertz equation was reliable (determination coefficients (R 2 ) greater than 0.96) to describe the kinetic behavior of anaerobic digestion of Pennisetum Hybrid. The best result, obtained by the treatment at 35 °C 2% NaOH for 24 h, resulted in the methane yield of 301.7 mL/g VS, corresponding to 21.0% improvement in the methane yield. Compositional, SEM, XRD and FTIR analysis confirmed that lignin removal, structural modification and cellulose crystalline variation were responsible for the improvement. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Excision of uranium oxide chains and ribbons in the novel one-dimensional uranyl iodates K(2)[(UO(2))3(IO(3))(4)O(2)] and Ba[(UO(2)2(IO(3))(2)O(2)](H(2)O).

    PubMed

    Bean, A C; Ruf, M; Albrecht-Schmitt, T E

    2001-07-30

    The alkali metal and alkaline-earth metal uranyl iodates K(2)[(UO(2))(3)(IO(3))(4)O(2)] and Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) have been prepared from the hydrothermal reactions of KCl or BaCl(2) with UO(3) and I(2)O(5) at 425 and 180 degrees C, respectively. While K(2)[(UO(2))(3)(IO(3))(4)O(2)] can be synthesized under both mild and supercritical conditions, the yield increases from <5% to 73% as the temperature is raised from 180 to 425 degrees C. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), however, has only been isolated from reactions performed in the mild temperature regime. Thermal measurements (DSC) indicate that K(2)[(UO(2))(3)(IO(3))(4)O(2)] is more stable than Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) and that both compounds decompose through thermal disproportionation at 579 and 575 degrees C, respectively. The difference in the thermal behavior of these compounds provides a basis for the divergence of their preparation temperatures. The structure of K(2)[(UO(2))(3)(IO(3))(4)O(2)] is composed of [(UO(2))(3)(IO(3))(4)O(2)](2)(-) chains built from the edge-sharing UO(7) pentagonal bipyramids and UO(6) octahedra. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) consists of one-dimensional [(UO(2))(2)(IO(3))(2)O(2)](2)(-) ribbons formed from the edge sharing of distorted UO(7) pentagonal bipyramids. In both compounds the iodate groups occur in both bridging and monodentate binding modes and further serve to terminate the edges of the uranium oxide chains. The K(+) or Ba(2+) cations separate the chains or ribbons in these compounds forming bonds with terminal oxygen atoms from the iodate ligands. Crystallographic data: K(2)[(UO(2))(3)(IO(3))(4)O(2)], triclinic, space group P_1, a = 7.0372(5) A, b = 7.7727(5) A, c = 8.9851(6) A, alpha = 93.386(1) degrees, beta = 105.668(1) degrees, gamma = 91.339(1) degrees, Z = 1; Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), monoclinic, space group P2(1)/c, a = 8.062(4) A, b = 6.940(3) A, c = 21.67(1), beta= 98.05(1) degrees, Z = 4.

  5. Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

  6. H2O Paradox and its Implications on H2O in Moon

    NASA Astrophysics Data System (ADS)

    Zhang, Youxue

    2017-04-01

    The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The

  7. Crystal and molecular structure of Sr{sub 2}(Edta) . 5H{sub 2}O, Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O, and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O strontium ethylenediaminetetraacetates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Poznyak, A. L.; Sergienko, V. S.

    2009-03-15

    Three Sr{sup 2+} compounds with the Edta{sup 4-} and H{sub 2}Edta{sup 2-} ligands-Sr{sub 2}(Edta) . 5H{sub 2}O (I), Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O (II), and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O (III)-are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta{sup 4-} ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with threemore » O atoms of the Edta{sup 4-} ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)-2.656(3) and 2.527(3)-2.683(2) A, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) A long. In II and III, the H{sub 2}Edta{sup 2-} anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H{sub 2}Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H{sub 2}Edta{sup 2-} ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)-2.732(2) and 2.482(2)-2.746(3) A, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) A, respectively. In II, all the structural elements are linked into wavy layers. The O-H-O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr{sup 2+} cations and H{sub 2}Edta{sup -} anions form a three-dimensional [Sr{sub 2}(H{sub 2}Edta)(H{sub 2}O){sub 3}]{sub n}{sup 2n+} framework. The Cl{sup -} anions are fixed in channels of the framework by hydrogen bonds with four water

  8. Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

    NASA Technical Reports Server (NTRS)

    Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

    1988-01-01

    A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

  9. Rapid reagent-less on-line H2O2 quantification in alkaline semiconductor etching solution, Part 2: Nephelometry application.

    PubMed

    Zlatev, Roumen; Stoytcheva, Margarita; Valdez, Benjamin

    2018-03-01

    A simple and rapid reagent less nephelometric method for on-line H 2 O 2 quantification in semiconductors etching solutions was developed, optimized, characterized and validated. The intensity of the light scattered by the oxygen gas suspension resulted from H 2 O 2 catalytic decomposition by immobilized MnO 2 was registered as analytical response. The influences of the light wave length, the agitation rate, the temperature and the catalyst surface area on the response amplitude were studied and optimization was done. The achieved linear concentration range from 10 to 150mmolL -1 at 0.9835 calibration curve correlation coefficient, precision from 3.65% to 0.95% and response time from 35 to 20s respectively, at sensitivity of 8.01µAmmol -1 L and LOD of 2.9mmolL -1 completely satisfy the semiconductor industry requirements. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

    DOE PAGES

    Li, Yuwei; Zhang, Lijun; Singh, David J.

    2017-10-16

    The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

  11. New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Yuwei; Zhang, Lijun; Singh, David J.

    The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

  12. Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

    2012-08-08

    Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

  13. On the role of the termolecular reactions 2O2 + H22HO2 and 2O2 + H2H + HO2 + O2 in formation of the first radicals in hydrogen combustion: ab initio predictions of energy barriers.

    PubMed

    Monge-Palacios, M; Rafatijo, Homayoon

    2017-01-18

    We have investigated the role of termolecular reactions in the early chemistry of hydrogen combustion. We performed molecular chemical dynamics simulations using ReaxFF in LAMMPS to identify potential initial reactions for a 1 : 4 mixture of H 2  : O 2 in the NVT ensemble at density 276.3 kg m -3 and ∼3000 K (∼4000 atm) and ∼4000 K (∼5000 atm), and then characterized the saddle points for those reactions using ab initio methods: CCSD(T) = FC/cc-pVTZ//MP2/6-31G, CCSD(T) = FULL/aug-cc-pVTZ//CCSD = FC/cc-pVTZ and CASSCF MP2/6-31G//MP2/6-31G. The main initial reaction is H 2 + O 2H + HO 2 , frequently occurring in the presence of a second O 2 as a third body; that is, 2O 2 + H 2H + HO 2 + O 2 . The second most frequent reaction is 2O 2 + H 22HO 2 . We found three saddle points on the triplet PES of these termolecular reactions: one for 2O 2 + H 2H + HO 2 + O 2 and two for 2O 2 + H 22HO 2 . In the latter case, one has a symmetric structure consistent with simultaneous formation of two HO 2 and the other corresponds to a bimolecular reaction between O 2 and H 2 that is "interrupted" by a second O 2 before going to completion. The classical barrier height of the symmetric saddle point for 2O 2 + H 22HO 2 is 49.8 kcal mol -1 . The barrier to H 2 + O 2H + HO 2 is 58.9 kcal mol -1 . The termolecular reaction will be competitive with H 2 + O 2H + HO 2 only at sufficiently high pressures.

  14. Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

    NASA Astrophysics Data System (ADS)

    Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

    1994-05-01

    Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

  15. Two Pore Channel 2 (TPC2) Inhibits Autophagosomal-Lysosomal Fusion by Alkalinizing Lysosomal pH*

    PubMed Central

    Lu, Yingying; Hao, Bai-Xia; Graeff, Richard; Wong, Connie W. M.; Wu, Wu-Tian; Yue, Jianbo

    2013-01-01

    Autophagy is an evolutionarily conserved lysosomal degradation pathway, yet the underlying mechanisms remain poorly understood. Nicotinic acid adenine dinucleotide phosphate (NAADP), one of the most potent Ca2+ mobilizing messengers, elicits Ca2+ release from lysosomes via the two pore channel 2 (TPC2) in many cell types. Here we found that overexpression of TPC2 in HeLa or mouse embryonic stem cells inhibited autophagosomal-lysosomal fusion, thereby resulting in the accumulation of autophagosomes. Treatment of TPC2 expressing cells with a cell permeant-NAADP agonist, NAADP-AM, further induced autophagosome accumulation. On the other hand, TPC2 knockdown or treatment of cells with Ned-19, a NAADP antagonist, markedly decreased the accumulation of autophagosomes. TPC2-induced accumulation of autophagosomes was also markedly blocked by ATG5 knockdown. Interestingly, inhibiting mTOR activity failed to increase TPC2-induced autophagosome accumulation. Instead, we found that overexpression of TPC2 alkalinized lysosomal pH, and lysosomal re-acidification abolished TPC2-induced autophagosome accumulation. In addition, TPC2 overexpression had no effect on general endosomal-lysosomal degradation but prevented the recruitment of Rab-7 to autophagosomes. Taken together, our data demonstrate that TPC2/NAADP/Ca2+ signaling alkalinizes lysosomal pH to specifically inhibit the later stage of basal autophagy progression. PMID:23836916

  16. Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

  17. Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

    PubMed

    Srithep, Sirinthip; Phattarapattamawong, Songkeart

    2017-06-01

    The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Effect of pretreatment on pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature.

    PubMed

    Huang, Shaoyong; Zhang, Changbin; He, Hong

    2013-06-01

    The effect of pretreatment on Pd/Al2O3 catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al2O3 catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al2O3 activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al2O3 pre-reduced at 300 degrees C/400 degrees C, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al2O3, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al2O3 catalyst for the catalytic oxidation of o-xylene at low temperature.

  19. Determination Co 2+ in vitamin B 12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H 2O 2 chemiluminescence reaction

    NASA Astrophysics Data System (ADS)

    Han, Lu; Zhang, Yumin; Kang, Jing; Tang, Jieli; Zhang, Yihua

    2011-11-01

    In this paper, three kinds of imidazole derivatives, 2-(4-methylphenyl)-4,5-di(2-furyl) imidazole (MDFI), 2-(4-nitrophenyl)-4,5-di(2-furyl) imidazole (NDFI), and 2-(4-tert-butylphenyl)-4,5-di(2-furyl) imidazole (t-BDFI) were synthesized. In an alkaline medium, the chemiluminescence (CL) reaction of imidazole derivatives with H 2O 2 has been investigated. It was also found that MDFI/H 2O 2 and t-BDFI/H 2O 2 systems gave strong CL. When Co 2+ was added into the two CL systems, the CL intensity was remarkably enhanced. In the optimum conditions, the CL intensity is linearly related to the logarithm of concentration of Co 2+. The linear ranges are 5 × 10 -9-2.5 × 10 -7 mol/L for MDFI/H 2O 2 system and 5 × 10 -9-2.5 × 10 -7 mol/L for t-BDFI/H 2O 2 system, and the corresponding detection limits are 1.2 × 10 -9 mol/L and 1.1 × 10 -9 mol/L, respectively. The method was applied to the determination of Co 2+ in vitamin B 12 injection. Furthermore, the CL mechanism was also discussed.

  20. Vibrational energy transfer and relaxation in O2 and H2O.

    PubMed

    Huestis, David L

    2006-06-01

    Near-resonant vibrational energy exchange between oxygen and water molecules is an important process in the Earth's atmosphere, combustion chemistry, and the chemical oxygen iodine laser (COIL). The reactions in question are (1) O2(1) + O2(0) --> O2(0) + O2(0); (2) O2(1) + H2O(000) --> O2(0) + H2O(000); (3) O2(1) + H2O(000) <--> O2(0) + H2O(010); (4) H2O(010) + H2O(000) --> H2O(000) + H2O(000); and (5) H2O(010) + O2(0) --> H2O(000) + O2(0). Reanalysis of the data available in the chemical kinetics literature provides reliable values for rate coefficients for reactions 1 and 4 and strong evidence that reactions 2 and 5 are slow in comparison with reaction 3. Analytical solution of the chemical rate equations shows that previous attempts to measure the rate of reaction 3 are unreliable unless the water mole fraction is higher than 1%. Reanalysis of data from the only experiment satisfying this constraint provides a rate coefficient of (5.5 +/- 0.4) x 10(-13) cm3/s at room temperature, between the values favored by the atmospheric and laser modeling communities.

  1. Effect of FA/O complexing agents and H2O2 on chemical mechanical polishing of ruthenium in weakly alkaline slurry

    NASA Astrophysics Data System (ADS)

    Bo, Duan; Weijing, An; Jianwei, Zhou; Shuai, Wang

    2015-07-01

    This paper investigated the effect of FA/O and hydrogen peroxide (H2O2) on ruthenium (Ru) removal rate (RR) and static etching rate (SER). It was revealed that Ru RR and SER first linearly increased then slowly decreaseed with the increasing H2O2 probably due to the formation of uniform Ru oxides on the surface during polishing. Their corrosion behaviors and states of surface oxidation were analyzed. In addition, FA/O could chelate Ru oxides (such as (RuO4)2- and RuO4- changed into soluble amine salts [R(NH3)4] (RuO4)2) and enhance Ru RR. The non-ionic surfactant AD was used to improve the Ru CMP performance. In particular, the addition of AD can lead to significant improvement of the surface roughness. Project supported by the Special Project Items No. 2 in National Long-Term Technology Development Plan (No. 2009ZX02308), the Natural Science Foundation of Hebei Province (No. E2013202247), the Science and Technology Plan Project of Hebei Province (Nos. Z2010112, 10213936), the Hebei Provincial Department of Education Fund (No. 2011128), and the Scientific Research Fund of Hebei Provincial Education (No. QN2014208).

  2. Ozonation and alkaline-peroxide pretreatment of wheat straw for Cryptococcus curvatus fermentation

    NASA Technical Reports Server (NTRS)

    Greenwalt, C. J.; Hunter, J. B.; Lin, S.; McKenzie, S.; Denvir, A.

    2000-01-01

    Crop residues in an Advanced Life Support System (ALS) contain many valuable components that could be recovered and used. Wheat is 60% inedible, with approximately 90% of the total sugars in the residue cellulose and hemicellulose. To release these sugars requires pretreatment followed by enzymatic hydrolysis. Cryptococcus curvatus, an oleaginous yeast, uses the sugars in cellulose and hemicellulose for growth and production of storage triglycerides. In this investigation, alkaline-peroxide and ozonation pretreatment methods were compared for their efficiency to release glucose and xylose to be used in the cultivation of C. curvatus. Leaching the biomass with water at 65 degrees C for 4 h prior to pretreatment facilitated saccharification. Alkaline-peroxide and ozone pretreatment were almost 100% and 80% saccharification efficient, respectively. The sugars derived from the hydrolysis of alkaline-peroxide-treated wheat straw supported the growth of C. curvatus and the production of edible single-cell oil.

  3. Aqueous Rechargeable Alkaline CoxNi2-xS2/TiO2 Battery.

    PubMed

    Liu, Jilei; Wang, Jin; Ku, Zhiliang; Wang, Huanhuan; Chen, Shi; Zhang, Lili; Lin, Jianyi; Shen, Ze Xiang

    2016-01-26

    An electrochemical energy storage system with high energy density, stringent safety, and reliability is highly desirable for next-generation energy storage devices. Here an aqueous rechargeable alkaline CoxNi2-xS2 // TiO2 battery system is designed by integrating two reversible electrode processes associated with OH(-) insertion/extraction in the cathode part and Li ion insertion/extraction in the anode part, respectively. The prototype CoxNi2-xS2 // TiO2 battery is able to deliver high energy/power densities of 83.7 Wh/kg at 609 W/kg (based on the total mass of active materials) and good cycling stabilities (capacity retention 75.2% after 1000 charge/discharge cycles). A maximum volumetric energy density of 21 Wh/l (based on the whole packaged cell) has been achieved, which is comparable to that of a thin-film battery and better than that of typical commercial supercapacitors, benefiting from the unique battery and hierarchical electrode design. This hybrid system would enrich the existing aqueous rechargeable LIB chemistry and be a promising battery technology for large-scale energy storage.

  4. Batievaite-(Y), Y2Ca2Ti[Si2O7]2(OH)2(H2O)4, a new mineral from nepheline syenite pegmatite in the Sakharjok massif, Kola Peninsula, Russia

    NASA Astrophysics Data System (ADS)

    Lyalina, L. M.; Zolotarev, A. A.; Selivanova, E. A.; Savchenko, Ye. E.; Krivovichev, S. V.; Mikhailova, Yu. A.; Kadyrova, G. I.; Zozulya, D. R.

    2016-12-01

    Batievaite-(Y), Y2Ca2Ti[Si2O7]2(OH)2(H2O)4, is a new mineral found in nepheline syenite pegmatite in the Sakharjok alkaline massif, Western Keivy, Kola Peninsula, Russia. The pegmatite mainly consists of nepheline, albite, alkali pyroxenes, amphiboles, biotite and zeolites. Batievaite-(Y) is a late-pegmatitic or hydrothermal mineral associated with meliphanite, fluorite, calcite, zircon, britholite-group minerals, leucophanite, gadolinite-subgroup minerals, titanite, smectites, pyrochlore-group minerals, zirkelite, cerianite-(Ce), rutile, behoite, ilmenite, apatite-group minerals, mimetite, molybdenite, and nickeline. Batievaite-(Y) is pale-cream coloured with white streak and dull, greasy or pearly luster. Its Mohs hardness is 5-5.5. No cleavage or parting was observed. The measured density is 3.45(5) g/cm3. Batievaite-(Y) is optically biaxial positive, α 1.745(5), β 1.747(5), γ 1.752(5) (λ 589 nm), 2 V meas. = 60(5)°, 2 V calc. = 65°. Batievaite-(Y) is triclinic, space group P-1, a 9.4024(8), b 5.5623(5), c 7.3784(6) Å, α 89.919(2), β 101.408(2), γ 96.621(2)°, V 375.65(6) Å3 and Z = 1. The eight strongest lines of the X-ray powder diffraction pattern [ d(Å)(I)( hkl)] are: 2.991(100)(11-2), 7.238(36)(00-1), 3.061(30)(300), 4.350(23)(0-1-1), 9.145(17)(100), 4.042(16)(11-1), 2.819(16)(3-10), 3.745(13)(2-10). The chemical composition determined by electron probe microanalysis (EPMA) is (wt.%): Nb2O5 2.25, TiO2 8.01, ZrO2 2.72, SiO2 29.96, Al2O3 0.56, Fe2O3 0.43, Y2O3 11.45, La2O3 0.22, Ce2O3 0.33, Nd2O3 0.02, Gd2O3 0.07, Dy2O3 0.47, Er2O3 1.07, Tm2O3 0.25, Yb2O3 2.81, Lu2O3 0.45, CaO 24.98, MnO 1.31, MgO 0.01, Na2O 1.13, K2O 0.02, F 2.88, Cl 0.19, H2O 6.75 (determined on the basis of crystal structure data), O = (F,Cl) -1.25, total 97.09 wt.%. The empirical formula based on the EPMA and single-crystal structure analyses is (Y0.81Ca0.65Mn0.15Zr0.12Yb0.11Er0.04Fe3+ 0.04Ce0.02Dy0.02Lu0.02La0.01Tm0.01)Σ2.00((H2O)0.75Ca0.70□0.55)Σ2.00Ca2.00(□0.61Na0

  5. 5-AIQ inhibits H{sub 2}O{sub 2}-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun

    2013-04-01

    Poly(adenosine 5′-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H{sub 2}O{sub 2}-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxidemore » dismutase and catalase accompanied the protective effect of 5-AIQ on H{sub 2}O{sub 2}-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H{sub 2}O{sub 2}-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H{sub 2}O{sub 2}-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. - Highlights: ► 5-AIQ, a PARP inhibitor, decreased H{sub 2}O{sub 2}-induced H9c2 cell death and apoptosis. ► 5-AIQ upregulated antioxidant Mn-SOD and catalase, while decreasing ROS production. ► 5-AIQ decreased H{sub 2}O{sub 2}-induced increase in cleaved caspase-3 and Bax and decrease in Bcl2. ► 5-AIQ activated Akt and

  6. Full-dimensional, high-level ab initio potential energy surfaces for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2} with application to hydrogen clathrate hydrates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen

    2015-08-28

    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H{sub 2}(H{sub 2}O) two-body and H{sub 2}(H{sub 2}O){sub 2} three-body potentials. The database for H{sub 2}(H{sub 2}O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are comparedmore » to computationally faster ones obtained via “purified” symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H{sub 2}, H{sub 2}O, and (H{sub 2}O){sub 2}, to obtain full PESs for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2}. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H{sub 2}(H{sub 2}O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H{sub 2}@(H{sub 2}O){sub 20}. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H{sub 2} from the calculated equilibrium structure.« less

  7. Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

    PubMed

    Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

    2014-08-30

    The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Ethanol production from rape straw by a two-stage pretreatment under mild conditions.

    PubMed

    Romero, Inmaculada; López-Linares, Juan C; Delgado, Yaimé; Cara, Cristóbal; Castro, Eulogio

    2015-08-01

    The growing interest on rape oil as raw material for biodiesel production has resulted in an increasing availability of rape straw, an agricultural residue that is an attractive renewable source for the production of second-generation bioethanol. Pretreatment is one of the key steps in such a conversion process. In this work, a sequential two-stage pretreatment with dilute sulfuric acid (130 °C, 60 min, 2% w/v H2SO4) followed by H2O2 (1-5% w/v) in alkaline medium (NaOH) at low temperature (60, 90 °C) and at different pretreatment times (30-90 min) was investigated. The first-acid stage allows the solubilisation of hemicellulose fraction into fermentable sugars. The second-alkaline peroxide stage allows the delignification of the solid material whilst the cellulose remaining in rape straw turned highly digestible by cellulases. Simultaneous saccharification and fermentation with 15% (w/v) delignified substrate at 90 °C, 5% H2O2 for 60 min, led to a maximum ethanol production of 53 g/L and a yield of 85% of the theoretical.

  9. Alkaline twin-screw extrusion pretreatment for fermentable sugar production

    PubMed Central

    2013-01-01

    Background The inevitable depletion of fossil fuels has resulted in an increasing worldwide interest in exploring alternative and sustainable energy sources. Lignocellulose, which is the most abundant biomass on earth, is widely regarded as a promising raw material to produce fuel ethanol. Pretreatment is an essential step to disrupt the recalcitrance of lignocellulosic matrix for enzymatic saccharification and bioethanol production. This paper established an ATSE (alkaline twin-screw extrusion pretreatment) process using a specially designed twin-screw extruder in the presence of alkaline solution to improve the enzymatic hydrolysis efficiency of corn stover for the production of fermentable sugars. Results The ATSE pretreatment was conducted with a biomass/liquid ratio of 1/2 (w/w) at a temperature of 99°C without heating equipment. The results indicated that ATSE pretreatment is effective in improving the enzymatic digestibility of corn stover. Sodium hydroxide loading is more influential factor affecting both sugar yield and lignin degradation than heat preservation time. After ATSE pretreatment under the proper conditions (NaOH loading of 0.06 g/g biomass during ATSE and 1 hour heat preservation after extrusion), 71% lignin removal was achieved and the conversions of glucan and xylan in the pretreated biomass can reach to 83% and 89% respectively via subsequent enzymatic hydrolysis (cellulase loading of 20 FPU/g-biomass and substrate consistency of 2%). About 78% of the original polysaccharides were converted into fermentable sugars. Conclusions With the physicochemical functions in extrusion, the ATSE method can effectively overcome the recalcitrance of lignocellulose for the production of fermentable sugars from corn stover. This process can be considered as a promising pretreatment method due to its relatively low temperature (99°C), high biomass/liquid ratio (1/2) and satisfied total sugar yield (78%), despite further study is needed for process

  10. Alkaline twin-screw extrusion pretreatment for fermentable sugar production.

    PubMed

    Liu, Chao; van der Heide, Evert; Wang, Haisong; Li, Bin; Yu, Guang; Mu, Xindong

    2013-01-01

    The inevitable depletion of fossil fuels has resulted in an increasing worldwide interest in exploring alternative and sustainable energy sources. Lignocellulose, which is the most abundant biomass on earth, is widely regarded as a promising raw material to produce fuel ethanol. Pretreatment is an essential step to disrupt the recalcitrance of lignocellulosic matrix for enzymatic saccharification and bioethanol production. This paper established an ATSE (alkaline twin-screw extrusion pretreatment) process using a specially designed twin-screw extruder in the presence of alkaline solution to improve the enzymatic hydrolysis efficiency of corn stover for the production of fermentable sugars. The ATSE pretreatment was conducted with a biomass/liquid ratio of 1/2 (w/w) at a temperature of 99°C without heating equipment. The results indicated that ATSE pretreatment is effective in improving the enzymatic digestibility of corn stover. Sodium hydroxide loading is more influential factor affecting both sugar yield and lignin degradation than heat preservation time. After ATSE pretreatment under the proper conditions (NaOH loading of 0.06 g/g biomass during ATSE and 1 hour heat preservation after extrusion), 71% lignin removal was achieved and the conversions of glucan and xylan in the pretreated biomass can reach to 83% and 89% respectively via subsequent enzymatic hydrolysis (cellulase loading of 20 FPU/g-biomass and substrate consistency of 2%). About 78% of the original polysaccharides were converted into fermentable sugars. With the physicochemical functions in extrusion, the ATSE method can effectively overcome the recalcitrance of lignocellulose for the production of fermentable sugars from corn stover. This process can be considered as a promising pretreatment method due to its relatively low temperature (99°C), high biomass/liquid ratio (1/2) and satisfied total sugar yield (78%), despite further study is needed for process optimization and cost reduction.

  11. Ilyukhinite (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 • 3H2O, a New Mineral of the Eudialyte Group

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Rastsvetaeva, R. K.; Rozenberg, K. A.; Aksenov, S. M.; Pekov, I. V.; Belakovsky, D. I.; Kristiansen, R.; Van, K. V.

    2017-12-01

    A new eudialyte-group mineral, ilyukhinite, ideally (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 · 3H2O, has been found in peralkaline pegmatite at Mt. Kukisvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. It occurs as brownish orange, with vitreous luster anhedral grains up to 1 mm across in hydrothermally altered peralkaline rock, in association with aegirine, murmanite, albite, microcline, rhabdophane-(Ce), fluorite, sphalerite and molybdenite. The Mohs hardness is 5; cleavage is not observed. D meas 2.67(2), D calc 2.703 g/cm3. Ilyukhinite is optically uniaxial (-): ω = 1.585(2), ɛ = 1.584(2). The IR spectrum is given. The average chemical composition of ilyukhinite (wt %; electron microprobe, ranges given in parentheses; H2O determined by gas chromatography) is as follows: 3.07 (3.63-4.43) Na2O, 0.32 (0.28-0.52) K2O, 10.63 (10.26-10.90) CaO, 3.06 (2.74-3.22) MnO, 1.15 (0.93-1.37) FeO, 0.79 (0.51-0.89) La2O3, 1.21 (0.97-1.44) Ce2O3, 0.41 (0.30-0.56) Nd2O3, 0.90 (0.77-1.12) TiO2, 10.94 (10.15-11.21) ZrO2, 1.40 (0.76-1.68) Nb2O5, 51.24 (49.98-52.28) SiO2, 1.14 (0.89-1.37) SO3, 0.27 (0.19—0.38) Cl, 10.9(5 )H2O,-0.06-O = C1, total is 98.27. The empirical formula is H36.04(Na3.82K0.20)(Ca5.65Ce0.22La0.14Nd0.07)(Mn1.285Fe0.48)(Zr2.645Ti0.34)Nb0.31Si25.41S0.42Cl0.23O86.82. The crystal structure has been solved ( R = 0.046). Ilyukhinite is trigonal, R3 m; a = 14.1695(6) Å, b = 31.026(1) Å, V = 5394.7(7) Å3, Z = 3. The strongest XRD reflections [ d, Å (I, %) ( hkl)] are 11.44 (82) (101), 7.09 (70) (110), 6.02 (44) (021), 4.371 (89) 205), 3.805 (47) (303, 033), 3.376 (41) (131), 2.985 (100) (315, 128), 2.852 (92) (404). Ilyukhinite was named in memory of Vladimir V. Ilyukhin (1934-1982), an outstanding Soviet crystallographer. The type specimen of ilyukhinite has been deposited in the collection of the Natural History Museum, University of Oslo, Norway.

  12. Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1).

    PubMed

    Li, Xiang; Wang, Haopeng; Bowen, Kit H

    2010-10-14

    The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

  13. Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.

    2010-10-01

    The hydrated nucleoside anions, uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1, have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine-(H2O)1 and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

  14. Alkaline Peroxide Delignification of Corn Stover

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mittal, Ashutosh; Katahira, Rui; Donohoe, Bryon S.

    Selective biomass fractionation into carbohydrates and lignin is a key challenge in the conversion of lignocellulosic biomass to fuels and chemicals. In the present study, alkaline hydrogen peroxide (AHP) pretreatment was investigated to fractionate lignin from polysaccharides in corn stover (CS), with a particular emphasis on the fate of the lignin for subsequent valorization. The influence of peroxide loading on delignification during AHP pretreatment was examined over the range of 30-500 mg H2O2/g dry CS at 50 degrees C for 3 h. Mass balances were conducted on the solid and liquid fractions generated after pretreatment for each of the threemore » primary components, lignin, hemicellulose, and cellulose. AHP pretreatment at 250 mg H2O2/g dry CS resulted in the pretreated solids with more than 80% delignification consequently enriching the carbohydrate fraction to >90%. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AHP pretreated residue shows that, under high peroxide loadings (>250 mg H2O2/g dry CS), most of the side chain structures were oxidized and the aryl-ether bonds in lignin were partially cleaved, resulting in significant delignification of the pretreated residues. Gel permeation chromatography (GPC) analysis shows that AHP pretreatment effectively depolymerizes CS lignin into low molecular weight (LMW) lignin fragments in the aqueous fraction. Imaging of AHP pretreated residues shows a more granular texture and a clear lamellar pattern in secondary walls, indicative of layers of varying lignin removal or relocalization. Enzymatic hydrolysis of this pretreated residue at 20 mg/g of glucan resulted in 90% and 80% yields of glucose and xylose, respectively, after 120 h. Overall, AHP pretreatment is able to selectively remove more than 80% of the lignin from biomass in a form that has potential for downstream valorization processes and enriches the solid pulp into a highly digestible material.« less

  15. Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems.

    PubMed

    Garcia, J C; Oliveira, J L; Silva, A E C; Oliveira, C C; Nozaki, J; de Souza, N E

    2007-08-17

    This work investigated the treatability of real textile effluents using several systems involving advanced oxidation processes (AOPs) such as UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/Fe2+/H2O2. The efficiency of each technique was evaluated according to the reduction levels observed in the UV absorbance of the effluents, COD, and organic nitrogen reduction, as well as mineralization as indicated by the formation of ammonium, nitrate, and sulfate ions. The results indicate the association of TiO2 and H2O2 as the most efficient treatment for removing organic pollutants from textile effluents. In spite of their efficiency, Fenton reactions based treatment proved to be slower and exhibited more complicated kinetics than the ones using TiO2, which are pseudo-first-order reactions. Decolorization was fast and effective in all the experiments despite the fact that only H2O2 was used.

  16. Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI = 2,4-Dinitroimidazolate)

    PubMed Central

    Zhang, Guo-Fang; Cai, Mei-Yu; Jing, Ping; He, Chong; Li, Ping; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

    2010-01-01

    Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O, 1, and Pb(DNI)2(H2O)4, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) Å, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) Å, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon. PMID:20526419

  17. The effect of thermal pre-treatment of titanium hydride (TiH2) powder in argon condition

    NASA Astrophysics Data System (ADS)

    Franciska P., L.; Erryani, Aprilia; Annur, Dhyah; Kartika, Ika

    2018-04-01

    Titanium hydride (TiH2) powders are used to enhance the foaming process in the formation of a highly porous metallic material with a cellular structure. But, the low temperature of hydrogen release is one of its problems. The present study, different thermal pre-treatment temperatures were employed to investigate the decomposition behavior of TiH2 to retard or delay a hydrogen gas release process during foaming. As a foaming agent, TiH2 was subjected to various heat treatments prior at 450 and 500°C during 2 hours in argon condition. To study the formation mechanism, the thermal behavior of titanium hydride and hydrogen release are investigated by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The morphology of pre-treated titanium hydride powders were examined using Scanning Electron Microscope (SEM) while unsure mapping and elemental composition of the pre-treated powders processed by Energy Dispersive Spectroscopy (EDS). To study the phase formation was characterized by X-ray diffraction analysis (XRD). In accordance with the results, an increase in pre-treatment temperature of TiH2 to higher degrees are changing the process of releasing hydrogen from titanium hydride powder. DTA/TGA results showed that thermal pre-treatment TiH2 at 450°C, released the hydrogen gas at 560°C in heat treatment when foaming process. Meanwhile, thermal pre-treatment in TiH2 at 500°C, released the hydrogen gas at 670°C when foaming process. There is plenty of direct evidence for the existence of oxide layers that showed by EDS analysis obtained in SEM. As oxygen is a light element and qualitative proof shows that the higher pre-treatment temperature produces more and thicker oxygen layers on the surface of the TiH2 powder particles. It might the thickness of oxide layer are different from different pre-treatment temperatures, which leading to the differences in the decomposition temperature. But from SEM result that oxidation of the powder does not

  18. Exploring surface characterization and electrostatic property of Hybrid Pennisetum during alkaline sulfite pretreatment for enhanced enzymatic hydrolysability.

    PubMed

    Yang, Ming; Wang, Jingfeng; Hou, Xincun; Wu, Juying; Fan, Xifeng; Jiang, Fan; Tao, Pan; Wang, Fan; Peng, Pai; Yang, Fangxia; Zhang, Junhua

    2017-11-01

    The surface characterization and electrostatic property of Hybrid Pennisetum (HP) after alkaline sulfite pretreatment were explored for enhanced enzymatic hydrolysability. The O/C ratio in HP increased from 0.34 to 0.60, and C1 concentration decreased from 62.5% to 31.6%, indicating that alkaline sulfite pretreatment caused poorer lignin but richer carbohydrate on HP surface. Zeta potential and sulfur element analysis indicated that more enzymes would preferably adsorb on the carbohydrate surface of alkaline sulfite pretreated HP because the lignin was sulfonated, which facilitated the decrease of non-productive adsorption. Glucose yield of alkaline sulfite pretreated HP reached to 100% by synergistic action of cellulase and xylanase in the hydrolysis, which was significantly higher than that of NaOH pretreated, and the concentration of glucose released was 1.52times higher. The results suggested that alkaline sulfite pretreatment had potential for improving the HP hydrolysability, and the surface characterization and electrostatic property facilitated the enzymatic digestibility. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. VUV photoionization cross sections of HO2, H2O2, and H2CO.

    PubMed

    Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

    2015-02-26

    The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

  20. H2O2 induced cost effective microwave disintegration of dairy waste activated sludge in acidic environment for efficient biomethane generation.

    PubMed

    Eswari, A Parvathy; Kavitha, S; Banu, J Rajesh; Karthikeyan, O Parthiba; Yeom, Ick-Tae

    2017-11-01

    This study aimed to improve the biomethane potential of dairy waste activated sludge (WAS) by H 2 O 2 -acidic pH induced microwave disintegration (HAMW-D) pretreatment approach. The results of HAMW-D compared with the microwave disintegration (MW-D) alone for energy and economic factors. In the two phase disintegration process, the H 2 O 2 concentration of about 0.5mg/g SS under acid pH of 5 was found to be optimum for effective dissociation of Extracellular Polymeric Substances (EPS) matrix. A higher liquefaction of about 46.6% was achieved in HAMW-D when compared to that of MW-D (30%). It subsequently improved the methane yield of about 250mL/g VS in HAMW-D, which was 9.6% higher than MW-D. A net profit of about 49€/ton was achieved for HAMW-D, therefore it is highly recommended for WAS pretreatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. The reaction of H2O2 with NO2 and NO

    NASA Technical Reports Server (NTRS)

    Gray, D.; Lissi, E.; Heicklen, J.

    1972-01-01

    The reactions of NO and NO2 with H2O2 have been examined at 25 C. Reaction mixtures were monitored by continuously bleeding through a pinhole into a monopole mass spectrometer. NO2 was also monitored by its optical absorption in the visible part of the spectrum. Reaction mixtures containing initially 1.5 - 2.5 torr of NO2 and 0.8 - 1.4 torr of H2O2 or 1 - 12 torr of NO and 0.5 - 1.5 torr of H2O2 were studied. The H2O2 - NO reaction was complex. There was an induction period followed by a marked acceleration in reactant removal. The final products of the reaction, NO2, probably H2O, and possibly HONO2 were produced mainly after all the H2O2 was removed. The HONO intermediate was shown to disproportionate to NO2 + NO + H2O in a relatively slow first order reaction. The acceleration in H2O2 removal after the NO - H2O2 reaction is started is caused by NO2 catalysis.

  2. Intrinsically modified thermoelectric performance of alkaline-earth isovalently substituted [Bi2AE2O4][CoO2]y single crystals

    NASA Astrophysics Data System (ADS)

    Sun, N.; Dong, S. T.; Zhang, B. B.; Chen, Y. B.; Zhou, J.; Zhang, S. T.; Gu, Z. B.; Yao, S. H.; Chen, Y. F.

    2013-07-01

    Alkaline-earth elements isovalently substituted into a [Bi2AE2O4][CoO2]y (AE2 = Ca2, Sr2, and CaSr) single crystal with a layered structure were grown by the optical floating zone method. Structural characterization by X-ray diffraction and electron microscopy showed that the layers were oriented perpendicular to the c-axis, as well as the growth of direction was parallel to the ab-plane. The thermoelectric properties, including the Seebeck effect, electrical conductivity and thermal conductivity were investigated. The results of the thermoelectric measurements showed that the full substitution of Ca for Sr in [Bi2Sr2-xCaxO4][CoO2]y has the best overall thermoelectric performance. Compared with the other two cases studied, the full Ca substituted crystal [Bi2Ca2O4][CoO2]y exhibits both reduced resistivity and thermal conductivity, but not a reduced Seebeck coefficient. The enhanced thermoelectric property in [Bi2Ca2O4][CoO2]y is mainly due to lower structural symmetry, which is confirmed by electron microscopy characterization. This work demonstrates that even isovalently substitution can play a crucial role in the thermoelectric effect of layered cobalt oxides.

  3. Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

    PubMed

    Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

    2016-04-05

    UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

  4. Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

    NASA Astrophysics Data System (ADS)

    Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

    2016-12-01

    Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

  5. CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

    Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

  6. CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

    DOE PAGES

    Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

    2016-08-26

    Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

  7. A Computational Investigation of the Oxidative Deboronation of BoroGlycine, H2N–CH2–B(OH)2, Using H2O and H2O2

    PubMed Central

    Larkin, Joseph D.; Markham, George D.; Milkevitch, Matt; Brooks, Bernard R.; Bock, Charles W.

    2014-01-01

    We report results from a computational investigation of the oxidative deboronation of BoroGlycine, H2N–CH2–B(OH)2, using H2O and H2O2 as the reactive oxygen species (ROS) to yield aminomethanol, H2N–CH2–OH; these results complement our study on the protodeboronation of BoroGlycine to produce methylamine, H2N–CH3 (Larkin et al. J. Phys. Chem. A, 111, 6489–6500, 2007). Second-order Møller-Plesset (MP2) perturbation theory with Dunning-Woon correlation-consistent (cc) basis sets were used for the calculations with comparisons made to results from Density Functional Theory (DFT) at the PBE1PBE/6-311++G(d,p)(cc-pVDZ) levels. The effects of a bulk aqueous environment were also incorporated into the calculations employing PCM and CPCM methodology. Using H2O as the ROS, the reaction H2O + H2N–CH2–B(OH)2H2N–CH2–OH + H–B(OH)2 was calculated to be endothermic, the value of ΔH2980 was +12.0 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and +13.7 kcal/mol in PCM aqueous media; the corresponding value for the activation barrier, ΔH‡, was +94.3 kcal/mol relative to the separated reactants in vacuo and +89.9 kcal/mol in PCM aqueous media. In contrast, the reaction H2O2 + H2N–CH2–B(OH)2H2N–CH2–OH + B(OH)3 was calculated to be highly exothermic with a ΔH2980 value of −100.9 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and −99.6 kcal/mol in CPCM aqueous media; the highest-energy transition state for the multi-step process associated with this reaction involved the rearrangement of H2N–CH2–B(OH)(OOH) to H2N–CH2–O–B(OH)2 with a ΔH‡ value of +23.2 kcal/mol in vacuo relative to the separated reactants. These computational results for BoroGlycine are in accord with the experimental observations for the deboronation of the FDA approved anti-cancer drug Bortezomib (Velcade™, PS-341) where it was found to be the principle deactivation pathway. (Labutti et al. Chem. Res. Toxicol., 19, 539–546

  8. EPR Oximetry for Investigation of Hyperbaric O2 Pre-treatment for Tumor Radiosensitization.

    PubMed

    Williams, Benjamin B; Hou, Huagang; Coombs, Rachel; Swartz, Harold M

    A number of studies have reported benefits associated with the application of hyperbaric oxygen treatment (HBO) delivered immediately prior to radiation therapy. While these studies provide evidence that pre-treatment with HBO may be beneficial, no measurements of intratumoral pO2 were carried out and they do not directly link the apparent benefits to decreased hypoxic fractions at the time of radiation therapy. While there is empirical evidence and some theoretical basis for HBO to enhance radiation therapy, without direct and repeated measurements of its effects on pO2, it is unlikely that the use of HBO can be understood and optimized for clinical applications. In vivo EPR oximetry is a technique uniquely capable of providing repeated direct measurements of pO2 through a non-invasive procedure in both animal models and human patients. In order to evaluate the ability of pretreatment with HBO to elevate tumor pO2, a novel small animal hyperbaric chamber system was constructed that allows simultaneous in vivo EPR oximetry. This chamber can be placed within the EPR magnet and is equipped with a variety of ports for multiplace gas delivery, thermoregulation, delivery of anesthesia, physiologic monitoring, and EPR detection. Initial measurements were performed in a subcutaneous RIF-1 tumor model in C3H/HeJ mice. The mean baseline pO2 value was 6.0 ± 1.2 mmHg (N = 7) and responses to two atmospheres absolute pressure HBO varied considerably across subjects, within tumors, and over time. When an increase in pO2 was observed, the effect was transient in all but one case, with durations lasting from 5 min to over 20 min, and returned to baseline levels during HBO administration. These results indicate that without direct measurements of pO2 in the tissue of interest, it is likely to be difficult to know the effects of HBO on actual tissue pO2.

  9. Lignin degradation in corn stalk by combined method of H2O2 hydrolysis and Aspergillus oryzae CGMCC5992 liquid-state fermentation.

    PubMed

    Zhang, Zhicai; Xia, Lili; Wang, Feng; Lv, Peng; Zhu, Maxiaoqi; Li, Jinhua; Chen, Keping

    2015-01-01

    Lignin peroxidase (LiP) is the primary enzyme responsible for lignin degradation. In our previous work, in order to shorten the pretreatment time and increase the lignin degradation, we have pretreated the corn stalk (CS) using a combination of Aspergillus oryzae CGMCC 5992 solid-state fermentation and H2O2 treatment. In the present study, one-factor-at-a-time design and response surface design were applied to optimize the nutritional constituents for LiP production in liquid-state fermentation by A. oryzae CGMCC 5992 and the conditions for CS degradation by A. oryzae CGMCC 5992. The optimal medium included CS of 30 g/L, glucose of 4.6 g/L, sodium nitrate of 1.2 g/L, corn steep liquor of 1 g/L, yeast extract of 1.2 g/L, and vitamin B1 of 0.15 g/L. Under these optimal conditions, the LiP production reached its maximum of 652.34 U/L. The optimal condition for CS degradation included CS of 20 g, A. oryzae CGMCC 5992 broth of 50 mL, 1.5 % H2O2 solution of 80 mL, H2O2 flow rate of 0.4 mL/min, water volume of 240 mL (water/material ratio of 12:1), hydrolysis temperature of 39 °C, and hydrolysis time of 8 h. Before hydrolysis, CS and water were pretreated at 113 °C for 11 min. Under these optimal conditions, the sugar yield reached its maximum of 46.28 %. Our newly developed method had great advantages in pretreatment of CS due to its quickness, convenience, safety, no special equipment and high sugar yield.Graphical abstractThe schematic diagram of corn straw hydrolysis.

  10. Solar treatment (H2O2, TiO2-P25 and GO-TiO2 photocatalysis, photo-Fenton) of organic micropollutants, human pathogen indicators, antibiotic resistant bacteria and related genes in urban wastewater.

    PubMed

    Moreira, Nuno F F; Narciso-da-Rocha, Carlos; Polo-López, M Inmaculada; Pastrana-Martínez, Luisa M; Faria, Joaquim L; Manaia, Célia M; Fernández-Ibáñez, Pilar; Nunes, Olga C; Silva, Adrián M T

    2018-05-15

    Solar-driven advanced oxidation processes were studied in a pilot-scale photoreactor, as tertiary treatments of effluents from an urban wastewater treatment plant. Solar-H 2 O 2 , heterogeneous photocatalysis (with and/or without the addition of H 2 O 2 and employing three different photocatalysts) and the photo-Fenton process were investigated. Chemical (sulfamethoxazole, carbamazepine, and diclofenac) and biological contaminants (faecal contamination indicators, their antibiotic resistant counterparts, 16S rRNA and antibiotic resistance genes), as well as the whole bacterial community, were characterized. Heterogeneous photocatalysis using TiO 2 -P25 and assisted with H 2 O 2 (P25/H 2 O 2 ) was the most efficient process on the degradation of the chemical organic micropollutants, attaining levels below the limits of quantification in less than 4 h of treatment (corresponding to Q UV  < 40 kJ L -1 ). This performance was followed by the same process without H 2 O 2 , using TiO 2 -P25 or a composite material based on graphene oxide and TiO 2 . Regarding the biological indicators, total faecal coliforms and enterococci and their antibiotic resistant (tetracycline and ciprofloxacin) counterparts were reduced to values close, or beneath, the detection limit (1 CFU 100 mL -1 ) for all treatments employing H 2 O 2 , even upon storage of the treated wastewater for 3-days. Moreover, P25/H 2 O 2 and solar-H 2 O 2 were the most efficient processes in the reduction of the abundance (gene copy number per volume of wastewater) of the analysed genes. However, this reduction was transient for 16S rRNA, intI1 and sul1 genes, since after 3-days storage of the treated wastewater their abundance increased to values close to pre-treatment levels. Similar behaviour was observed for the genes qnrS (using TiO 2 -P25), bla CTX-M and bla TEM (using TiO 2 -P25 and TiO 2 -P25/H 2 O 2 ). Interestingly, higher proportions of sequence reads affiliated to the phylum Proteobacteria

  11. The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

    NASA Astrophysics Data System (ADS)

    Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing

    2018-07-01

    The addition reaction of CH2OO + H2O → CH2(OH)OOH without and with X (X = H2CO3, CH3COOH and HCOOH) and H2O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH2OO + H2O → CH2(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2OO...H2O is favourable one. Water-assisted CH2OO + H2O → CH2(OH)OOH can occur by H2O moiety of (H2O)2 or the whole (H2O)2 forming cyclic structure with CH2OO, where the latter form is more favourable. Because the concentration of H2CO3 is unknown, the influence of CH3COOH, HCOOH and H2O were calculated within 0-30 km altitude of the Earth's atmosphere. The results calculated within 0-5 km altitude show that H2O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%-77.26% and 0.04%-1.76%. Within 5-30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%-98.28%. However, compared with the reaction of CH2OO + HCOOH, the rate of CH2OO...H2O + HCOOH is much slower.

  12. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2011-03-01

    "H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

  13. Influence of surface properties on the mechanism of H2S removal by alkaline activated carbons.

    PubMed

    Yan, Rong; Chin, Terence; Ng, Yuen Ling; Duan, Huiqi; Liang, David Tee; Tay, Joo Hwa

    2004-01-01

    Alkaline activated carbons are widely used as adsorbents of hydrogen sulfide (H2S), one of the major odorous compounds arising from sewage treatment facilities. Although a number of studies have explored the effects of various parameters, mechanisms of H2S adsorption by alkaline carbons are not yet fully understood. The major difficulty seems to lie in the fact that little is known with certainty about the predominant reactions occurring on the carbon surface. In this study, the surface properties of alkaline activated carbons were systematically investigated to further exploit and better understand the mechanisms of H2S adsorption by alkaline activated carbons. Two commercially available alkaline activated carbons and their representative exhausted samples (8 samples collected at different height of the column after H2S breakthrough tests) were studied. The 8 portions of the exhausted carbon were used to represent the H2S/carbon reaction process. The surface properties of both the original and the exhausted carbons were characterized using the sorption of nitrogen (BET test), surface pH, Boehm titration, thermal and FTIR analysis. Porosity and surface area provide detailed information about the pore structure of the exhausted carbons with respect to the reaction extent facilitating the understanding of potential pore blockages. Results of Boehm titration and FTIR both demonstrate the significant effects of surface functional groups, and identification of oxidation products confirmed the different mechanisms involved with the two carbons. From the DTG curves of thermal analysis, two well-defined peaks representing two products of surface reactions (i.e., sulfur and sulfuric acid) were observed from the 8 exhausted portions with gradually changing patterns coinciding with the extent of the reaction. Surface pH values of the exhausted carbons show a clear trend of pH drop along the reaction extent, while pH around 2 was observed for the bottom of the bed indicating

  14. Anaerobic co-digestion of microalgal biomass and wheat straw with and without thermo-alkaline pretreatment.

    PubMed

    Solé-Bundó, Maria; Eskicioglu, Cigdem; Garfí, Marianna; Carrère, Hélène; Ferrer, Ivet

    2017-08-01

    This study aimed at analyzing the anaerobic co-digestion of microalgal biomass grown in wastewater and wheat straw. To this end, Biochemical Methane Potential (BMP) tests were carried out testing different substrate proportions (20-80, 50-50 and 80-20%, on a volatile solid basis). In order to improve their biodegradability, the co-digestion of both substrates was also evaluated after applying a thermo-alkaline pretreatment (10% CaO at 75°C for 24h). The highest synergies in degradation rates were observed by adding at least 50% of wheat straw. Therefore, the co-digestion of 50% microalgae - 50% wheat straw was investigated in mesophilic lab-scale reactors. The results showed that the methane yield was increased by 77% with the co-digestion as compared to microalgae mono-digestion, while the pretreatment only increased the methane yield by 15% compared to the untreated mixture. Thus, the anaerobic co-digestion of microalgae and wheat straw was successful even without applying a thermo-alkaline pretreatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Low-heat, mild alkaline pretreatment of switchgrass for anaerobic digestion.

    PubMed

    Jin, Guang; Bierma, Tom; Walker, Paul M

    2014-01-01

    This study examines the effectiveness of alkaline pretreatment under mild heat conditions (100°C or 212°F) on the anaerobic co-digestion of switchgrass. The effects of alkaline concentration, types of alkaline, heating time and rinsing were evaluated. In addition to batch studies, continuous-feed studies were performed in triplicate to identify potential digester operational problems caused by switchgrass co-digestion while accounting for uncertainty due to digester variability. Few studies have examined anaerobic digestion of switchgrass or the effects of mild heating to enhance alkaline pretreatment prior to biomass digestion. Results indicate that pretreatment can significantly enhance digestion of coarse-ground (≤ 0.78 cm particle size) switchgrass. Energy conversion efficiency as high as 63% was observed, and was comparable or superior to fine-grinding as a pretreatment method. The optimal NaOH concentration was found to be 5.5% (wt/wt alkaline/biomass) with a 91.7% moisture level. No evidence of operational problems such as solids build-up, poor mixing, or floating materials were observed. These results suggest the use of waste heat from a generator could reduce the concentration of alkaline required to adequately pretreat lignocellulosic feedstock prior to anaerobic digestion.

  16. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

    PubMed

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-14

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  17. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-01

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  18. Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS)3(pbh)2H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidene)benzo­hydrazide, C13H11N3O

    PubMed Central

    Paschalidis, Damianos G.; Harrison, William T. A.

    2016-01-01

    The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O]tris(thiocyanato-κN)praseodymium(III) mono­hydrate, [Pr(NCS)3(C13H11N3O)2H2O, (I), and aqua(nitrato-κ2 O,O′)[N′-(pyri­din-2-ylmethylidene-κN)benzohydrazide-κ2 N′,O](thiocyanato-κN)neo­dym­ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr3+ ion in (I) is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio­cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio­cyanate ion, a bidentate nitrate ion and a water mol­ecule to generate a distorted NdN5O5 bicapped square anti­prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case. PMID:26958385

  19. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon.

    PubMed

    Soulard, P; Tremblay, B

    2015-12-14

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed.

  20. TES/Aura L2 Water Vapor (H2O) Limb V6 (TL2H2OL)

    Atmospheric Science Data Center

    2018-03-01

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access: OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  1. Anaerobic digestion of thermal-alkaline-pretreated cephalosporin bacterial residues for methane production.

    PubMed

    Li, Guixia; Zhong, Weizhang; Wang, Rui; Chen, Jiaqi; Li, Zaixing

    2017-08-01

    Optimum anaerobic conditions of cephalosporin bacterial residues after thermal-alkaline pretreatment were determined by orthogonal experiments. And through biochemical methane potential tests (BMPs) for cephalosporin bacterial residues, the ability for bacterial degradation of cephalosporin was also evaluated. The thermal-alkaline pretreatment with the optimum values of 6% NaOH at 105 °C for 15 min significantly improved digestion performance. With the thermal-alkaline pretreatment, the specific methane yield of the pretreated cephalosporin bacterial residue increased by 254.79% compared with that of the un-pretreated cephalosporin bacterial residue. The results showed that anaerobic digestion of thermal-alkaline-pretreated cephalosporin bacterial residues could be one of the options for efficient methane production and waste treatment. This work investigates the thermal-alkaline pretreatment of cephalosporin bacterial residues, which can increase their methane yield by 254.79% compared with no pretreatment. The digestion performance is significantly improved under the condition of 6% NaOH at 105 °C for 15 min. The results show that anaerobic digestion of thermal-alkaline-pretreated cephalosporin bacterial residues could be one of the options for efficient methane production and waste treatment.

  2. Progesterone amplifies oxidative stress signal and promotes NO production via H2O2 in mouse kidney arterial endothelial cells.

    PubMed

    Yuan, Xiao-Hua; Fan, Yang-Yang; Yang, Chun-Rong; Gao, Xiao-Rui; Zhang, Li-Li; Hu, Ying; Wang, Ya-Qin; Jun, Hu

    2016-01-01

    The role of progesterone on the cardiovascular system is controversial. Our present research is to specify the effect of progesterone on arterial endothelial cells in response to oxidative stress. Our result showed that H2O2 (150 μM and 300 μM) induced cellular antioxidant response. Glutathione (GSH) production and the activity of Glutathione peroxidase (GPx) were increased in H2O2-treated group. The expression of glutamate cysteine ligase catalytic subunit (GCLC) and modifier subunit (GCLM) was induced in response to H2O2. However, progesterone absolutely abolished the antioxidant response through increasing ROS level, inhibiting the activity of Glutathione peroxidase (GPx), decreasing GSH level and reducing expression of GClC and GCLM. In our study, H2O2 induced nitrogen monoxide (NO) production and endothelial nitric oxide synthase (eNOS) expression, and progesterone promoted H2O2-induced NO production. Progesterone increased H2O2-induced expression of hypoxia inducible factor-α (HIFα) which in turn regulated eNOS expression and NO synthesis. Further study demonstrated that progesterone increased H2O2 concentration of culture medium which may contribute to NO synthesis. Exogenous GSH decreased the content of H2O2 of culture medium pretreated by progesterone combined with H2O2 or progesterone alone. GSH also inhibited expression of HIFα and eNOS, and abolished NO synthesis. Collectively, our study demonstrated for the first time that progesterone inhibited cellular antioxidant effect and increased oxidative stress, promoted NO production of arterial endothelial cells, which may be due to the increasing H2O2 concentration and amplified oxidative stress signal. Copyright © 2015. Published by Elsevier Ltd.

  3. Candidate Water Vapor Lines to Locate the H2O Snowline through High-dispersion Spectroscopic Observations. III. Submillimeter H2 16O and H2 18O Lines

    NASA Astrophysics Data System (ADS)

    Notsu, Shota; Nomura, Hideko; Walsh, Catherine; Honda, Mitsuhiko; Hirota, Tomoya; Akiyama, Eiji; Millar, T. J.

    2018-03-01

    In this paper, we extend the results presented in our former papers on using ortho-{{{H}}}2{}16{{O}} line profiles to constrain the location of the H2O snowline in T Tauri and Herbig Ae disks, to include submillimeter para-{{{H}}}2{}16{{O}} and ortho- and para-{{{H}}}2{}18{{O}} lines. Since the number densities of the ortho- and para-{{{H}}}2{}18{{O}} molecules are about 560 times smaller than their 16O analogs, they trace deeper into the disk than the ortho-{{{H}}}2{}16{{O}} lines (down to z = 0, i.e., the midplane). Thus these {{{H}}}2{}18{{O}} lines are potentially better probes of the position of the H2O snowline at the disk midplane, depending on the dust optical depth. The values of the Einstein A coefficients of submillimeter candidate water lines tend to be lower (typically <10‑4 s‑1) than infrared candidate water lines. Thus in the submillimeter candidate water line cases, the local intensity from the outer optically thin region in the disk is around 104 times smaller than that in the infrared candidate water line cases. Therefore, in the submillimeter lines, especially {{{H}}}2{}18{{O}} and para-{{{H}}}2{}16{{O}} lines with relatively lower upper state energies (∼a few 100 K) can also locate the position of the H2O snowline. We also investigate the possibility of future observations with ALMA to identify the position of the water snowline. There are several candidate water lines that trace the hot water gas inside the H2O snowline in ALMA Bands 5–10.

  4. Transgenic Centipedegrass (Eremochloa ophiuroides [Munro] Hack.) Overexpressing S-Adenosylmethionine Decarboxylase (SAMDC) Gene for Improved Cold Tolerance Through Involvement of H2O2 and NO Signaling.

    PubMed

    Luo, Jianhao; Liu, Mingxi; Zhang, Chendong; Zhang, Peipei; Chen, Jingjing; Guo, Zhenfei; Lu, Shaoyun

    2017-01-01

    Centipedegrass ( Eremochloa ophiuroides [Munro] Hack.) is an important warm-season turfgrass species. Transgenic centipedgrass plants overexpressing S-adenosylmethionine decarboxylase from bermudagrass ( CdSAMDC1 ) that was induced in response to cold were generated in this study. Higher levels of CdSAMDC1 transcript and sperimidine (Spd) and spermin (Spm) concentrations and enhanced freezing and chilling tolerance were observed in transgenic plants as compared with the wild type (WT). Transgenic plants had higher levels of polyamine oxidase (PAO) activity and H 2 O 2 than WT, which were blocked by pretreatment with methylglyoxal bis (guanylhydrazone) or MGBG, inhibitor of SAMDC, indicating that the increased PAO and H 2 O 2 were a result of expression of CdSAMDC1 . In addition, transgenic plants had higher levels of nitrate reductase (NR) activity and nitric oxide (NO) concentration. The increased NR activity were blocked by pretreatment with MGBG and ascorbic acid (AsA), scavenger of H 2 O 2 , while the increased NO level was blocked by MGBG, AsA, and inhibitors of NR, indicating that the enhanced NR-derived NO was dependent upon H 2 O 2 , as a result of expression CdSAMDC1 . Elevated superoxide dismutase (SOD) and catalase (CAT) activities were observed in transgenic plants than in WT, which were blocked by pretreatment with MGBG, AsA, inhibitors of NR and scavenger of NO, indicating that the increased activities of SOD and CAT depends on expression of CdSAMDC1 , H 2 O 2 , and NR-derived NO. Our results suggest that the elevated cold tolerance was associated with PAO catalyzed production of H 2 O 2 , which in turn led to NR-derived NO production and induced antioxidant enzyme activities in transgenic plants.

  5. TES/Aura L2 Water Vapor (H2O) Limb V6 (TL2H2OLS)

    Atmospheric Science Data Center

    2018-03-01

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access:  OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  6. Submillimeter H2O and H2O+emission in lensed ultra- and hyper-luminous infrared galaxies at z 2-4

    NASA Astrophysics Data System (ADS)

    Yang, C.; Omont, A.; Beelen, A.; González-Alfonso, E.; Neri, R.; Gao, Y.; van der Werf, P.; Weiß, A.; Gavazzi, R.; Falstad, N.; Baker, A. J.; Bussmann, R. S.; Cooray, A.; Cox, P.; Dannerbauer, H.; Dye, S.; Guélin, M.; Ivison, R.; Krips, M.; Lehnert, M.; Michałowski, M. J.; Riechers, D. A.; Spaans, M.; Valiante, E.

    2016-11-01

    We report rest-frame submillimeter H2O emission line observations of 11 ultra- or hyper-luminous infrared galaxies (ULIRGs or HyLIRGs) at z 2-4 selected among the brightest lensed galaxies discovered in the Herschel-Astrophysical Terahertz Large Area Survey (H-ATLAS). Using the IRAM NOrthern Extended Millimeter Array (NOEMA), we have detected 14 new H2O emission lines. These include five 321-312ortho-H2O lines (Eup/k = 305 K) and nine J = 2 para-H2O lines, either 202-111(Eup/k = 101 K) or 211-202(Eup/k = 137 K). The apparent luminosities of the H2O emission lines are μLH2O 6-21 × 108 L⊙ (3 <μ< 15, where μ is the lens magnification factor), with velocity-integrated line fluxes ranging from 4-15 Jy km s-1. We have also observed CO emission lines using EMIR on the IRAM 30 m telescope in seven sources (most of those have not yet had their CO emission lines observed). The velocity widths for CO and H2O lines are found to be similar, generally within 1σ errors in the same source. With almost comparable integrated flux densities to those of the high-J CO line (ratios range from 0.4 to 1.1), H2O is found to be among the strongest molecular emitters in high-redshift Hy/ULIRGs. We also confirm our previously found correlation between luminosity of H2O (LH2O) and infrared (LIR) that LH2O LIR1.1-1.2, with ournew detections. This correlation could be explained by a dominant role of far-infrared pumping in the H2O excitation. Modelling reveals that the far-infrared radiation fields have warm dust temperature Twarm 45-75 K, H2O column density per unit velocity interval NH2O /ΔV ≳ 0.3 × 1015 cm-2 km-1 s and 100 μm continuum opacity τ100> 1 (optically thick), indicating that H2O is likely to trace highly obscured warm dense gas. However, further observations of J ≥ 4 H2O lines are needed to better constrain the continuum optical depth and other physical conditions of the molecular gas and dust. We have also detected H2O+ emission in three sources. A tight correlation

  7. Studies of proton irradiated H2O + CO2 and H2O + CO ices and analysis of synthesized molecules

    NASA Technical Reports Server (NTRS)

    Moore, M. H.; Khanna, R.; Donn, B.

    1991-01-01

    Infrared spectra of H2O + CO2 and H2O + CO ices before and after proton irradiation showed that a major reaction in both mixtures was the interconversion of CO2 yields CO. Radiation synthesized organic compounds such as carbonic acid were identified in the H2O + CO2 ice. Different chemical pathways dominate in the H2O + CO ice in which formaldehyde, methanol, ethanol, and methane were identified. Sublimed material was also analyzed using a mass spectrometer. Implications of these results are discussed in reference to comets.

  8. [Mechanism and performance of styrene oxidation by O3/H2O2].

    PubMed

    He, Jue-Cong; Huang, Qian-Ru; Ye, Qi-Hong; Luo, Yu-Wei; Zhang, Zai-Li; Fan, Qing-Juan; Wei, Zai-Shan

    2013-10-01

    It can produce a large number of free radicals in O3/H2O2, system, ozone and free radical coupling oxidation can improve the styrene removal efficiency. Styrene oxidation by O3/H2O2 was investigated. Ozone dosage, residence time, H2o2 volume fraction, spray density and molar ratio of O3/C8H8 on styrene removal were evaluated. The experimental results showed that styrene removal efficiency achieved 85.7%. The optimal residence time, H2O2, volume fraction, spray density and O3/C8H8 molar ratio were 20. 6 s, 10% , 1.72 m3.(m2.h)-1 and 0.46, respectively. The gas-phase degradation intermediate products were benzaldehyde(C6H5CHO) and benzoic acid (C6H5 COOH) , which were identified by means of gas chromatography-mass spectrometry(GC-MS). The degradation mechanism of styrene is presented.

  9. LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

    NASA Astrophysics Data System (ADS)

    Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

    2016-01-01

    Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

  10. Photodegradation of the antineoplastic cyclophosphamide: a comparative study of the efficiencies of UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2 processes.

    PubMed

    Lutterbeck, Carlos Alexandre; Machado, Ênio Leandro; Kümmerer, Klaus

    2015-02-01

    Anticancer drugs are harmful substances that can have carcinogenic, mutagenic, teratogenic, genotoxic, and cytotoxic effects even at low concentrations. More than 50 years after its introduction, the alkylating agent cyclophosphamide (CP) is still one of the most consumed anticancer drug worldwide. CP has been detected in water bodies in several studies and is known as being persistent in the aquatic environment. As the traditional water and wastewater treatment technologies are not able to remove CP from the water, different treatment options such as advanced oxidation processes (AOPs) are under discussion to eliminate these compounds. The present study investigated the degradation of CP by three different AOPs: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. The light source was a Hg medium-pressure lamp. Prescreening tests were carried out and afterwards experiments based on the optimized conditions were performed. The primary elimination of the parent compounds and the detection of transformation products (TPs) were monitored with LC-UV-MS/MS analysis, whereas the degree of mineralization was monitored by measuring the dissolved organic carbon (DOC). Ecotoxicological assays were carried out with the luminescent bacteria Vibrio fischeri. CP was completely degraded in all treatments and UV/Fe(2+)/H2O2 was the fastest process, followed by UV/H2O2 and UV/TiO2. All the reactions obeyed pseudo-first order kinetics. Considering the mineralization UV/Fe(2+)/H2O2 and UV/TiO2 were the most efficient process with mineralization degrees higher than 85%, whereas UV/H2O2 achieved 72.5% of DOC removal. Five transformation products were formed during the reactions and identified. None of them showed significant toxicity against V. fischeri. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Catalase activity is stimulated by H2O2 in rich culture medium and is required for H2O2 resistance and adaptation in yeast☆

    PubMed Central

    Martins, Dorival; English, Ann M.

    2014-01-01

    Catalases are efficient scavengers of H2O2 and protect cells against H2O2 stress. Examination of the H2O2 stimulon in Saccharomyces cerevisiae revealed that the cytosolic catalase T (Ctt1) protein level increases 15-fold on H2O2 challenge in synthetic complete media although previous work revealed that deletion of the CCT1 or CTA1 genes (encoding peroxisomal/mitochondrial catalase A) does not increase the H2O2 sensitivity of yeast challenged in phosphate buffer (pH 7.4). This we attributed to our observation that catalase activity is depressed when yeast are challenged with H2O2 in nutrient-poor media. Hence, we performed a systematic comparison of catalase activity and cell viability of wild-type yeast and of the single catalase knockouts, ctt1∆ and cta1∆, following H2O2 challenge in nutrient-rich medium (YPD) and in phosphate buffer (pH 7.4). Ctt1 but not Cta1 activity is strongly induced by H2O2 when cells are challenged in YPD but suppressed when cells are challenged in buffer. Consistent with the activity results, exponentially growing ctt1∆ cells in YPD are more sensitive to H2O2 than wild-type or cta1∆ cells, whereas in buffer all three strains exhibit comparable H2O2 hypersensitivity. Furthermore, catalase activity is increased during adaptation to sublethal H2O2 concentrations in YPD but not in buffer. We conclude that induction of cytosolic Ctt1 activity is vital in protecting yeast against exogenous H2O2 but this activity is inhibited by H2O2 when cells are challenged in nutrient-free media. PMID:24563848

  12. The roles of two O-donor ligands in the Fe2+-binding and H2O2-sensing by the Fe2+-dependent H2O2 sensor PerR.

    PubMed

    Ji, Chang-Jun; Yang, Yoon-Mo; Kim, Jung-Hoon; Ryu, Su-Hyun; Youn, Hwan; Lee, Jin-Won

    2018-05-10

    PerR is a metal-dependent peroxide sensing transcription factor which controls the expression of genes involved in peroxide resistance. The function of Bacillus subtilis PerR is mainly dictated by the regulatory metal ion (Fe 2+ or Mn 2+ ) coordinated by three N-donor ligands (His37, His91, and His93) and two O-donor ligands (Asp85 and Asp104). While H 2 O 2 sensing by PerR is mediated by Fe 2+ -dependent oxidation of N-donor ligand (either His37 or His91), one of the O-donor ligands (Asp104), but not Asp85, has been proposed as the key residue that regulates the sensitivity of PerR to H 2 O 2 . Here we systematically investigated the relative roles of two O-donor ligands of PerR in metal-binding affinity and H 2 O 2 sensitivity in vivo and in vitro. Consistent with the previous report, in vitro the D104E-PerR could not sense low levels of H 2 O 2 in the presence of excess Fe 2+ sufficient for the formation of the Fe 2+ -bound D104E-PerR. However, the expression of PerR-regulated reporter fusion was not repressed by D104E-PerR in the presence of Fe 2+ , suggesting that Fe 2+ is not an effective corepressor for this mutant protein in vivo. Furthermore, in vitro metal titration assays indicate that D104E-PerR has a significantly reduced affinity for Fe 2+ , but not for Mn 2+ , when compared to wild type PerR. These data indicate that the type of O-donor ligand (Asp vs. Glu) at position 104 is an important determinant in providing high Fe 2+ -binding affinity required for the sensing of the physiologically relevant Fe 2+ -levels, in addition to its role in rendering PerR highly sensitive to physiological levels of H 2 O 2 . In comparison, the D85E-PerR did not show a perturbed change in Fe 2+ -binding affinity, however, it displayed a slightly decreased sensitivity to H 2 O 2 both in vivo and in vitro, suggesting that the type of O-donor ligand (Asp vs. Glu) at position 85 may be important for the fine-tuning of H 2 O 2 sensitivity. Copyright © 2018 Elsevier

  13. Improved volatile fatty acids anaerobic production from waste activated sludge by pH regulation: Alkaline or neutral pH?

    PubMed

    Ma, Huijun; Chen, Xingchun; Liu, He; Liu, Hongbo; Fu, Bo

    2016-02-01

    In this study, the anaerobic fermentation was carried out for volatile fatty acids (VFAs) production at different pH (between 7.0 and 10.0) conditions with untreated sludge and heat-alkaline pretreated waste activated sludge. In the fermentation with untreated sludge, the extent of hydrolysis of organic matters and extent of acidification at alkaline pH are 54.37% and 30.37%, respectively, resulting in the highest VFAs yield at 235.46mg COD/gVS of three pH conditions. In the fermentation with heat-alkaline pretreated sludge, the acidification rate and VFAs yield at neutral pH are 30.98% and 240.14mg COD/gVS, respectively, which are higher than that at other pH conditions. With the glucose or bovine serum albumin as substrate for VFAs production, the neutral pH showed a higher VFAs concentration than the alkaline pH condition. The results of terminal restriction fragment length polymorphism (T-RFLP) analysis indicated that the alkaline pH caused low microbial richness. Based on the results in this study, we demonstrated that the alkaline pH is favor of hydrolysis of organic matter in sludge while neutral pH improved the acidogenesis for the VFAs production from sludge. Our finding is obvious different to the previous research and helpful for the understanding of how heat-alkaline pretreatment and alkaline fermentation influence the VFAs production, and beneficial to the development of VFAs production process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. ESR investigation of ROS generated by H2O2 bleaching with TiO2 coated HAp.

    PubMed

    Saita, Makiko; Kobayashi, Kyo; Kobatashi, Kyou; Yoshino, Fumihiko; Hase, Hiriko; Nonami, Toru; Kimoto, Katsuhiko; Lee, Masaichi-Chang-il

    2012-01-01

    It is well known that clinical bleaching can be achieved with a solution of 30% hydrogen peroxide (H2O2) or H2O2/titanium dioxide (TiO2) combination. This study examined the hypothesis that TiO2 coated with hydroxyapatite (HAp-TiO2) can generate reactive oxygen species (ROS). ROS are generated via photocatalysis using electron spin resonance (ESR). The bleaching properties of HAp-TiO2 in the presence of H2O2 can be measured using hematoporphyrin litmus paper and extracted teeth. We demonstrate that superoxides (O2(•-)) and hydroxyl radicals (HO(•)) can be generated through excitation of anatase TiO2, rutile TiO2, anatase HAp-TiO2, and rutile HAp-TiO2 in the presence of H2O2. The combination of R HAp-TiO2 with H2O2 produced the highest level of HO(•) generation and the most marked bleaching effects of all the samples. The superior bleaching effects exhibited by R HAp-TiO2 with H2O2 suggest that this combination may lead to novel methods for the clinical application of bleaching treatments.

  15. Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

    PubMed

    Mizuse, Kenta; Fujii, Asuka

    2011-04-21

    Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

  16. Ab initio studies on Al(+)(H(2)O)(n), HAlOH(+)(H(2)O)(n-1), and the size-dependent H(2) elimination reaction.

    PubMed

    Siu, Chi-Kit; Liu, Zhi-Feng; Tse, John S

    2002-09-11

    We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations

  17. Pilot-Scale Batch Alkaline Pretreatment of Corn Stover

    DOE PAGES

    Kuhn, Erik M.; O’Brien, Marykate H.; Ciesielski, Peter N.; ...

    2015-12-18

    The goal of biomass pretreatment is to increase the enzymatic digestibility of the plant cell wall polysaccharides to produce sugars for upgrading to biofuels. Alkaline pretreatment has the ability to solubilize much of the lignin in biomass while the carbohydrates remain insoluble. With an increased research focus to produce high-value products from lignin, a low molecular weight, lignin-rich stream in a biorefinery is desirable. Here, this work reports on batch alkaline pretreatment of corn stover conducted using a three-factor, two-level central composite experimental design in a pilot-scale reactor to determine the relationship between sodium hydroxide (NaOH) loading, temperature, and anthraquinonemore » (AQ) charge on solids solubilization, component yields, and enzymatic digestibility of the residual solids. Operating conditions were 100 to 140 °C, 40 to 70 mg NaOH/g dry corn stover, and 0.05% to 0.2% (w/w) AQ loading. An enzymatic hydrolysis screening study was performed at 2% cellulose loading. Empirical modeling results showed that NaOH loading and temperature are both significant factors, solubilizing 15% to 35% of the solids and up to 54% of the lignin. Enzymatic hydrolysis of the residual solids produced good monomeric glucose (>90%) and xylose (>70%) yields at the more severe pretreatment conditions. We also found that the AQ charge was not a significant factor at the conditions studied, so efforts to reduce xylan and increase lignin solubilization using this compound were not successful. Lastly, while good lignin solubilization was achieved, effectively recovering this stream remains a challenge, and demonstrating performance in continuous reactors is still needed.« less

  18. Pilot-Scale Batch Alkaline Pretreatment of Corn Stover

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kuhn, Erik M.; O’Brien, Marykate H.; Ciesielski, Peter N.

    The goal of biomass pretreatment is to increase the enzymatic digestibility of the plant cell wall polysaccharides to produce sugars for upgrading to biofuels. Alkaline pretreatment has the ability to solubilize much of the lignin in biomass while the carbohydrates remain insoluble. With an increased research focus to produce high-value products from lignin, a low molecular weight, lignin-rich stream in a biorefinery is desirable. Here, this work reports on batch alkaline pretreatment of corn stover conducted using a three-factor, two-level central composite experimental design in a pilot-scale reactor to determine the relationship between sodium hydroxide (NaOH) loading, temperature, and anthraquinonemore » (AQ) charge on solids solubilization, component yields, and enzymatic digestibility of the residual solids. Operating conditions were 100 to 140 °C, 40 to 70 mg NaOH/g dry corn stover, and 0.05% to 0.2% (w/w) AQ loading. An enzymatic hydrolysis screening study was performed at 2% cellulose loading. Empirical modeling results showed that NaOH loading and temperature are both significant factors, solubilizing 15% to 35% of the solids and up to 54% of the lignin. Enzymatic hydrolysis of the residual solids produced good monomeric glucose (>90%) and xylose (>70%) yields at the more severe pretreatment conditions. We also found that the AQ charge was not a significant factor at the conditions studied, so efforts to reduce xylan and increase lignin solubilization using this compound were not successful. Lastly, while good lignin solubilization was achieved, effectively recovering this stream remains a challenge, and demonstrating performance in continuous reactors is still needed.« less

  19. Net alkalinity and net acidity 2: Practical considerations

    USGS Publications Warehouse

    Kirby, C.S.; Cravotta, C.A.

    2005-01-01

    The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the

  20. Effect of residual H2O2 from advanced oxidation processes on subsequent biological water treatment: A laboratory batch study.

    PubMed

    Wang, Feifei; van Halem, Doris; Liu, Gang; Lekkerkerker-Teunissen, Karin; van der Hoek, Jan Peter

    2017-10-01

    H 2 O 2 residuals from advanced oxidation processes (AOPs) may have critical impacts on the microbial ecology and performance of subsequent biological treatment processes, but little is known. The objective of this study was to evaluate how H 2 O 2 residuals influence sand systems with an emphasis on dissolved organic carbon (DOC) removal, microbial activity change and bacterial community evolution. The results from laboratory batch studies showed that 0.25 mg/L H 2 O 2 lowered DOC removal by 10% while higher H 2 O 2 concentrations at 3 and 5 mg/L promoted DOC removal by 8% and 28%. A H 2 O 2 dosage of 0.25 mg/L did not impact microbial activity (as measured by ATP) while high H 2 O 2 dosages, 1, 3 and 5 mg/L, resulted in reduced microbial activity of 23%, 37% and 37% respectively. Therefore, DOC removal was promoted by the increase of H 2 O 2 dosage while microbial activity was reduced. The pyrosequencing results illustrated that bacterial communities were dominated by Proteobacteria. The presence of H 2 O 2 showed clear influence on the diversity and composition of bacterial communities, which became more diverse under 0.25 mg/L H 2 O 2 but conversely less diverse when the dosage increased to 5 mg/L H 2 O 2 . Anaerobic bacteria were found to be most sensitive to H 2 O 2 as their growth in batch reactors was limited by both 0.25 and 5 mg/L H 2 O 2 (17-88% reduction). In conclusion, special attention should be given to effects of AOPs residuals on microbial ecology before introducing AOPs as a pre-treatment to biological (sand) processes. Additionally, the guideline on the maximum allowable H 2 O 2 concentration should be properly evaluated. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

  1. An Investigation of Armenite, BaCa2Al6Si9O302H2O.H2O Molecules and H Bonding in Microporous Silicates

    NASA Astrophysics Data System (ADS)

    Geiger, C. A.; Gatta, G.; Xue, X.; McIntyre, G.

    2012-12-01

    The crystal chemistry of armenite, ideally BaCa2Al6Si9O30.2H2O, a double-ring structure belonging to the milarite group, was studied to better understand the nature of extra-framework "Ca-oxygen-anion-H2O-molecule quasi-clusters" and H bonding behavior in microporous silicates. Neutron and X-ray single-crystal diffraction and IR powder and 1H NMR spectroscopic measurements were made. Four crystallographically independent Ca and H2O molecule sites were refined from the diffraction data, whereby both sites appear to have partial occupancies such that locally a Ca atom can have only a single H2O molecule bonded to it through an ion-dipole interaction. The Ca cation is further bonded to six O atoms of the framework forming a quasi cluster around it. The neutron results give the first static description of the protons in armenite, allowing bond distances and angles relating to the H2O molecules and H bonds to be determined. The IR spectrum of armenite is characterized in the OH-stretching region at RT by two broad bands at roughly 3470 and 3410 cm-1 and by a single H2O bending mode at 1654 cm-1. At 10 K four intense OH bands are located at 3479, 3454, 3401 and 3384 cm-1 and two H2O bending modes at 1650 and 1606 cm-1. The 1H MAS NMR spectrum shows a single strong resonance near 5.3 ppm and a smaller one near 2.7 ppm. The former can be assigned to H2O molecules bonded to Ca and the latter to weakly bonded H2O located at a site at the center of the structural double ring and it is partially occupied. The nature of H bonding in the microporous Ca-bearing zeolites scolecite, wairakite and epistilbite are also analyzed. The average OH stretching wavenumber shown by the IR spectra of armenite (~3435 cm-1) and scolecite (~3430 cm-1) are similar, while the average OH wavenumbers for wairakite (~3475 cm-1) and epistilbite (~3500 cm-1) are greater. In all cases the average OH stretching wavenumber is more similar to that of liquid water (~3400 cm-1) than of ice (~3220 cm-1). The

  2. Microchannel Reactor System Design & Demonstration For On-Site H2O2 Production by Controlled H2/O2 Reaction

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Adeniyi Lawal

    We successfully demonstrated an innovative hydrogen peroxide (H2O2) production concept which involved the development of flame- and explosion-resistant microchannel reactor system for energy efficient, cost-saving, on-site H2O2 production. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for controlled direct combination of H2 and O2 in all proportions including explosive regime, at a low pressure and a low temperature to produce about 1.5 wt% H2O2 as proposed. In the second phase of the program, as a prelude to full-scale commercialization, we demonstrated our H2O2 production approach by ‘numbering up’ the channels in a multi-channel microreactor-based pilot plant tomore » produce 1 kg/h of H2O2 at 1.5 wt% as demanded by end-users of the developed technology. To our knowledge, we are the first group to accomplish this significant milestone. We identified the reaction pathways that comprise the process, and implemented rigorous mechanistic kinetic studies to obtain the kinetics of the three main dominant reactions. We are not aware of any such comprehensive kinetic studies for the direct combination process, either in a microreactor or any other reactor system. We showed that the mass transfer parameter in our microreactor system is several orders of magnitude higher than what obtains in the macroreactor, attesting to the superior performance of microreactor. A one-dimensional reactor model incorporating the kinetics information enabled us to clarify certain important aspects of the chemistry of the direct combination process as detailed in section 5 of this report. Also, through mathematical modeling and simulation using sophisticated and robust commercial software packages, we were able to elucidate the hydrodynamics of the complex multiphase flows that take place in the microchannel. In conjunction with the kinetics information, we were able to validate the experimental data. If fully implemented across the

  3. Arsenite oxidation by H 2O 2 in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Pettine, Maurizio; Campanella, Luigi; Millero, Frank J.

    1999-09-01

    The rates of the oxidation of As( III) with H 2O 2 were measured in NaCl solutions as a function of pH (7.5-10.3), temperature (10-50C) and ionic strength ( I = 0.01-4). The rate of the oxidation of As( III) with H 2O 2 can be described by the general expression: d[As( III)]/ dt = k[As( III)] [H 2O 2] where k (mol/L -1 min -1) can be determined from (σ = ±0.12) log k=5.29+1.41 pH-0.57 I+1.40 I0.5-4898/ T. The effect of pH on the rates indicates that the reaction is due to AsO( OH) 2-+ H2O2k 1→productsAsO2( OH) 2-+ H2O2k 2→products, AsO33-+ H2O2k 3→products where k = k1 α AsO(OH) 2- + k2 α AsO 2(OH) 2- + k3 α AsO 3 3- and α i are the molar fraction of species i. The values of k1 = 42 ± 20, k2 = (8 ± 1) × 10 4, and k3 = (72 ± 18) × 10 6 mol/L -1 min -1 were found at 25C and I = 0.01 mol/L. The undissociated As(OH) 3 does not react with H 2O 2. The effect of ionic strength on the rate constants has been attributed to the effect of ionic strength on the speciation of As( III). The rate expression has been shown to be valid for NaClO 4 solutions, northern Adriatic sea waters, and Tiber River waters. The cations Fe 2+ and Cu 2+ were found to exert a catalytic effect on the rates. Cu 2+ plays a role at concentration levels (>0.1 μmol/L) which are typical of polluted aquatic systems, while Fe 2+ is important at levels which may be found in lacustrine environments (>5-10 μmol/L). The reaction of As( III) with H 2O 2 may play a role in marine and lacustrine surface waters limiting the accumulation of As( III) resulting from biologically mediated reduction processes of As( V).

  4. I + (H2O)2 → HI + (H2O)OH Forward and Reverse Reactions. CCSD(T) Studies Including Spin-Orbit Coupling.

    PubMed

    Wang, Hui; Li, Guoliang; Li, Qian-Shu; Xie, Yaoming; Schaefer, Henry F

    2016-03-03

    The potential energy profile for the atomic iodine plus water dimer reaction I + (H2O)2 → HI + (H2O)OH has been explored using the "Gold Standard" CCSD(T) method with quadruple-ζ correlation-consistent basis sets. The corresponding information for the reverse reaction HI + (H2O)OH → I + (H2O)2 is also derived. Both zero-point vibrational energies (ZPVEs) and spin-orbit (SO) coupling are considered, and these notably alter the classical energetics. On the basis of the CCSD(T)/cc-pVQZ-PP results, including ZPVE and SO coupling, the forward reaction is found to be endothermic by 47.4 kcal/mol, implying a significant exothermicity for the reverse reaction. The entrance complex I···(H2O)2 is bound by 1.8 kcal/mol, and this dissociation energy is significantly affected by SO coupling. The reaction barrier lies 45.1 kcal/mol higher than the reactants. The exit complex HI···(H2O)OH is bound by 3.0 kcal/mol relative to the asymptotic limit. At every level of theory, the reverse reaction HI + (H2O)OH → I + (H2O)2 proceeds without a barrier. Compared with the analogous water monomer reaction I + H2O → HI + OH, the additional water molecule reduces the relative energies of the entrance stationary point, transition state, and exit complex by 3-5 kcal/mol. The I + (H2O)2 reaction is related to the valence isoelectronic bromine and chlorine reactions but is distinctly different from the F + (H2O)2 system.

  5. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Smith, R. Scott; Li, Zhenjun; Chen, Long

    The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupymore » the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.« less

  6. Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Miliordos, Evangelos; Xantheas, Sotiris S.

    We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as theymore » contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

  7. Evidence for P(2)-purinoceptors contribution in H(2)O(2)-induced contraction of rat aorta in the absence of endothelium.

    PubMed

    Shen, J Z; Zheng, X F; Kwan, C Y

    2000-08-18

    , PKC, PLA(2) and cyclooxygenase. Lastly, removal of extracellular Ca(2+) or pretreatment with procaine (10 mM) and dantrolene (30 microM), two putative intracellular Ca(2+) release blockers, or with Ni(2+) (100 microM) and tetrandrine (5 microM), two Ca(2+) channel blockers, all significantly inhibited H(2)O(2) and ATP-induced contractions. However, nifedipine (1 microM), a voltage-dependent L-type Ca(2+) channel blocker, was without effect. Our results demonstrate that H(2)O(2)-induced phasic contraction of rat aorta involves, at least in part, the activation of P(2)-purinoceptors in the aortic smooth muscle cells

  8. Influence of Ar/O2/H2O Feed Gas and N2/O2/H2O Environment on the Interaction of Time Modulated MHz Atmospheric Pressure Plasma Jet (APPJ) with Model Polymers

    NASA Astrophysics Data System (ADS)

    Oehrlein, Gottlieb; Luan, Pingshan; Knoll, Andrew; Kondeti, Santosh; Bruggeman, Peter

    2016-09-01

    An Ar/O2/H2O fed time modulated MHz atmospheric pressure plasma jet (APPJ) in a sealed chamber was used to study plasma interaction with model polymers (polystyrene, poly-methyl methacrylate, etc.). The amount of H2O in the feed gas and/or present in the N2, O2, or N2/O2 environment was controlled. Short lived species such as O atoms and OH radicals play a crucial role in polymer etching and surface modifications (obtained from X-ray photoelectron spectroscopy of treated polymers without additional atmospheric exposure). Polymer etching depth for Ar/air fed APPJ mirrors the decay of gas phase O atoms with distance from the APPJ nozzle in air and is consistent with the estimated O atom flux at the polymer surface. Furthermore, whereas separate O2 or H2O admixture to Ar enhances polymer etching, simultaneous addition of O2 and H2O to Ar quenches polymer etching. This can be explained by the mutual quenching of O with OH, H and HO2 in the gas phase. Results where O2 and/or H2O in the environment were varied are consistent with these mechanisms. All results will be compared with measured and simulated species densities reported in the literature. We gratefully acknowledge funding from US Department of Energy (DE-SC0001939) and National Science Foundation (PHY-1415353).

  9. Combined alkaline and ultrasonic pretreatment of sludge before aerobic digestion.

    PubMed

    Jin, Yiying; Li, Huan; Mahar, Rasool Bux; Wang, Zhiyu; Nie, Yongfeng

    2009-01-01

    Alkaline and ultrasonic sludge disintegration can be used as the pretreatment of waste activated sludge (WAS) to promote the subsequent anaerobic or aerobic digestion. In this study, different combinations of these two methods were investigated. The evaluation was based on the quantity of soluble chemical oxygen demand (SCOD) in the pretreated sludge as well as the degradation of organic matter in the subsequent aerobic digestion. For WAS samples with combined pretreatment, the released COD levels were higher than those with ultrasonic or alkaline pretreatment alone. When combined with the ultrasonic treatment, NaOH treatment was more efficient than Ca(OH)2 for WAS solubilization. The COD levels released in various sequential options of combined NaOH and ultrasonic treatments were in the the following descending order: simultaneous treatment > NaOH treatment followed by ultrasonic treatment > ultrasonic treatment followed by NaOH treatment. For simultaneous treatment, low NaOH dosage (100 g/kg dry solid), short duration (30 min) of NaOH treatment, and low ultrasonic specific energy (7500 kJ/kg dry solid) were suitable for sludge disintegration. Using combined NaOH and ultrasonic pretreatment with optimal parameters, the degradation efficiency of organic matter was increased from 38.0% to 50.7%, which is much higher than that with ultrasonic (42.5%) or with NaOH pretreatment (43.5%) in the subsequent aerobic digestion at the same retention time.

  10. Au/n-ZnO rectifying contact fabricated with hydrogen peroxide pretreatment

    NASA Astrophysics Data System (ADS)

    Gu, Q. L.; Cheung, C. K.; Ling, C. C.; Ng, A. M. C.; Djurišić, A. B.; Lu, L. W.; Chen, X. D.; Fung, S.; Beling, C. D.; Ong, H. C.

    2008-05-01

    Au contacts were deposited on n-type ZnO single crystals with and without hydrogen peroxide pretreatment for the ZnO substrate. The Au/ZnO contacts fabricated on substrates without H2O2 pretreatment were Ohmic and those with H2O2 pretreatment were rectifying. With an aim of fabricating a good quality Schottky contact, the rectifying property of the Au/ZnO contact was systemically investigated by varying the treatment temperature and duration. The best performing Schottky contact was found to have an ideality factor of 1.15 and a leakage current of ˜10-7 A cm-2. A multispectroscopic study, including scanning electron microscopy, positron annihilation spectroscopy, deep level transient spectroscopy, x-ray photoelectron spectroscopy, and photoluminescence, showed that the H2O2 treatment removed the OH impurity and created Zn-vacancy related defects hence decreasing the conductivity of the ZnO surface layer, a condition favorable for forming good Schottky contact. However, the H2O2 treatment also resulted in a deterioration of the surface morphology, leading to an increase in the Schottky contact ideality factor and leakage current in the case of nonoptimal treatment time and temperature.

  11. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  12. Synthesis and characterization of polymer eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O as well as the interaction of [Y III(pdta)(H 2O)] 22- with BSA

    NASA Astrophysics Data System (ADS)

    Liu, Bin; Wang, Jun; Wang, Xin; Liu, Bing-Mi; He, Ling-Ling; Xu, Shu-Kun

    2010-12-01

    The eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O (en = ethylenediamine and H 4pdta = 1,3-propylenediamine- N, N, N', N'-tetraacetic acid) was synthesized, meanwhile its molecular and crystal structures were determined by single-crystal X-ray diffraction technology. The interaction between [Y III(pdta)(H 2O)] 22- and bovine serum albumin (BSA) was investigated by UV-vis and fluorescence spectra. The results indicate that [Y III(pdta)(H 2O)] 22- quenched effectively the intrinsic fluorescence of BSA via a static quenching process with the binding constant ( Ka) of the order of 10 4. Meanwhile, the binding and damaging sites to BSA molecules were also estimated by synchronous fluorescence. Results indicate that the hydrophobic environments around Trp and Tyr residues were all slightly changed. The thermodynamic parameters (Δ G = -25.20 kJ mol -1, Δ H = -26.57 kJ mol -1 and Δ S = -4.58 J mol -1 K -1) showed that the reaction was spontaneous and exothermic. What is more, both Δ H and Δ S were negative values indicated that hydrogen bond and Van der Waals forces were the predominant intermolecular forces between [Y III(pdta)(H 2O)] 22- and BSA.

  13. Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

    PubMed

    Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

    2012-04-19

    The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

  14. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT ETERNAL Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Wignall, J.; Lyons, Marv; Ertl, G.; Alefeld, Georg; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2013-03-01

    ''H2O H2O everywhere; ne'er a drop to drink''[Coleridge(1798)] now: ''H2 H2 everywhere; STILL ne'er a drop to drink'': ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): { ∖{}O/H2O{ ∖}} =[16]/[18] ∖sim 90{ ∖%} O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [ ∖underline {3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9 /2007)] crucial geomorphology which ONLY maximal-buoyancy H2 can exploit, to again make ''Mountains into Fountains'', ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': ''terraforming''(and ocean-rebasificaton!!!) ONLY VIA Siegel[APS March MTGS.:1960s-2000ss) DIFFUSIVE-MAGNETORESISTANCE (DMR) proprietary MAGNETIC-HYDROGEN-VALVE(MHV) ALL-IMPORTANT PRECLUDED RADIAL-diffusion, permitting ONLY AXIAL-H2-BALLISTIC-flow (``G.A''.''/DoE''/''Terrapower''/''Intellectual-Ventures''/ ''Gileland''/ ''Myhrvold''/''Gates'' ``ARCHIMEDES'') in ALREADY IN-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/ famine)

  15. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Lyons, M.; Siegel, E.

    2010-03-01

    ``Water water everywhere; ne'er a drop to drink''[Coleridg(1798)]; now:``Hydrogen hydrogen everywhere;STILL ne'er a drop to drink'': ONLY H2 can be ``FLYING-WATER''/``chemical-rain-in-pipelines''/ ``Hindenberg-effect (H2-UP;H2O-DOWN): atomic-weights ratio: O/H2O=[16]/[18]˜90%; O already in air uphill; NO H2O pumping need! In water-starved glacial-melting world, rescue ONLY by Siegel[3rd Intl.Conf.Alt.Energy,Hemisphere/Springer(1980)- vol.5/ p.459]Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating- system. Rosenfeld[Sci.315,1396(3/9/2007)]-Biello[Sci.Am.(3/9/ 2007)]crucial geomorphology which ONLY maximal-buoyancy light- est-element H2 can exploit, to again make ``Mountains into Fount- ains": Siegel ``terra-forming''(and ocean-rebasificaton!!!) long pre-``Holdren''-``Ciccerine" ``geo-enginering'', only via Siegel proprietary magnetic-hydrogen-valve permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Sci.300,1740(03)]global-pandemics (cancers/blindness/famine)dire-warning about H2-(ALONE)economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!

  16. Hydrodynamic cavitation-assisted alkaline pretreatment as a new approach for sugarcane bagasse biorefineries.

    PubMed

    Terán Hilares, Ruly; Dos Santos, Júlio César; Ahmed, Muhammad Ajaz; Jeon, Seok Hwan; da Silva, Silvio Silvério; Han, Jong-In

    2016-08-01

    Hydrodynamic cavitation (HC) was employed in order to improve the efficiency of alkaline pretreatment of sugarcane bagasse (SCB). Response surface methodology (RSM) was used to optimize pretreatment parameters: NaOH concentration (0.1-0.5M), solid/liquid ratio (S/L, 3-10%) and HC time (15-45min), in terms of glucan content, lignin removal and enzymatic digestibility. Under an optimal HC condition (0.48M of NaOH, 4.27% of S/L ratio and 44.48min), 52.1% of glucan content, 60.4% of lignin removal and 97.2% of enzymatic digestibility were achieved. Moreover, enzymatic hydrolysis of the pretreated SCB resulted in a yield 82% and 30% higher than the untreated and alkaline-treated controls, respectively. HC was found to be a potent and promising approach to pretreat lignocellulosic biomass. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

    PubMed

    Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, Zdenek; Kay, Bruce D

    2014-07-17

    The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K.

  18. Trapping {BW12}2 tungstoborate: synthesis and crystal structure of hybrid [{(H2BW12O42)2O}{Mo6O6S6(OH)4(H2O)2}]14- anion.

    PubMed

    Korenev, V S; Abramov, P A; Vicent, C; Mainichev, D A; Floquet, S; Cadot, E; Sokolov, M N; Fedin, V P

    2012-12-28

    Reaction between monolacunary {BW(11)} tungstoborate and oxothiocationic building block, {Mo(2)O(2)S(2)}, results in the formation of a new polyoxothiometalate with a unique architecture in which two [H(2)BW(12)O(43)](9-) tungstoborate subunits are linked together with a hexamolybdate [Mo(V)(6)O(6)S(6)(OH)(4)(H(2)O)(2)](2+) bridge.

  19. Cosmetic wastewater treatment by the ZVI/H2O2 process.

    PubMed

    Bogacki, Jan; Marcinowski, Piotr; Zapałowska, Ewa; Maksymiec, Justyna; Naumczyk, Jeremi

    2017-10-01

    The ZVI/H 2 O 2 process was applied for cosmetic wastewater treatment. Two commercial zero-valent iron (ZVI) types with different granulations were chosen: Hepure Ferrox PRB and Hepure Ferrox Target. In addition, the pH and stirring method influence on ZVI/H 2 O 2 process efficiency was studied. During the ZVI and ZVI/H 2 O 2 processes, linear Fe ions concentration increase was observed. The addition of H 2 O 2 significantly accelerated the iron dissolution process. The highest COD removal was obtained using finer ZVI (Hepure Ferrox Target) for doses of reagents ZVI/H 2 O 2 1500/1600 mg/L, in a H 2 O 2 /COD weight ratio 2:1, at pH 3.0 with stirring on a magnetic stirrer. After 120 min of the process, 84.0% COD removal (from 796 to 127 mg/L) was achieved. It was found that the efficiency of the process depends, as in the case of the Fenton process, on the ratio of the reagents (ZVI/H 2 O 2 ) and their dose in relation to the COD (H 2 O 2 /COD) but does not depend on the dose of the iron itself. Statistical analysis confirms that COD removal efficiency depends primarily on H 2 O 2 /COD ratio and ZVI granulation, but ZVI dose influence is not statistically significant. The head space, solid-phase microextraction, gas chromatography, mass spectrometry results confirm high efficiency of the ZVI/H 2 O 2 process.

  20. Luminescence Spectroscopy and Crystal Field Simulations of Europium Propylenediphosphonate EuH[O 3P(CH 2) 3PO 3] and Europium Glutarate [Eu(H 2O)] 2[O 2C(CH 2) 3CO 2] 3·4H 2O

    NASA Astrophysics Data System (ADS)

    Serpaggi, F.; Férey, G.; Antic-Fidancev, E.

    1999-12-01

    The results of investigations on the photoluminescence of two europium hybrid compounds, EuH[O3P(CH2)3PO3] (Eu[diph]) and [Eu(H2O)]2[O2C(CH2)3CO2]3·4H2O (Eu[glut]), are presented. In both compounds one local environment is found for the rare earth (Re) ion and the symmetry of the Re polyhedron is low (Cs) as evidenced by the Eu3+ luminescence studies. The electrostatic crystal field (cf) parameters of the 7F multiplet are obtained by the application of the phenomenological cf theory. The simulations using C2v symmetry for the rare earth ion give good agreement between the calculated and the experimental 7F0-4 energy level schemes. The observed optical data are discussed in relation to the crystal structure of the compounds.

  1. A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

    PubMed

    Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

    2013-03-01

    The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

  2. Alkaline sulfide pretreatment of an antimonial refractory Au-Ag ore for improved cyanidation

    NASA Astrophysics Data System (ADS)

    Alp, Ibrahim; Celep, Oktay; Deveci, Haci

    2010-11-01

    This paper presents the alkaline sulfide pretreatment of an antimonial refractory gold and silver ore. In the ore, gold occurs mainly as gold-silver alloys and as associated with quartz and framboidal pyrite grains, and, to a small extent, as the inclusions within antimonial sulfides. Silver is present extensively as antimonial sulfides such as andorite. Alkaline sulfide pretreatment was shown to allow the decomposition of the antimonial sulfide minerals (up to 98% Sb removal) and to remarkably improve the amenability of gold (e.g., from <49% up to 83%) and silver (e.g., from <18% up to 90%) to subsequent cyanide leaching. An increase in reagent concentration (1-4 mol/L Na2S or NaOH) and temperature (20-80°C), and a decrease in particle size seem to produce an enhancing effect on metal extraction. These findings suggest that alkaline sulfide leaching can be suitably used as a chemical pretreatment method prior to the conventional cyanidation for antimonial refractory gold and silver ores.

  3. H2O2_COD_EPA; MEC_acclimation

    EPA Pesticide Factsheets

    H2O2_COD_EPA: Measurements of hydrogen peroxide and COD concentrations for water samples from the MEC reactors.MEC_acclimation: raw data for current and voltage of the anode in the MEC reactor.This dataset is associated with the following publication:Sim, J., J. An, E. Elbeshbishy, R. Hodon, and H. Lee. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells. Bioresource Technology. Elsevier Online, New York, NY, USA, 195: 31-36, (2015).

  4. Synthesis, structure, optical, photoluminescence and magnetic properties of K2[Co(C2O4)2(H2O)2]·4H2O

    NASA Astrophysics Data System (ADS)

    Narsimhulu, M.; Hussain, K. A.

    2018-06-01

    The synthesis, crystal structure, optical, photoluminescence and magnetic behaviour of potassium bis(oxalato)cobaltate(II)tertrahydrate{K2[Co(C2O4)2(H2O)2]·4H2O} are described. The compound was grown at room temperature from mixture of aqueous solutions by slow evaporation method. The X-ray crystallographic data showed that the compound belongs to the monoclinic crystal system with P21/n space group and Z = 4. The UV-visible diffuse absorbance spectra exhibited bands at 253, 285 and 541 nm in the visible and ultraviolet regions. The optical band gap of the compound was estimated as 3.4 eV. At room temperature, an intense photoluminescence was observed from this material around 392 nm when it excited at 254 nm. The variable temperature dc magnetic susceptibility measurements exposed paramagnetic behaviour at high temperatures and antiferromagnetic ordering at low temperatures.

  5. Calcium-calmodulin is required for abscisic acid-induced antioxidant defense and functions both upstream and downstream of H2O2 production in leaves of maize (Zea mays) plants.

    PubMed

    Hu, Xiuli; Jiang, Mingyi; Zhang, Jianhua; Zhang, Aying; Lin, Fan; Tan, Mingpu

    2007-01-01

    * Using pharmacological and biochemical approaches, the role of calmodulin (CaM) and the relationship between CaM and hydrogen peroxide (H(2)O(2)) in abscisic acid (ABA)-induced antioxidant defense in leaves of maize (Zea mays) plants were investigated. * Treatment with ABA or H(2)O(2) led to significant increases in the concentration of cytosolic Ca(2+) in the protoplasts of mesophyll cells and in the expression of the calmodulin 1 (CaM1) gene and the content of CaM in leaves of maize plants, and enhanced the expression of the antioxidant genes superoxide dismutase 4 (SOD4), cytosolic ascorbate peroxidase (cAPX), and glutathione reductase 1 (GR1) and the activities of the chloroplastic and cytosolic antioxidant enzymes. The up-regulation of the antioxidant enzymes was almost completely blocked by pretreatments with two CaM antagonists. * Pretreatments with CaM antagonists almost completely inhibited ABA-induced H(2)O(2) production throughout ABA treatment, but pretreatment with an inhibitor or scavenger of reactive oxygen species (ROS) did not affect the initial increase in the contents of CaM induced by ABA. * Our results suggest that Ca(2+)-CaM is involved in ABA-induced antioxidant defense, and that cross-talk between Ca(2+)-CaM and H(2)O(2) plays a pivotal role in ABA signaling.

  6. Characterization of a real time H2O2 monitor for use in studies on H2O2 production by antibodies and cells.

    PubMed

    Sharma, Harish A; Balcavage, Walter X; Waite, Lee R; Johnson, Mary T; Nindl, Gabi

    2003-01-01

    It was recently shown that antibodies catalyze a reaction between water and ultraviolet light (UV) creating singlet oxygen and ultimately H2O2. Although the in vivo relevance of these antibody reactions is unclear, it is interesting that among a wide variety of non-antibody proteins tested, the T cell receptor is the only protein with similar capabilities. In clinical settings UV is believed to exert therapeutic effects by eliminating inflammatory epidermal T cells and we hypothesized that UV-triggered H2O2 production is involved in this process. To test the hypothesis we developed tools to study production of H2O2 by T cell receptors with the long-term goal of understanding, and improving, UV phototherapy. Here, we report the development of an inexpensive, real time H2O2 monitoring system having broad applicability. The detector is a Clark oxygen electrode (Pt, Ag/AgCl) modified to detect UV-driven H2O2 production. Modifications include painting the electrode black to minimize UV effects on the Ag/AgCl electrode and the use of hydrophilic, large pore Gelnots electrode membranes. Electrode current was converted to voltage and then amplified and recorded using a digital multimeter coupled to a PC. A reaction vessel with a quartz window was developed to maintain constant temperature while permitting UV irradiation of the samples. The sensitivity and specificity of the system and its use in cell-free and cell-based assays will be presented. In a cellfree system, production of H2O2 by CD3 antibodies was confirmed using our real time H2O2 monitoring method. Additionally we report the finding that splenocytes and Jurkat T cells also produce H2O2 when exposed to UV light.

  7. X-ray-induced dissociation of H.sub.2O and formation of an O.sub.2-H.sub.2 alloy at high pressure

    DOEpatents

    Mao, Ho-kwang [Washington, DC; Mao, Wendy L [Washington, DC

    2011-11-29

    A novel molecular alloy of O.sub.2 and H.sub.2 and a method of producing such a molecular alloy are provided. When subjected to high pressure and extensive x-radiation, H.sub.2O molecules cleaved, forming O--O and H--H bonds. In the method of the present invention, the O and H framework in ice VII was converted into a molecular alloy of O.sub.2 and H.sub.2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrate that this crystalline solid differs from previously known phases.

  8. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    PubMed Central

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  9. Alkaline peroxide pretreatment of corn stover for enzymatic saccharification and ethanol production

    USDA-ARS?s Scientific Manuscript database

    Alkaline hydrogen peroxide (AHP) pretreatment and enzymatic saccharification were evaluated for conversion of corn stover cellulose and hemicellulose to fermentable sugars. Corn stover used in this study contained 37.0±0.2% cellulose, 26.8±0.2% hemicellulose and 18.0±0.1% lignin on dry basis. Unde...

  10. High-Level ab initio electronic structure calculations of Water Clusters (H2O)16 and (H2O)17: a new global minimum for (H2O)16

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yoo, Soohaeng; Apra, Edoardo; Zeng, Xiao Cheng

    The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at the MP2 and CCSD(T) levels of theory and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17 the CCSD(T) calculations confirm the previously found at the MP2 level of theory "interior" arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum.

  11. High-Level ab-initio Electronic Structure Calculations of Water Clusters (H2O)16 and (H2O)17 : a New Global Minimum for (H2O)16

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yoo, Soohaeng; Apra, Edoardo; Zeng, X.C.

    The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at both the MP2 and CCSD(T) levels of theory, and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17, the CCSD(T) calculations confirm the previously found at the MP2 level of theory interior arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum

  12. Minimising alkalinity and pH spikes from Portland cement-bound Bauxsol (seawater-neutralized red mud) pellets for pH circum-neutral waters.

    PubMed

    Despland, Laure M; Clark, Malcolm W; Aragno, Michel; Vancov, Tony

    2010-03-15

    Bauxsol reagents (powder, slurry, or pellet forms) are powerful tools in environmental remediation and water and sewage treatment However, when used in circum-neutral water treatments, cement-bound Bauxsol pellets produce a sustained pH and alkalinity spike due to the presence of unreacted CaO in the cement binder. This study developed a pellet treatment system to minimize the alkalinity/pH spike. The recipe for pelletization consisted of Bauxsol powder, ordinary Portland cement (OPC), hydrophilic fumed silica, aluminum powder, a viscosity modifier, and water. Several batches (including different ratios and sizes) were run using modified makeup waters (H(2)0 + CO(2) or NaHCO(3)) or curing brines (CO(2), NaHCO(3), or Mg/CaCl(2)). Alkalinity, pH stability, and slake durability tests were performed on pellets before and/or after curing. The best result for reducing the alkalinity/pH spike was obtained from a MgCl(2), CaCl(2) bath treatment using a Bauxsol:cement ratio of 2.8:1 (pH 8.28; alkalinity 75.1 mg/L) for a 100 g batch or 245:1 (pH 8.05; alkalinity 35.4 mg/L) for a 1 kg batch. Although brine curing does provide a control on pH/alkalinity release, the pellets may still contain unreacted CaO. Therefore, a freshwater rinse of pellets before treating circum-neutral waters is recommended as is the continued investigation of alternative pellet binders.

  13. Degradation of 5-FU by means of advanced (photo)oxidation processes: UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2--Comparison of transformation products, ready biodegradability and toxicity.

    PubMed

    Lutterbeck, Carlos Alexandre; Wilde, Marcelo Luís; Baginska, Ewelina; Leder, Christoph; Machado, Ênio Leandro; Kümmerer, Klaus

    2015-09-15

    The present study investigates the degradation of the antimetabolite 5-fluorouracil (5-FU) by three different advanced photo oxidation processes: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. Prescreening experiments varying the H2O2 and TiO2 concentrations were performed in order to set the best catalyst concentrations in the UV/H2O2 and UV/TiO2 experiments, whereas the UV/Fe(2+)/H2O2 process was optimized varying the pH, Fe(2+) and H2O2 concentrations by means of the Box-Behnken design (BBD). 5-FU was quickly removed in all the irradiation experiments. The UV/Fe(2+)/H2O2 and UV/TiO2 processes achieved the highest degree of mineralization, whereas the lowest one resulted from the UV/H2O2 treatment. Six transformation products were formed during the advanced (photo)oxidation processes and identified using low and high resolution mass spectrometry. Most of them were formed and further eliminated during the reactions. The parent compound of 5-FU was not biodegraded, whereas the photolytic mixture formed in the UV/H2O2 treatment after 256 min showed a noticeable improvement of the biodegradability in the closed bottle test (CBT) and was nontoxic towards Vibrio fischeri. In silico predictions showed positive alerts for mutagenic and genotoxic effects of 5-FU. In contrast, several of the transformation products (TPs) generated along the processes did not provide indications for mutagenic or genotoxic activity. One exception was TP with m/z 146 with positive alerts in several models of bacterial mutagenicity which could demand further experimental testing. Results demonstrate that advanced treatment can eliminate parent compounds and its toxicity. However, transformation products formed can still be toxic. Therefore toxicity screening after advanced treatment is recommendable. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Fluid inclusion volatile analysis by gas chromatography with photoionization micro-thermal conductivity detectors: Applications to magmatic MoS 2 and other H 2O-CO 2 and H 2O-CH 4 fluids

    NASA Astrophysics Data System (ADS)

    Bray, C. J.; Spooner, E. T. C.

    1992-01-01

    the Cretaceous Boss Mtn. monzogranite stock-related MoS 2 deposit, central British Columbia of ~97 mol% H 2O, ~3% CO 2, ~ 140-150 ppm N 2, and ~16-39 ppm CH 4 (~300-350°C) are reasonable in comparison with high temperature (~400-900°C) volcanic gas analyses from four, active calc-alkaline volcanoes; e.g., the H 2O contents of volcanic gases from the White Island (New Zealand), Mount St. Helens (Washington, USA), Merapi (Bali, Indonesia), and Momotombo (Nicaragua) volcanoes are 88-95%, >90% (often >95%), 88-95% and ~93%, respectively; CO 2 contents are ~3-10%, 1-10%, 3-8%, and ~3.5%. CO 2/N 2 ratios for the Boss Mtn. MoS 2 fluids of ~ 190-220 are in the range for known volcanic gas ratios (e.g., ~ 150- 240; White Island). The ∑S content of the Boss Mtn. MoS 2 fluid prior to S loss by sulphide precipitation may have been ~2 mol% since CO 2/∑S molar ratios of analysed high-temperature volcanic gases are ~ 1.5. This estimate is supported by ∑S contents for White Island, Merapi and Momotombo volcanic gases of ~2%, ~0.5-2.5%, and ~2%. COS has been determined in H 2O-CO 2 fluid inclusions of interpreted magmatic origin from the Boss Mtn. MoS 2 deposit and the Tanco zoned granitic pegmatite, S.E. Manitoba at ~50-100 ppm molar levels, which are consistent with levels in volcanic gases. It appears that low, but significant, concentrations of C 2-C 4 alkanes (~ 1-20 ppm), C 2-C 4 alkenes (~ 1-480 ppb) and alkynes (e.g., C 3H 4) have been detected in magmatically derived fluids (Boss Mtn. MoS 2 deposit; Tanco granitic pegmatite). Significantly higher, low molecular weight hydrocarbon concentrations have been determined in a CH 4-rich (~ 2%), externally derived fluid of possible metamorphic or deep crustal origin trapped as inclusions in metasomatic wall-rock tourmaline adjacent to the Tanco pegmatite (e.g., 300/470 ppm C 2H 6; 50/90 ppm C 3H 8; 3-60 ppm C 2H 4/C 3H 6 n-C 4H 10).

  15. Synthesis of zinc sulfide nanoparticles during zinc oxidization by H2S and H2S/H2O supercritical fluids

    NASA Astrophysics Data System (ADS)

    Vostrikov, A. A.; Fedyaeva, O. N.; Sokol, M. Ya.; Shatrova, A. V.

    2014-12-01

    Formation of zinc sulfide nanoparticles was detected during interaction of bulk samples with hydrogen sulfide at supercritical parameters. Synthesis proceeds with liberation of H2 by the reaction nZn + nH2S = (ZnS) n + nH2. It has been found by the X-ray diffraction method, scanning electron microscopy, and mass spectrometry that the addition of water stimulates coupled reactions of nanoparticle synthesis nZn + nH2O = (ZnO) n + nH2 and (ZnO) n + nH2S = (ZnS) n + nH2O and brings about an increase in the synthesis rate and morphological changes of (ZnS) n nanoparticles.

  16. Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

    PubMed Central

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-01-01

    The title compounds, calcium perchlorate tetra­hydrate and calcium perchlorate hexa­hydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetra­hydrate consists of one Ca2+ cation eightfold coordinated in a square-anti­prismatic fashion by four water mol­ecules and four O atoms of four perchlorate tetra­hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra­hedra. The structure of the hexa­hydrate contains two different Ca2+ cations, each coordinated by six water mol­ecules and two O atoms of two perchlorate tetra­hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra­hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra­hedra. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

  17. Mechanism and toxicity research of benzalkonium chloride oxidation in aqueous solution by H2O2/Fe(2+) process.

    PubMed

    Zhang, Qian; Xia, Yu-Feng; Hong, Jun-Ming

    2016-09-01

    As widely used disinfectants, the pollution caused by benzalkonium chloride (BAC) has attracted a lot of attention in recent years. Since it is not suitable for biodegradation, BAC was degraded firstly by Fenton advanced oxidation technologies (AOTs) in this research to enhance the biodegradability of the pollutions. The result revealed that the optimal molar ratio of H2O2/Fe(2+) for BAC degradation was 10:1, and the COD removal rate was 32 %. To clarify the pathway of degradation, the technique of GC-MS was implemented herein to identify intermediates and the toxicity of those BAC intermediates were also novelty tested through microbial fuel cells (MFC). The findings indicated that ten transformation products including benzyl dimethyl amine and dodecane were formed during the H2O2/Fe(2+) processes, which means the degradation pathway of BAC was initiated both on the hydrophobic (alkyl chain) and hydrophilic (benzyl and ammonium moiety) region of the surfactant. The toxicity of BAC before and after treated by Fenton process was monitored through MFC system. The electricity generation was improved 337 % after BAC was treated by H2O2/Fe(2+) oxidation processes which indicated that the toxicity of those intermediates were much lower than BAC. The mechanism and toxicity research in this paper could provide the in-depth understanding to the pathway of BAC degradation and proved the possibility of AOTs for the pretreatment of a biodegradation process.

  18. Synthesis and X-ray Crystallography of [Mg(H2O)6][AnO2(C2H5COO)3]2 (An = U, Np, or Pu).

    PubMed

    Serezhkin, Viktor N; Grigoriev, Mikhail S; Abdulmyanov, Aleksey R; Fedoseev, Aleksandr M; Savchenkov, Anton V; Serezhkina, Larisa B

    2016-08-01

    Synthesis and X-ray crystallography of single crystals of [Mg(H2O)6][AnO2(C2H5COO)3]2, where An = U (I), Np (II), or Pu (III), are reported. Compounds I-III are isostructural and crystallize in the trigonal crystal system. The structures of I-III are built of hydrated magnesium cations [Mg(H2O)6](2+) and mononuclear [AnO2(C2H5COO)3](-) complexes, which belong to the AB(01)3 crystallochemical group of uranyl complexes (A = AnO2(2+), B(01) = C2H5COO(-)). Peculiarities of intermolecular interactions in the structures of [Mg(H2O)6][UO2(L)3]2 complexes depending on the carboxylate ion L (acetate, propionate, or n-butyrate) are investigated using the method of molecular Voronoi-Dirichlet polyhedra. Actinide contraction in the series of U(VI)-Np(VI)-Pu(VI) in compounds I-III is reflected in a decrease in the mean An═O bond lengths and in the volume and sphericity degree of Voronoi-Dirichlet polyhedra of An atoms.

  19. High-resolution photoelectron spectroscopy of TiO3H2-: Probing the TiO2- + H2O dissociative adduct

    NASA Astrophysics Data System (ADS)

    DeVine, Jessalyn A.; Abou Taka, Ali; Babin, Mark C.; Weichman, Marissa L.; Hratchian, Hrant P.; Neumark, Daniel M.

    2018-06-01

    Slow electron velocity-map imaging spectroscopy of cryogenically cooled TiO3H2- anions is used to probe the simplest titania/water reaction, TiO20/- + H2O. The resultant spectra show vibrationally resolved structure assigned to detachment from the cis-dihydroxide TiO(OH)2- geometry based on density functional theory calculations, demonstrating that for the reaction of the anionic TiO2- monomer with a single water molecule, the dissociative adduct (where the water is split) is energetically preferred over a molecularly adsorbed geometry. This work represents a significant improvement in resolution over previous measurements, yielding an electron affinity of 1.2529(4) eV as well as several vibrational frequencies for neutral TiO(OH)2. The energy resolution of the current results combined with photoelectron angular distributions reveals Herzberg-Teller coupling-induced transitions to Franck-Condon forbidden vibrational levels of the neutral ground state. A comparison to the previously measured spectrum of bare TiO2- indicates that reaction with water stabilizes neutral TiO2 more than the anion, providing insight into the fundamental chemical interactions between titania and water.

  20. Physical limit of stability in supercooled D2O and D2O+H2O mixtures

    NASA Astrophysics Data System (ADS)

    Kiselev, S. B.; Ely, J. F.

    2003-01-01

    The fluctuation theory of homogeneous nucleation was applied for calculating the physical boundary of metastable states, the kinetic spinodal, in supercooled D2O and D2O+H2O mixtures. The kinetic spinodal in our approach is completely determined by the surface tension and equation of state of the supercooled liquid. We developed a crossover equation of state for supercooled D2O, which predicts a second critical point of low density water-high density water equilibrium, CP2, and represents all available experimental data in supercooled D2O within experimental accuracy. Using Turnbull's expression for the surface tension we calculated with the crossover equation of state for supercooled D2O the kinetic spinodal, TKS, which lies below the homogeneous nucleation temperature, TH. We show that CP2 always lies inside in the so-called "nonthermodynamic habitat" and physically does not exist. However, the concept of a second "virtual" critical point is physical and very useful. Using this concept we have extended this approach to supercooled D2O+H2O mixtures. As an example, we consider here an equimolar D2O+H2O mixture in normal and supercooled states at atmospheric pressure, P=0.1 MPa.

  1. H2O2/TiO2 photocatalytic oxidation of metol. Identification of intermediates and reaction pathways.

    PubMed

    Aceituno, Mónica; Stalikas, Constantine D; Lunar, Loreto; Rubio, Soledad; Pérez-Bendito, Dolores

    2002-08-01

    The applicability of H2O2 to increase the efficiency of TiO2 photocatalytic degradations was investigated. The photographic developer metol [N-methyl-p-aminophenol] that does not adsorb on the surface of TiO2 particulates was used as a model for this purpose. It was proved that metol was mineralised under oxidation with H2O2/TiO2/UV through different thermal and photochemical reactions. Identification of intermediates by both HPLC-electron impact-MS and HPLC-electrospray ionisation-MS helped to elucidate the role of H2O2 and TiO2 in the degradation process and to establish degradation pathways. Intermediates yielded were partially oxygenated aromatic species and dimers, which were amenable to oxidation. The optimal degradation conditions found for mineralisation were 0.4 M H2O2, 5 mg/ml TiO2, pH 9 and irradiation centred at 360 nm (4.9 mW/cm2). The use of oxidants opens an interesting medium to the treatment of effluents containing a diversity of organics since they increase substantially the efficiency of TiO2 photocatalytic degradations.

  2. The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

    PubMed

    Vallet, V; Wahlgren, U; Schimmelpfennig, B; Szabó, Z; Grenthe, I

    2001-12-05

    The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO

  3. Effect of alkaline addition on anaerobic sludge digestion with combined pretreatment of alkaline and high pressure homogenization.

    PubMed

    Fang, Wei; Zhang, Panyue; Zhang, Guangming; Jin, Shuguang; Li, Dongyi; Zhang, Meixia; Xu, Xiangzhe

    2014-09-01

    To improve anaerobic digestion efficiency, combination pretreatment of alkaline and high pressure homogenization was applied to pretreat sewage sludge. Effect of alkaline dosage on anaerobic sludge digestion was investigated in detail. SCOD of sludge supernatant significantly increased with the alkaline dosage increase after the combined pretreatment because of sludge disintegration. Organics were significantly degraded after the anaerobic digestion, and the maximal SCOD, TCOD and VS removal was 73.5%, 61.3% and 43.5%, respectively. Cumulative biogas production, methane content in biogas and biogas production rate obviously increased with the alkaline dosage increase. Considering both the biogas production and alkaline dosage, the optimal alkaline dosage was selected as 0.04 mol/L. Relationships between biogas production and sludge disintegration showed that the accumulative biogas was mainly enhanced by the sludge disintegration. The methane yield linearly increased with the DDCOD increase as Methane yield (ml/gVS)=4.66 DDCOD-9.69. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Alkaline-sulfite pretreatment and use of surfactants during enzymatic hydrolysis to enhance ethanol production from sugarcane bagasse.

    PubMed

    Mesquita, Jéssica Faria; Ferraz, André; Aguiar, André

    2016-03-01

    Sugarcane bagasse is a by-product from the sugar and ethanol industry which contains approximately 70 % of its dry mass composed by polysaccharides. To convert these polysaccharides into fuel ethanol it is necessary a pretreatment step to increase the enzymatic digestibility of the recalcitrant raw material. In this work, sugarcane bagasse was pretreated by an alkaline-sulfite chemithermomechanical process for increasing its enzymatic digestibility. Na2SO3 and NaOH ratios were fixed at 2:1, and three increasing chemical loads, varying from 4 to 8 % m/m Na2SO3, were used to prepare the pretreated materials. The increase in the alkaline-sulfite load decreased the lignin content in the pretreated material up to 35.5 % at the highest chemical load. The pretreated samples presented enhanced glucose yields during enzymatic hydrolysis as a function of the pretreatment severity. The maximum glucose yield (64 %) was observed for the samples pretreated with the highest chemical load. The use of 2.5 g l(-1) Tween 20 in the hydrolysis step further increased the glucose yield to 75 %. Semi-simultaneous hydrolysis and fermentation of the pretreated materials indicated that the ethanol yield was also enhanced as a function of the pretreatment severity. The maximum ethanol yield was 56 ± 2 % for the sample pretreated with the highest chemical load. For the sample pretreated with the lowest chemical load (2 % m/m NaOH and 4 % m/m Na2SO3), adding Tween 20 during the hydrolysis process increased the ethanol yield from 25 ± 3 to 39.5 ± 1 %.

  5. Development of an E-H2O2/TiO2 photoelectrocatalytic oxidation system for water and wastewater treatment.

    PubMed

    Li, X Z; Liu, H S

    2005-06-15

    In this study, an innovative E-H2O2/TiO2 (E-H2O2 = electrogenerated hydrogen peroxide) photoelectrocatalytic (PEC) oxidation system was successfully developed for water and wastewater treatment. A TiO2/Ti mesh electrode was applied in this photoreactor as the anode to conduct PEC oxidation, and a reticulated vitreous carbon (RVC) electrode was used as the cathode to electrogenerate hydrogen peroxide simultaneously. The TiO2/Ti mesh electrode was prepared with a modified anodic oxidation process in a quadrielectrolyte (H2SO4-H3PO4-H2O2-HF) solution. The crystal structure, surface morphology, and film thickness of the TiO2/Ti mesh electrode were characterized by X-ray diffraction and scanning electron microscopy. The analytical results showed that a honeycomb-type anatase film with a thickness of 5 microm was formed. Photocatalytic oxidation (PC) and PEC oxidation of 2,4,6-trichlorophenol (TCP) in an aqueous solution were performed under various experimental conditions. Experimental results showed that the TiO2/Ti electrode, anodized in the H2SO4-H3PO4-H2O2-HF solution, had higher photocatalytic activity than the TiO2/Ti electrode anodized in the H2SO4 solution. It was found that the maximum applied potential would be around 2.5 V, corresponding to an optimum applied current density of 50 microA cm(-2) under UV-A illumination. The experiments confirmed that the E-H2O2 on the RVC electrode can significantly enhance the PEC oxidation of TCP in aqueous solution. The rate of TCP degradation in such an E-H2O2-assisted TiO2 PEC reaction was 5.0 times that of the TiO2 PC reaction and 2.3 times that of the TiO2 PEC reaction. The variation of pH during the E-H2O2-assisted TiO2 PEC reaction, affected by individual reactions, was also investigated. It was found that pH was well maintained during the TCP degradation in such an E-H2O2/TiO2 reaction system. This is beneficial to TCP degradation in an aqueous solution.

  6. Ab initio and transition state theory study of the OH + HO2H2O + O2(3Σg-)/O2(1Δg) reactions: yield and role of O2(1Δg) in H2O2 decomposition and in combustion of H2.

    PubMed

    Monge-Palacios, M; Sarathy, S Mani

    2018-02-07

    Reactions of hydroxyl (OH) and hydroperoxyl (HO 2 ) are important for governing the reactivity of combustion systems. We performed post-CCSD(T) ab initio calculations at the W3X-L//CCSD = FC/cc-pVTZ level to explore the triplet ground-state and singlet excited-state potential energy surfaces of the OH + HO 2H 2 O + O 2 ( 3 Σ g - )/O 2 ( 1 Δ g ) reactions. Using microcanonical and multistructural canonical transition state theories, we calculated the rate constant for the triplet and singlet channels over the temperature range 200-2500 K, represented by k(T) = 3.08 × 10 12 T 0.07  exp(1151/RT) + 8.00 × 10 12 T 0.32  exp(-6896/RT) and k(T) = 2.14 × 10 6 T 1.65  exp(-2180/RT) in cm 3 mol -1 s -1 , respectively. The branching ratios show that the yield of singlet excited oxygen is small (<0.5% below 1000 K). To ascertain the importance of singlet oxygen channel, our new kinetic information was implemented into the kinetic model for hydrogen combustion recently updated by Konnov (Combust. Flame, 2015, 162, 3755-3772). The updated kinetic model was used to perform H 2 O 2 thermal decomposition simulations for comparison against shock tube experiments performed by Hong et al. (Proc. Combust. Inst., 2013, 34, 565-571), and to estimate flame speeds and ignition delay times in H 2 mixtures. The simulation predicted a larger amount of O 2 ( 1 Δ g ) in H 2 O 2 decomposition than that predicted by Konnov's original model. These differences in the O 2 ( 1 Δ g ) yield are due to the use of a higher ab initio level and a more sophisticated methodology to compute the rate constant than those used in previous studies, thereby predicting a significantly larger rate constant. No effect was observed on the rate of the H 2 O 2 decomposition and on the flame speeds and ignition delay times of different H 2 -oxidizer mixtures. However, if the oxidizer is seeded with O 3 , small differences appear in the flame speed. Given that O 2 ( 1 Δ g ) is much more reactive than O

  7. (C6N2H16)[Co(H2O)6](SO4)2.2H2O: A new hybrid material based on sulfate templated by diprotonated trans-1,4-diaminocyclohexane

    NASA Astrophysics Data System (ADS)

    Hamdi, N.; Ngopoh, F. A. I.; da Silva, I.; El Bali, B.; Lachkar, M.

    2018-03-01

    Employing trans-1,4-diaminocyclohexane (DACH) as template, the new hybrid sulphate (C6N2H16)[Co(H2O)6](SO4)2.2H2O was prepared in solution. Single-crystal X-ray diffraction analysis shows that it crystallizes in the monoclinic system (S.G.: P 21/n), with the following unit-cell parameters (Å,°): a = 6.2897(2), b = 12.3716(6), c = 13.1996(4), β = 98.091(3) V = 1016.89(7) Å3, Z = 4. Its 3D crystal structure is made upon isolated [Co(H2O)6] octahedra, regular [SO4] tetrahedra, protonated DACH and free H2O molecules, which interact through N-H···O and O-H···O hydrogen bonds. The Fourier transform infrared result exhibits bands corresponding to the vibrations of DACH, sulfate group and water molecules. The thermal decomposition of the phase consists mainly in the loss of the organic moiety and one sulfate group, leading thus to the formation of anhydrous cobalt sulfate.

  8. UV and VUV photolysis vs. UV/H2O2 and VUV/H2O2, treatment for removal of clofibric acid from aqueous solution.

    PubMed

    Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

    2011-07-01

    Clofibric acid (CA), a metabolite of lipid regulators, was investigated in ultra-pure water and sewage treatment plant (STP) effluent at 10 degrees C under UV, vacuum UV (VUV), UV/H2O2 and VUV/H2O2 processes. The influences of NO3-, HCO3- and humic acid (HA) on CA photolysis in all processes were examined. The results showed that all the experimental data well fitted the pseudo-first-order kinetic model, and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated accordingly. Direct photolysis of CA through UV irradiation was the main process, compared with the indirect oxidation of CA due to the slight generation of hydroxyl radicals dissociated from water molecules under UV irradiation below 200 nm monochromatic wavelength emission. In contrast, indirect oxidation was the main CA degradation mechanism in UV/H2O2 and VUV/H2O2, and VUV/H2O2 was the most effective process for CA degradation. The addition of 20 mg L(-1) HA could significantly inhibit CA degradation, whereas, except for UV irradiation, the inhibitive effects of NO3- and HCO3- (1.0 x 10(-3) and 0.1 mol L(-1), respectively) on CA degradation were observed in all processes, and their adverse effects were more significant in UV/H2O2 and VUV/H2O2 processes, particularly at the high NO3- and HCO3- concentrations. The degradation rate decreased 1.8-4.9-fold when these processes were applied to a real STP effluent owing to the presence of complex constituents. Of the four processes, VUV/H2O2 was the most effective, and the CA removal efficiency reached over 99% after 40 min in contrast to 80 min in both the UV/H2O2 and VUV processes and 240 min in the UV process.

  9. Turbulence in Supercritical O2/H2 and C7H16/N2 Mixing Layers

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Harstad, Kenneth; Okong'o, Nora

    2003-01-01

    This report presents a study of numerical simulations of mixing layers developing between opposing flows of paired fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence. The simulations were performed for two different fluid pairs O2/H2 and C7H16/N2 at similar reduced initial pressures (reduced pressure is defined as pressure divided by critical pressure). Thermodynamically, O2/H2 behaves more nearly like an ideal mixture and has greater solubility, relative to C7H16/N2, which departs strongly from ideality. Because of a specified smaller initial density stratification, the C7H16/N2 layers exhibited greater levels of growth, global molecular mixing, and turbulence. However, smaller density gradients at the transitional state for the O2/H2 system were interpreted as indicating that locally, this system exhibits enhanced mixing as a consequence of its greater solubility and closer approach to ideality. These thermodynamic features were shown to affect entropy dissipation, which was found to be larger for O2/H2 and concentrated in high-density-gradient-magnitude regions that are distortions of the initial density-stratification boundary. In C7H16/N2, the regions of largest dissipation were found to lie in high-density-gradient-magnitude regions that result from mixing of the two fluids.

  10. Infrared spectra of seeded hydrogen clusters: (para-H2)N-N2O and (ortho-H2)N-N2O, N = 2-13.

    PubMed

    Tang, Jian; McKellar, A R W

    2005-09-15

    High-resolution infrared spectra of clusters containing para-H2 and/or ortho-H2 and a single nitrous oxide molecule are studied in the 2225-cm(-1) region of the upsilon1 fundamental band of N2O. The clusters are formed in pulsed supersonic jet expansions from a cooled nozzle and probed using a tunable infrared diode laser spectrometer. The simple symmetric rotor-type spectra generally show no resolved K structure, with prominent Q-branch features for ortho-H2 but not para-H2 clusters. The observed vibrational shifts and rotational constants are reported. There is no obvious indication of superfluid effects for para-H2 clusters up to N=13. Sharp transitions due to even larger clusters are observed, but no definite assignments are possible. Mixed (para-H2)N-(ortho-H2)M-N2O cluster line positions can be well predicted by linear interpolation between the corresponding transitions of the pure clusters.

  11. Application of TAED/H2O2 system for low temperature bleaching of crude cellulose extracted from jute fiber

    NASA Astrophysics Data System (ADS)

    Wen, Zuoqiang; Zou, Linbo; Wang, Weiming

    2018-03-01

    Tetraacetylethylenediamine (TAED) activated hydrogen peroxide system had been applied for bleaching of crude cellulose extracted from jute fiber. Comparing with conventional hydrogen peroxide bleaching system, those results showed that bleaching temperature and time could be effectively reduced, and a preferable whiteness could be produced under faint alkaline condition. And the optimum conditions for activated bleaching system could be summarized as molar ratio of H2O2/TAED 1:0.7, pH 8, pure hydrogen peroxide 0.09 mol/L, temperature 70 °C and time 60min.

  12. The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Davidson, Stephen D.; Sun, Junming; Wang, Yong

    The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway,more » evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.« less

  13. Cytoprotective Effect of Hydroalcoholic Extract of Pinus eldarica Bark against H2O2-Induced Oxidative Stress in Human Endothelial Cells

    PubMed Central

    Babaee, Fatemeh; Safaeian, Leila; Zolfaghari, Behzad; Haghjoo Javanmard, Shaghayegh

    2016-01-01

    Background: Pinus eldarica is a widely growing pine in Iran consisting of biologically active constituents with antioxidant properties. This study investigates the effect of hydroalcoholic extract of P. eldarica bark against oxidative damage induced by hydrogen peroxide (H2O2) in human umbilical vein endothelial cells (HUVECs). Methods: The total phenolic content of P. eldarica extract was determined using Folin-Ciocalteu method. The cytotoxicity of P. eldarica extract (25-1000 µg/ml) on HUVECs was assessed using 3-(4,5- Dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) method. Cytoprotective effect of P. eldarica extract (25-500 µg/ml) on H2O2-induced oxidative stress was also evaluated by MTT assay. The intra- and extra-cellular hydroperoxides concentration and ferric reducing antioxidant power (FRAP) were measured in pretreated cells. Results: The total phenolic content of P. eldarica extract was estimated as 37.04±1.8% gallic acid equivalent. P. eldarica extract (25-1000 µg/ml) had no cytotoxic effect on HUVECs viability. The pretreatment of HUVECs with P. eldarica extract at the concentrations of 50-500 µg/ml significantly reduced the cytotoxicity of H2O2. P. eldarica extract decreased hydroperoxides concentration and increased FRAP value in intra-cellular fluid at the concentration range of 100-500 µg/ml and in extra-cellular fluid at the concentration range of 25-500 µg/ml. Conclusions: This study revealed the antioxidant and cytoprotective effects of P. eldarica extract against H2O2-induced oxidative stress in HUVECs. Concerning the high content of phenolic compounds in P. eldarica, more research is needed to evaluate its clinical value in endothelial dysfunction and in other oxidative conditions. PMID:26931383

  14. High temperature kinetic study of the reactions H + O2 = OH + O and O + H2 = OH + H in H2/O2 system by shock tube-laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Ryu, Si-Ok; Hwang, Soon Muk; Dewitt, Kenneth J.

    1995-01-01

    The reactions: (1) H + O2 = OH + O; and (2) O + H2 = OH + H are the most important elementary reactions in gas phase combustion. They are the main chain-branching reaction in the oxidation of H2 and hydrocarbon fuels. In this study, rate coefficients of the reactions and have been measured over a wide range of composition, pressure, density and temperature behind the reflected shock waves. The experiments were performed using the shock tube - laser absorption spectroscopic technique to monitor OH radicals formed in the shock-heated H2/O2/Ar mixtures. The OH radicals were detected using the P(1)(5) line of (0,0) band of the A(exp 2) Sigma(+) from X(exp 2) Pi transition of OH at 310.023 nm (air). The data were analyzed with the aid of computer modeling. In the experiments great care was exercised to obtain high time resolution, linearity and signal-to-noise. The results are well represented by the Arrhenius expressions. The rate coefficient expression for reaction (1) obtained in this study is k(1) = (7.13 +/- 0.31) x 10(exp 13) exp(-6957+/- 30 K/T) cu cm/mol/s (1050 K less than or equal to T less than or equal to 2500 K) and a consensus expression for k(1) from a critical review of the most recent evaluations of k(1) (including our own) is k(1) = 7.82 x 10(exp 13) exp(-7105 K/T) cu cm/mol/s (960 K less than or equal to T less than or equal to 5300 K). The rate coefficient expression of k(2) is given by k(2) = (1.88 +/- 0.07) x 10(exp 14) exp(-6897 +/- 53 K/T) cu cm/mol/s (1424 K less than or equal to T less than or equal to 2427 K). For k(1), the temperature dependent A-factor and the correlation between the values of k(1) and the inverse reactant densities were not found. In the temperature range of this study, non-Arrhenius expression of k(2) which shows the upward curvature was not supported.

  15. Transcriptome Analysis of H2O2-Treated Wheat Seedlings Reveals a H2O2-Responsive Fatty Acid Desaturase Gene Participating in Powdery Mildew Resistance

    PubMed Central

    Tang, Lichuan; Zhao, Guangyao; Zhu, Mingzhu; Chu, Jinfang; Sun, Xiaohong; Wei, Bo; Zhang, Xiangqi; Jia, Jizeng; Mao, Long

    2011-01-01

    Hydrogen peroxide (H2O2) plays important roles in plant biotic and abiotic stress responses. However, the effect of H2O2 stress on the bread wheat transcriptome is still lacking. To investigate the cellular and metabolic responses triggered by H2O2, we performed an mRNA tag analysis of wheat seedlings under 10 mM H2O2 treatment for 6 hour in one powdery mildew (PM) resistant (PmA) and two susceptible (Cha and Han) lines. In total, 6,156, 6,875 and 3,276 transcripts were found to be differentially expressed in PmA, Han and Cha respectively. Among them, 260 genes exhibited consistent expression patterns in all three wheat lines and may represent a subset of basal H2O2 responsive genes that were associated with cell defense, signal transduction, photosynthesis, carbohydrate metabolism, lipid metabolism, redox homeostasis, and transport. Among genes specific to PmA, ‘transport’ activity was significantly enriched in Gene Ontology analysis. MapMan classification showed that, while both up- and down- regulations were observed for auxin, abscisic acid, and brassinolides signaling genes, the jasmonic acid and ethylene signaling pathway genes were all up-regulated, suggesting H2O2-enhanced JA/Et functions in PmA. To further study whether any of these genes were involved in wheat PM response, 19 H2O2-responsive putative defense related genes were assayed in wheat seedlings infected with Blumeria graminis f. sp. tritici (Bgt). Eight of these genes were found to be co-regulated by H2O2 and Bgt, among which a fatty acid desaturase gene TaFAD was then confirmed by virus induced gene silencing (VIGS) to be required for the PM resistance. Together, our data presents the first global picture of the wheat transcriptome under H2O2 stress and uncovers potential links between H2O2 and Bgt responses, hence providing important candidate genes for the PM resistance in wheat. PMID:22174904

  16. H2O2/HCl and heat-treated Ti-6Al-4V stimulates pre-osteoblast proliferation and differentiation.

    PubMed

    Shi, Geng-sheng; Ren, Ling-fei; Wang, Lin-zhi; Lin, Hai-sheng; Wang, Sha-bin; Tong, Yong-qing

    2009-09-01

    The purpose of the present study was to evaluate the bioactivity of chemical treatment of titanium alloy (Ti-6Al-4V) in vitro. Smooth-surface discs of Ti-6Al-4V were used in this study. Sandblasted, dual acid-etched and H(2)O(2)/HCl heat-treated discs were set as test group, and sandblasted, dual acid-etched discs as control group. SEM and XRD analysis revealed a porous anatase gel layer on rough surface in the test group and a rough surface in the control group. Mouse pre-osteoblasts (MC3T3-E1 cells) were cultured on these 2 group discs, and then cell proliferation and differentiation were examined 4 days, 7 days, and 14 days after cell seeding. Cell proliferation was greatly stimulated at all time points when cultured in test group (P < .05). The alkaline phosphatase (ALP) activity and osteocalcin (OC) production were much higher in the test group compared with the control group at every time point investigated (P < .05). Furthermore, in the test group, the expressions of alkaline phosphatase-2, osteocalcin, and collagen type I alpha 1 mRNAs were significantly up-regulated as compared with those in the control group (P < .05 or P < .01). The results suggested that H(2)O(2)/HCl and heat-treatment might facilitate better integration of Ti-6Al-4V implants with bone.

  17. Removal of pharmaceutically active compounds from synthetic and real aqueous mixtures and simultaneous disinfection by supported TiO2/UV-A, H2O2/UV-A, and TiO2/H2O2/UV-A processes.

    PubMed

    Bosio, Morgana; Satyro, Suéllen; Bassin, João Paulo; Saggioro, Enrico; Dezotti, Márcia

    2018-05-01

    Pharmaceutically active compounds are carried into aquatic bodies along with domestic sewage, industrial and agricultural wastewater discharges. Psychotropic drugs, which can be toxic to the biota, have been detected in natural waters in different parts of the world. Conventional water treatments, such as activated sludge, do not properly remove these recalcitrant substances, so the development of processes able to eliminate these compounds becomes very important. Advanced oxidation processes are considered clean technologies, capable of achieving high rates of organic compounds degradation, and can be an efficient alternative to conventional treatments. In this study, the degradation of alprazolam, clonazepam, diazepam, lorazepam, and carbamazepine was evaluated through TiO 2 /UV-A, H 2 O 2 /UV-A, and TiO 2 /H 2 O 2 /UV-A, using sunlight and artificial irradiation. While using TiO 2 in suspension, best results were found at [TiO 2 ] = 0.1 g L -1 . H 2 O 2 /UV-A displayed better results under acidic conditions, achieving from 60 to 80% of removal. When WWTP was used, degradation decreased around 50% for both processes, TiO 2 /UV-A and H 2 O 2 /UV-A, indicating a strong matrix effect. The combination of both processes was shown to be an adequate approach, since removal increased up to 90%. H 2 O 2 /UV-A was used for disinfecting the aqueous matrices, while mineralization was obtained by TiO 2 -photocatalysis.

  18. Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

    NASA Technical Reports Server (NTRS)

    Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

    2004-01-01

    The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

  19. Pt/SnO2-based CO-oxidation catalysts for CO2 lasers

    NASA Technical Reports Server (NTRS)

    Upchurch, Billy T.; Schryer, David R.; Hess, Robert V.; Brown, Kenneth G.; Van Norman, John D.

    1990-01-01

    The activity of Pt/SnO2-based CO-oxidation catalysts has been maximized by optimizing pretreatment conditions and catalyst formulation. The role of H2O in activating these catalysts and of CO2 retention in deactivating them has been determined as has the interaction of these catalysts with rare-isotope C(0-18) and (O-18)2.

  20. Comparison of seven types of thermo-chemical pretreatments on the structural features and anaerobic digestion of sunflower stalks.

    PubMed

    Monlau, F; Barakat, A; Steyer, J P; Carrere, H

    2012-09-01

    Sunflower stalks can be used for the production of methane, but their recalcitrant structure requires the use of thermo-chemical pretreatments. Two thermal (55 and 170°C) and five thermo-chemical pretreatments (NaOH, H(2)O(2), Ca(OH)(2), HCl and FeCl(3)) were carried out, followed by anaerobic digestion. The highest methane production (259 ± 6 mL CH(4)g(-1) VS) was achieved after pretreatment at 55°C with 4% NaOH for 24h. Acidic pretreatments at 170°C removed more than 90% of hemicelluloses and uronic acids whereas alkaline and oxidative pretreatments were more effective in dissolving lignin. However, no pretreatment was effective in reducing the crystallinity of cellulose. Methane production rate was positively correlated with the amount of solubilized matter whereas methane potential was negatively correlated with the amount of lignin. Considering that the major challenge is obtaining increased methane potential, alkaline pretreatments can be recommended in order to optimize the anaerobic digestion of lignocellulosic substrates. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. Degradation of p-Nitrophenol by Lignin and Cellulose Chars: H2O2-Mediated Reaction and Direct Reaction with the Char.

    PubMed

    Yang, Jing; Pignatello, Joseph J; Pan, Bo; Xing, Baoshan

    2017-08-15

    Chars and other black carbons are reactive toward certain compounds. Such reactivity has been attributed to reduction of O 2 by persistent free radicals in the solid to H 2 O 2 , which then back-reacts with the solid to generate reactive oxygen species (ROS; especially HO • ). We studied the decomposition of p-nitrophenol (PNP) by pure lignin and cellulose chars aged in moist air or a vacuum at room temperature for up to a month. In air, the chars chemisorbed oxygen, a portion of which was liberated as H 2 O 2 when the char was submerged in water. The evolved H 2 O 2 was simultaneously decomposed by the char. PNP reacted predominantly in the sorbed state and only reduction products (phenol, catechol) were identified. Aging the char in air sharply (within hours) reduced H 2 O 2 -producing capacity and free radical concentration, but more gradually reduced PNP decay rate over the month-long period. PNP decay was only modestly suppressed (12-30%) by H 2 O 2 removal (catalase), and had little effect on the free radical signal (<6 radicals annihilated per 1000 PNP reacted). Contrasting with previous studies, the results show that direct reaction of PNP with char predominates over H 2 O 2 -dependent reactions, and the vast majority of direct-reacting sites are nonradical in character. Nonradical sites are also responsible in part for H 2 O 2 decomposition; in fact, H 2 O 2 pretreatment depleted PNP reactive sites. Lignin char was generally more reactive than cellulose char. The Fe impurity in lignin played no role. The results are relevant to the fate of pollutants in black carbon-rich environments and the use of carbons in remediation.

  2. Effect of alkaline earth oxides on the physical and spectroscopic properties of Dy3+- doped Li2O-B2O3 glasses for white emitting material application

    NASA Astrophysics Data System (ADS)

    Shamshad, L.; Rooh, G.; Kirdsiri, K.; Srisittipokakun, N.; Damdee, B.; Kim, H. J.; Kaewkhao, J.

    2017-02-01

    Li2O-MO-B2O3:0.5Dy2O3 glasses mixed with four different alkaline earth modifier oxides MgO, CaO, SrO and BaO were synthesized by melt quench technique. Their physical properties like density, molar volume and refractive index were measured at room temperature and the effect of alkaline earth modifier oxides were studied. Also, optical absorption and photoluminescence spectra of these glasses have been acquired at room temperature. The Judd-Ofelt theory was effectively used to characterize these spectra and spectral intensities (ƒcal), Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6) and certain radiative properties have been determined. Radiative life-times (τR), branching ratios (βcal), and emission cross-sections (σp) and optical gain parameters (σp × τR) were calculated from the Judd-Ofelt intensity parameters and the variation in these parameters with the variation of glass matrix are discussed. Yellow/Blue (Y/B) ratio and chromacity color coordinates (x,y) are calculated from the emission spectra which indicates the white light generation from all the investigated samples. The correlated color temperature (CCT) for the studied glasses is found to be 4418 K. The fluorescence decay time (τexp) of the 4F9/2 level of Dy3+ has been measured from the decay profiles and compared with calculated lifetimes (τcal). Among all the studied glass matrices, the glass containing BaO exhibits high value of branching ratio, large emission cross-section and high optical gain parameter for 6F9/2 → 6H13 at 575 nm. The results indicates the suitability of all the studied glasses for laser action and white light generation.

  3. H-TiO(2) @MnO(2) //H-TiO(2) @C core-shell nanowires for high performance and flexible asymmetric supercapacitors.

    PubMed

    Lu, Xihong; Yu, Minghao; Wang, Gongming; Zhai, Teng; Xie, Shilei; Ling, Yichuan; Tong, Yexiang; Li, Yat

    2013-01-11

    A flexible solid-state asymmetric supercapacitor device with H-TiO(2) @MnO(2) core-shell NWs as the positive electrode and H-TiO(2) @C core-shell NWs as the negative electrode is developed. This device operates in a 1.8 V voltage window and is able to deliver a high specific capacitance of 139.6 F g(-1) and maximum volumetric energy density of 0.30 mWh cm(-3) with excellent cycling performance and good flexibility. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Hydrothermal synthesis and structural characterization of an organic–inorganic hybrid sandwich-type tungstoantimonate [Cu(en){sub 2}(H{sub 2}O)]{sub 4}[Cu(en){sub 2}(H{sub 2}O){sub 2}][Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]·6H{sub 2}O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Yingjie; College of Medicine, Henan University, Kaifeng, Henan 475004; Cao, Jing

    An organic–inorganic hybrid sandwich-type tungstoantimonate [Cu(en){sub 2}(H{sub 2}O)]{sub 4}[Cu(en){sub 2}(H{sub 2}O){sub 2}][Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]·6H{sub 2}O (1) has been synthesized by reaction of Sb{sub 2}O{sub 3}, Na{sub 2}WO{sub 4}·2H{sub 2}O, CuCl{sub 22H{sub 2}O with en (en=ethanediamine) under hydrothermal conditions and structurally characterized by elemental analysis, inductively coupled plasma atomic emission spectrometry, IR spectrum and single-crystal X-ray diffraction. 1 displays a centric dimeric structure formed by two equivalent trivacant Keggin [α-SbW{sub 9}O{sub 33}]{sup 9−} subunits sandwiching a hexagonal (Cu{sub 2}Na{sub 4}) cluster. Moreover, those related hexagonal hexa-metal cluster sandwiched tungstoantimonates have been also summarized and compared. The variable-temperature magneticmore » measurements of 1 exhibit the weak ferromagnetic exchange interactions within the hexagonal (Cu{sub 2}Na{sub 4}) cluster mediated by the oxygen bridges. - Graphical abstract: An organic–inorganic hybrid (Cu{sub 2}Na{sub 4}) sandwiched tungstoantimonate [Cu(en){sub 2}(H{sub 2}O)]{sub 4}[Cu (en){sub 2}(H{sub 2}O){sub 2}][Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]·6H{sub 2}O was synthesized and magnetic properties was investigated. Display Omitted - Highlights: • Organic–inorganic hybrid sandwich-type tungstoantimonate. • (Cu{sub 2}Na{sub 4} sandwiched) tungstoantimonate [Cu{sub 2}Na{sub 4}(α-SbW{sub 9}O{sub 33}){sub 2}]{sup 10−}. • Ferromagnetic tungstoantimonate.« less

  5. Borate mineral assemblages in the system Na2OCaOMgOB2O3H2O

    USGS Publications Warehouse

    Christ, C.L.; Truesdell, A.H.; Erd, Richard C.

    1967-01-01

    he significant known hydrated borate mineral assemblages (principally of the western United States) in the system Na2OCaOz.sbnd;MgOB2O3H2O are expressible in three ternary composition diagrams. Phase rule interpretation of the diagrams is consistent with observation, if the activity of H2O is generally considered to be determined by the geologic environment. The absence of conflicting tie-lines on a diagram indicates that the several mineral assemblages of the diagram were formed under relatively narrow ranges of temperature and pressure. The known structural as well as empirical formulas for the minerals are listed, and the more recent (since 1960) crystal structure findings are discussed briefly. Schematic Gibbs free energy-composition diagrams based on known solubility-temperature relations in the systems Na2B4O7-H2O and Na2B4O7-NaCl-H2O, are highly useful in the interpretation and prediction of the stability relations in these systems; in particular these diagrams indicate clearly that tincalconite, although geologically important, is everywhere a metastable phase. Crystal-chemical considerations indicate that the same thermodynamic and kinetic behavior observed in the Na2B4O7-H2O system will hold in the Ca2B6O11-H2O system. This conclusion is confirmed by the petrologic evidence. The chemical relations among the mineral assemblages of a ternary diagram are expressed by a schematic "activity-activity" diagram. These activity-activity diagrams permit the tracing-out of the paragenetic sequences as a function of changing cation and H2O activities. ?? 1967.

  6. Integrated experimental and technoeconomic evaluation of two-stage Cu-catalyzed alkaline–oxidative pretreatment of hybrid poplar

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bhalla, Aditya; Fasahati, Peyman; Particka, Chrislyn A.

    2018-05-17

    When applied to recalcitrant lignocellulosic feedstocks, multi-stage pretreatments can provide more processing flexibility to optimize or balance process outcomes such as increasing delignification, preserving hemicellulose, and maximizing enzymatic hydrolysis yields. We previously reported that adding an alkaline pre-extraction step to a copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in improved sugar yields, but the process still utilized relatively high chemical inputs (catalyst and H2O2) and enzyme loadings. We hypothesized that by increasing the temperature of the alkaline pre-extraction step in water or ethanol, we could reduce the inputs required during Cu-AHP pretreatment and enzymatic hydrolysis without significant loss inmore » sugar yield. We also performed technoeconomic analysis to determine if ethanol or water was the more cost-effective solvent during alkaline pre-extraction and if the expense associated with increasing the temperature was economically justified.« less

  7. Reaction of N2O5 with H2O on carbonaceous surfaces

    NASA Technical Reports Server (NTRS)

    Brouwer, L.; Rossi, M. J.; Golden, D. M.

    1986-01-01

    The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

  8. New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

    2006-01-01

    We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

  9. Free nitrous acid serving as a pretreatment method for alkaline fermentation to enhance short-chain fatty acid production from waste activated sludge.

    PubMed

    Zhao, Jianwei; Wang, Dongbo; Li, Xiaoming; Yang, Qi; Chen, Hongbo; Zhong, Yu; Zeng, Guangming

    2015-07-01

    Alkaline condition (especially pH 10) has been demonstrated to be a promising method for short-chain fatty acid (SCFA) production from waste activated sludge anaerobic fermentation, because it can effectively inhibit the activities of methanogens. However, due to the limit of sludge solubilization rate, long fermentation time is required but SCFA yield is still limited. This paper reports a new pretreatment method for alkaline fermentation, i.e., using free nitrous acid (FNA) to pretreat sludge for 2 d, by which the fermentation time is remarkably shortened and meanwhile the SCFA production is significantly enhanced. Experimental results showed the highest SCFA production of 370.1 mg COD/g VSS (volatile suspended solids) was achieved at 1.54 mg FNA/L pretreatment integration with 2 d of pH 10 fermentation, which was 4.7- and 1.5-fold of that in the blank (uncontrolled) and sole pH 10 systems, respectively. The total time of this integration system was only 4 d, whereas the corresponding time was 15 d in the blank and 8 d in the sole pH 10 systems. The mechanism study showed that compared with pH 10, FNA pretreatment accelerated disruption of both extracellular polymeric substances and cell envelope. After FNA pretreatment, pH 10 treatment (1 d) caused 38.0% higher substrate solubilization than the sole FNA, which indicated that FNA integration with pH 10 could cause positive synergy on sludge solubilization. It was also observed that this integration method benefited hydrolysis and acidification processes. Therefore, more SCFA was produced, but less fermentation time was required in the integrated system. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

    NASA Astrophysics Data System (ADS)

    Teolis, B. D.; Plainaki, C.; Cassidy, T. A.; Raut, U.

    2017-10-01

    O2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self-consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10-7 to 5 × 10-3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long-standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an 30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low-energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1-6) × 10-3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

  11. Interfacial contributions of H2O2 decomposition-induced reaction current on mesoporous Pt/TiO2 systems

    NASA Astrophysics Data System (ADS)

    Ray, Nathan J.; Styrov, Vladislav V.; Karpov, Eduard G.

    2017-12-01

    We report on conversion of energy released due to chemical reactions into current for the decomposition of aqueous hydrogen peroxide solution on single phases Pt and TiO2, in addition to Pt and TiO2 simultaneously. We observe that H2O2 decomposition-induced current on TiO2 drastically overshadows the current generated by H2O2 decomposition on Pt. Photo-effects avoided, H2O2 decomposition was found to yield a conversion efficiency of 10-3 electrons generated per H2O2 molecule. Further understanding of chemical reaction-induced current shows promise as a metric with which the surface reaction may be monitored and could be greatly extended into the field of analytical chemistry.

  12. Synthesis, DFT calculations of structure, vibrational and thermal decomposition studies of the metal complex Pb[Mn(C3H2O4)2(H2O)2].

    PubMed

    Gil, Diego M; Carbonio, Raúl E; Gómez, María Inés

    2015-04-15

    The metallo-organic complex Pb[Mn(C3H2O4)2(H2O)2] was synthesized and characterized by IR and Raman spectroscopy and powder X-ray diffraction methods. The cell parameters for the complex were determined from powder X-ray diffraction using the autoindexing program TREOR, and refined by the Le Bail method with the Fullprof program. A hexagonal unit cell was determined with a=b=13.8366(7)Å, c=9.1454(1)Å, γ=120°. The DFT calculated geometry of the complex anion [Mn(C3H2O4)2(H2O)2](2-) is very close to the experimental data reported for similar systems. The IR and Raman spectra and the thermal analysis of the complex indicate that only one type of water molecules is present in the structure. The thermal decomposition of Pb[Mn(C3H2O4)2(H2O)2] at 700 °C in air produces PbO and Pb2MnO4 as final products. The crystal structure of the mixed oxide is very similar to that reported for Pb3O4. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Inhibitory Effect of Dissolved Silica on the H2O2 Decomposition by Iron(III) and Manganese(IV) Oxides: Implications for H2O2-based In Situ Chemical Oxidation

    PubMed Central

    Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

    2011-01-01

    The decomposition of H2O2 on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H2O2, because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand and montmorillonite that were pre-equilibrated with 0.05 – 1.5 mM SiO2 were significantly less reactive toward H2O2 decomposition than their original counterparts, with the H2O2 loss rates inversely proportional to the SiO2 concentration. In the goethite/H2O2 system, the overall •OH yield, defined as the percentage of decomposed H2O2 producing •OH, was almost halved in the presence of 1.5 mM SiO2. Dissolved SiO2 also slows the H2O2 decomposition on manganese(IV) oxide. The presence of dissolved SiO2 results in greater persistence of H2O2 in groundwater, lower H2O2 utilization efficiency and should be considered in the design of H2O2-based treatment systems. PMID:22129132

  14. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  15. The model of nano-scale copper particle removal from silicon surface in high pressure CO2 + H2O and CO2 + H2O + IPA cleaning solutions.

    PubMed

    Tan, Xin; Chai, Jiajue; Zhang, Xiaogang; Chen, Jiawei

    2011-12-01

    This study focuses on the description of the static forces in CO2-H2O and CO2-H2O-IPA cleaning solutions with a separate fluid phase entrapped between nano-scale copper particles and a silicon surface. Calculations demonstrate that increasing the pressure of the cleaning system decreases net adhesion force (NAF) between the particle and silicon. The NAF of a particle for in CO2-H2O-IPA system is less than that in CO2-H2O system, suggesting that the particles enter into bulk layer more easily as the CO2-H2O cleaning system is added IPA.

  16. Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

    NASA Technical Reports Server (NTRS)

    Carter, H. G.; Bullock, R. E.

    1972-01-01

    Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

  17. Morphology-defined interaction of copper phthalocyanine with O2/H2O

    NASA Astrophysics Data System (ADS)

    Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; Gredig, Thomas; Ivanov, Ilia N.

    2016-10-01

    Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but interaction with ambient gas/vapor may lead to changes in its electronic properties and limit OPV device lifetimes. CuPc films of thickness 25 and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. We measured electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. CuPc films deposited at 250°C showed a factor of 5 higher uptake of O2 as detected by a quartz crystal microbalance (QCM), possibly due to the formation of β-CuPc at T>200°C which allows higher O2 mobility between stacked molecules. While weight-based measurements stabilize after ˜10 min of gas exposure, resistance response stabilizes over times >1 h, suggesting that mass change occurs by rapid adsorption at active surface sites whereas resistive response is dominated by slow diffusion of adsorbates into the bulk film. The 25 nm films exhibit higher resistive response than 100 nm films after an hour of O2/H2O exposure due to fast analyte diffusion down to the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold.

  18. Microwave assisted alkaline pretreatment to enhance enzymatic saccharification of catalpa sawdust.

    PubMed

    Jin, Shuguang; Zhang, Guangming; Zhang, Panyue; Li, Fan; Wang, Siqi; Fan, Shiyang; Zhou, Shuqiong

    2016-12-01

    Catalpa sawdust, a promising biofuel production biomass, was pretreated by microwave-water, -NaOH, and -Ca(OH) 2 to enhance enzymatic digestibility. After 48h enzymatic hydrolysis, microwave-Ca(OH) 2 pretreated sample showed the highest reducing sugar yield. The content of hemicellulose and lignin in catalpa sawdust decreased after microwave-alkali pretreatment. SEM observation showed that the catalpa sawdust surface with microwave-Ca(OH) 2 pretreatment suffered the most serious erosion. Crystallinity index of catalpa sawdust increased after all three kinds of pretreatment. The optimum conditions of microwave-Ca(OH) 2 pretreatment were particle size of 40mesh, Ca(OH) 2 dosage of 2.25% (w/v), microwave power of 400W, pretreatment time of 6min, enzyme loading of 175FPU/g, and hydrolysis time of 96h, and the reducing sugar yield of microwave-Ca(OH) 2 pretreated catalpa sawdust reached 402.73mg/g, which increased by 682.15% compared with that of raw catalpa sawdust. The catalpa sawdust with microwave-Ca(OH) 2 pretreatment is promising for biofuel production with great potential. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Application of optimized alkaline pretreatment for enhancing the anaerobic digestion of different sunflower stalks varieties.

    PubMed

    Monlau, Florian; Aemig, Quentin; Barakat, Abdellatif; Steyer, Jean-Philippe; Carrère, Hélène

    2013-01-01

    The use of lignocellulosic residues such as sunflower stalks (SS) for the production of bioenergy such as methane is a promising alternative to fossil fuels. However, their recalcitrant structure justifies the use of pretreatment to enhance the accessibility of holocelluloses and their further conversion into methane. First, different conditions of alkaline pretreatment (i.e. duration and NaOH concentration (g/100 g TS) at a fixed temperature of 55 degrees C) were tested to enhance the methane potential of the stalks of the Serin sunflower (193 mL of methane per gram of volatile solids (VS)). The greatest improvement to the methane potential (262 mL CH4 g(-1) VS) was observed at 55 degrees C, 24 h, 4 g NaOH/100 g TS. Fourier Transform Infrared spectra highlighted an accumulation of lignin in the digestate and the degradation of holocelluloses during the anaerobic process, both for pretreated and untreated SS. In a second stage, this optimum condition for alkaline pretreatment (55 degrees C, 24 h, 4 g NaOH/100 g TS) was applied to the stalks of three other varieties of sunflower. Alkaline pretreatment was effective in the delignification of the stalks of the different sunflower varieties, with lignin reduction varying from 23.3% to 36.3% VS. This reduction of lignin was concomitant with the enhancement of methane potential as compared to that of raw SS, with an increase ranging from 29% to 44% for the different SS.

  20. Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses A 2O–2MO–4SiO 2 with molecular dynamics simulations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Konstantinou, Konstantinos; Sushko, Petr; Duffy, Dorothy M.

    2015-05-15

    A series of mixed cation silicate glasses of the composition A2O2MO – 4SiO2, with A=Li,Na,K and M=Ca,Sr,Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions , whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observedmore » that that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radii ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.« less

  1. Aniracetam attenuates H2O2-induced deficiency of neuron viability, mitochondria potential and hippocampal long-term potentiation of mice in vitro.

    PubMed

    Wang, Yong-Fu; Li, Chao-Cui; Cai, Jing-Xia

    2006-09-01

    Objective It is known that free radicals are involved in neurodegeneration and cognitive dysfunction, as seen in Alzheimer' s disease (AD) and aging. The present study examines the protective effects of aniracetam against H2O2-induced toxicity to neuron viability, mitochondria potential and hippocampal long-term potentiation (LTP). Methods Tetrazolium salt 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) was used to detect neuronal viability. MitoTracker Red (CMX Ros), a fluorescent stain for mitochondria, was used to measure mitochondria potential. Electrophysiological technique was carried out to record hippocampal LTP. Results H2O2 exposure impaired the viability of neurons, reduced mitochondria potential, and decreased LTP in the CA1 region of hippocampus. These deficient effects were significantly rescued by pre-treatment with aniracetam (10-100 mu mol/L). Conclusion These results indicate that aniracetam has a strong neuroprotective effect against H2O2-induced toxicity, which could partly explain the mechanism of its clinical application in neurodegenerative diseases.

  2. Synthesis, crystal structure and thermal study of the hybrid nickel sulfate: C6N2H16[Ni(H2O)6(SO4)2].2H2O

    NASA Astrophysics Data System (ADS)

    Ngopoh, F. A. I.; Hamdi, N.; Chaouch, S.; Lachkar, M.; da Silva, I.; El Bali, B.

    2018-03-01

    A new inorganic-organic hybrid open framework nickel sulfate C6N2H16[Ni(H2O)6(SO4)2].2H2O has been synthesized by slow evaporation in aqueous solution using trans-1,4-diaminocyclohexane as structure-directing agent. It was characterized by single-crystal X-ray diffraction, infrared spectroscopy and analyzed by TGA-DSC. The compound crystallizes in the monoclinic space group P21/n, with the unit cell parameters of a = 6.2586 Å, b = 12.3009 Å, c = 13.2451 Å, β = 98,047°, Z = 4. Its crystal structure consists of isolated polyhedrons [Ni(H2O)6]2+ and [SO4]2- and free water which connects through hydrogen bonds. This association results in the porous framework where the protonated organic molecule trans-1,4-diaminocyclohexane is located as a counter ion. The IR spectra Shows the bands corresponding to the sulfate anion, water molecule and diprotonated trans-1-4-diaminocyclohexane. Thermal study indicates the loss of water molecules and the degradation of trans-1-4-diaminocyclohexane.

  3. Activation of Nrf2 by H2O2: de novo synthesis versus nuclear translocation.

    PubMed

    Covas, Gonçalo; Marinho, H Susana; Cyrne, Luísa; Antunes, Fernando

    2013-01-01

    The most common mechanism described for the activation of the transcription factor Nrf2 is based on the inhibition of its degradation in the cytosol followed by its translocation to the nucleus. Recently, Nrf2 de novo synthesis was proposed as an additional mechanism for the rapid upregulation of Nrf2 by hydrogen peroxide (H2O2). Here, we describe a detailed protocol, including solutions, pilot experiments, and experimental setups, which allows exploring the role of H2O2, delivered either as a bolus or as a steady state, in endogenous Nrf2 translocation and synthesis. We also show experimental data, illustrating that H2O2 effects on Nrf2 activation in HeLa cells are strongly dependent both on the H2O2 concentration and on the method of H2O2 delivery. The de novo synthesis of Nrf2 is triggered within 5min of exposure to low concentrations of H2O2, preceding Nrf2 translocation to the nucleus which is slower. Evidence of de novo synthesis of Nrf2 is observed only for low H2O2 steady-state concentrations, a condition that is prevalent in vivo. This study illustrates the applicability of the steady-state delivery of H2O2 to uncover subtle regulatory effects elicited by H2O2 in narrow concentration and time ranges. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. H2/O2 three-body rates at high temperatures

    NASA Technical Reports Server (NTRS)

    Marinelli, William J.; Kessler, William J.; Carleton, Karen L.

    1991-01-01

    Hydrogen atoms are produced in the presence of excess O2, and the first-order decay are studied as a function of temperature and pressure in order to obtain the rate coefficient for the three-body reaction between H-atoms and O2. Attention is focused on the kinetic scheme employed as well as the reaction cell and photolysis and probe laser system. A two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical-thickness or O2-absorption problems. Results confirm measurements reported previously for the H + O2 + N2 reaction at 300 K and extend these measurements to higher temperatures. Preliminary data indicate non-Arrehenius-type behavior of this reaction rate coefficient as a function of temperature. Measurements of the rate coefficient for H + O2 + Ar reaction at 300 K give a rate coefficient of 2.1 +/- 0.1 x 10 to the -32nd cm exp 6/molecule sec.

  5. KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

    PubMed

    Schlueter, John A; Geiser, Urs; Funk, Kylee A

    2008-02-01

    The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

  6. D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

    NASA Astrophysics Data System (ADS)

    Foustoukos, Dionysis I.; Mysen, Bjorn O.

    2012-06-01

    A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

  7. Cyanide oxidation by singlet oxygen generated via reaction between H2O2 from cathodic reduction and OCl(-) from anodic oxidation.

    PubMed

    Tian, Shichao; Li, Yibing; Zeng, Huabin; Guan, Wei; Wang, Yan; Zhao, Xu

    2016-11-15

    Cyanide is widely present in electroplating wastewater or metallurgical effluents. In the present study, the electrochemical destruction of cyanide with various anode and cathode compositions under alkaline conditions was investigated. The results indicated that the electrochemical system using RuO2/Ti as anode and activated carbon fiber (ACF) as cathode in the presence of sodium chloride was efficient for the cyanide removal. In this system, in situ generation of HClO by anodic oxidation of Cl(-) at RuO2/Ti anode occurred with the H2O2 generation by O2 reduction at ACF cathode. As confirmed by the electron spin resonance technique, the reaction between HClO and H2O2 led to the generation of singlet oxygen, which was responsible for the cyanide removal. Further experiment indicated that the cyanide removal efficiency increased with the increase of the current density or the sodium chloride concentration. Cyanate was identified as main product in the system. Besides, the system exhibited good stability for the cyanide removal, which was beneficial to its practical application. Copyright © 2016. Published by Elsevier Inc.

  8. Adenosine decreases oxidative stress and protects H2O2-treated neural stem cells against apoptosis through decreasing Mst1 expression.

    PubMed

    Gholinejad, Masoumeh; Jafari Anarkooli, Iraj; Taromchi, Amirhossein; Abdanipour, Alireza

    2018-05-01

    Overproduction of free radicals during oxidative stress induces damage to key biomolecules and activates programed cell death pathways. Neuronal cell death in the nervous system leads to a number of neurodegenerative diseases. The aim of the present study was to evaluate the neuroprotective effect of adenosine on inhibition of apoptosis induced by hydrogen peroxide (H 2 O 2 ) in bone marrow-derived neural stem cells (B-dNSCs), with focus on its regulatory effect on the expression of mammalian sterile 20-like kinase 1 ( Mst1 ), as a novel proapoptotic kinase. B-dNSCs were exposed to adenosine at different doses (2, 4, 6, 8 and 10 µM) for 48 h followed by 125 µM H 2 O 2 for 30 min. Using MTT, terminal deoxynucleotidyl transferase dUTP nick-end labeling and real-time reverse transcription polymerase chain reaction assays, the effects of adenosine on cell survival, apoptosis and Mst1 , nuclear factor (erythroid-derived 2)-like 2 and B-cell lymphoma 2 and adenosine A1 receptor expression were evaluated in pretreated B-dNSCs compared with controls (cells treated with H 2 O 2 only). Firstly, results of the MTT assay indicated 6 µM adenosine to be the most protective dose in terms of promotion of cell viability. Subsequent assays using this dosage indicated that apoptosis rate and Mst1 expression in B-dNSCs pretreated with 6 µM adenosine were significantly decreased compared with the control group. These findings suggest that adenosine protects B-dNSCs against oxidative stress-induced cell death, and therefore, that it may be used to promote the survival rate of B-dNSCs and as a candidate for the treatment of oxidative stress-mediated neurological diseases.

  9. Effects of variation in background mixing ratios of N2, O2, and Ar on the measurement of δ18O-H2O and δ2H-H2O values by cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, Jennifer E.; Rella, Chris W.

    2017-08-01

    Cavity ring-down spectrometers have generally been designed to operate under conditions in which the background gas has a constant composition. However, there are a number of observational and experimental situations of interest in which the background gas has a variable composition. In this study, we examine the effect of background gas composition on a cavity ring-down spectrometer that measures δ18O-H2O and δ2H-H2O values based on the amplitude of water isotopologue absorption features around 7184 cm-1 (L2120-i, Picarro, Inc.). For background mixtures balanced with N2, the apparent δ18O values deviate from true values by -0.50 ± 0.001 ‰ O2 %-1 and -0.57 ± 0.001 ‰ Ar %-1, and apparent δ2H values deviate from true values by 0.26 ± 0.004 ‰ O2 %-1 and 0.42 ± 0.004 ‰ Ar %-1. The artifacts are the result of broadening, narrowing, and shifting of both the target absorption lines and strong neighboring lines. While the background-induced isotopic artifacts can largely be corrected with simple empirical or semi-mechanistic models, neither type of model is capable of completely correcting the isotopic artifacts to within the inherent instrument precision. The development of strategies for dynamically detecting and accommodating background variation in N2, O2, and/or Ar would facilitate the application of cavity ring-down spectrometers to a new class of observations and experiments.

  10. Energetics of CO2 and H2O adsorption on zinc oxide.

    PubMed

    Gouvêa, Douglas; Ushakov, Sergey V; Navrotsky, Alexandra

    2014-08-05

    Adsorption of H2O and CO2 on zinc oxide surfaces was studied by gas adsorption calorimetry on nanocrystalline samples prepared by laser evaporation in oxygen to minimize surface impurities and degassed at 450 °C. Differential enthalpies of H2O and CO2 chemisorption are in the range -150 ±10 kJ/mol and -110 ±10 kJ/mol up to a coverage of 2 molecules per nm(2). Integral enthalpy of chemisorption for H2O is -96.8 ±2.5 kJ/mol at 5.6 H2O/nm(2) when enthalpy of water condensation is reached, and for CO2 is -96.6 ±2.5 kJ/mol at 2.6 CO2/nm(2) when adsorption ceases. These values are consistent with those reported for ZnO prepared by other methods after similar degas conditions. The similar energetics suggests possible competition of CO2 and H2O for binding to ZnO surfaces. Exposure of bulk and nanocrystalline ZnO with preadsorbed CO2 to water vapor results in partial displacement of CO2 by H2O. In contrast, temperature-programmed desorption (TPD) indicates that a small fraction of CO2 is retained on ZnO surfaces up to 800 °C, under conditions where all H2O is desorbed, with adsorption energies near -200 kJ/mol. Although molecular mechanisms of adsorption were not studied, the thermodynamic data are consistent with dissociative adsorption of H2O at low coverage and with several different modes of CO2 binding.

  11. A neodymium(III)-ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)].H2O.

    PubMed

    Trombe, Jean-Christian; Galy, Jean; Enjalbert, Renée

    2002-10-01

    The title compound, diammonium aqua-mu-carbonato-tri-mu-oxalato-dineodymium(III) hydrate, (NH(4))(2)[Nd(2)(CO(3))(C(2)O(4))(3)(H(2)O)].H(2)O, involving the two ligands oxalate and carbonate, has been prepared hydrothermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (1/2, 1/2, 1/2). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three-dimensional network. The carbonate group acts as a bis-chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis-chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.

  12. Synthesis and structure of heptaaqua(nitrilotris(methylenephosphonato))(dibarium)sodium monohydrate [Na(H{sub 2}O){sub 3}(μ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(μ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: xps@ftiudm.ru; Zakirova, R. M., E-mail: ftt@udsu.ru

    Crystals of the monohydrate form of heptaaqua(nitrilotris(methylenephosphonato))(dibarium) sodium [Na(H{sub 2}O{sub )3}(µ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(µ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O are obtained; space group P2{sub 1}/c, Z = 4; a = 13.9117(10) Å, b = 11.54030(10) Å, and c = 24.1784(17) Å, ß = 148.785(18)°. The Na atom is coordinated octahedrally by one oxygen atom of a phosphonate group and five water molecules, including two bridging molecules. Ba atoms occupy two inequivalent crystallographic positions with coordination number eight and nine. The coordination spheres of both Ba atoms include two water molecules. Each ligand is bound to one Namore » atom and five Ba atoms forming three Ba–O–P–O and five Ba–O–P–C–N–C–P–O chelate cycles. In addition to the coordination bonds, molecules, including the solvate water molecule, are involved in hydrogen bonds in the crystal packing.« less

  13. A Novel Dimeric Ni-Substituted beta-Keggin Silicotungstate: Structure and Magnetic Properties of K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O.

    PubMed

    Kortz, Ulrich; Jeannin, Yves P.; Tézé, André; Hervé, Gilbert; Isber, Samih

    1999-08-09

    The novel dimeric polyoxometalate [{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)](12)(-) (1) has been synthesized and characterized by IR spectroscopy, polarography, elemental analysis, thermogravimetric analysis, and magnetic measurements. An X-ray single-crystal analysis was carried out on K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O, which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.701(4) Å, b = 24.448(11) Å, c = 13.995(5) Å, beta = 99.62(3) degrees, and Z = 4. The anion consists of two [beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)] Keggin moieties linked via two OH bridging groups, leading to a planar Ni(2)(OH)(2) unit. The two half-units are related by an inversion center and each contain one Ni atom in the rotated triad. The formation of the new anion involves insertion, isomerization, and dimerization. Magnetic measurements show that the central Ni(4) unit exhibits ferromagnetic (J' = 4.14 cm(-)(1)) as well as weak antiferromagnetic (J = -0.65 cm(-)(1)) Ni-Ni exchange interactions.

  14. Experimental studies on cycling stable characteristics of inorganic phase change material CaCl2·6H2O-MgCl2·6H2O modified with SrCl2·6H2O and CMC

    NASA Astrophysics Data System (ADS)

    He, Meizhi; Yang, Luwei; Zhang, Zhentao

    2018-01-01

    By means of mass ratio method, binary eutectic hydrated salts inorganic phase change thermal energy storage system CaCl2·6H2O-20wt% MgCl2·6H2O was prepared, and through adding nucleating agent 1wt% SrCl2·6H2O and thickening agent 0.5wt% carboxy methyl cellulose (CMC), inoganic phase change material (PCM) modified was obtained. With recording cooling-melting curves simultaneously, this PCM was frozen and melted for 100 cycles under programmable temperature control. After per 10 cycles, the PCM was charaterized by differential scanning calorimeter (DSC), X-ray diffraction (XRD) and density meter, then analysing variation characteristics of phase change temperature, supercooling degree, superheat degree, latent heat, crystal structure and density with the increase of cycle index. The results showed that the average values of average phase change temperature for cooling and heating process were 25.70°C and 27.39°C respectively with small changes. The average values of average supercooling and superheat degree were 0.59°C and 0.49°C respectively, and the maximum value was 1.10°C. The average value and standard deviation of latent heat of fusion were 120.62 J/g and 1.90 J/g respectively. Non-molten white solid sediments resulted from phase separation were tachyhydrite (CaMg2Cl6·12H2O), which was characterized by XRD. Measuring density of the PCM after per 10 cycles, and the results suggested that the total mass of tachyhydrite was limited. In summary, such modified inoganic PCM CaCl2·6H2O-20wt% MgCl2·6H2O-1wt% SrCl2·6H2O-0.5wt% CMC could stay excellent circulation stability within 100 cycles, and providing reference value in practical use.

  15. Three-dimensional WS2 nanosheet networks for H2O2 produced for cell signaling

    NASA Astrophysics Data System (ADS)

    Tang, Jing; Quan, Yingzhou; Zhang, Yueyu; Jiang, Min; Al-Enizi, Abdullah M.; Kong, Biao; An, Tiance; Wang, Wenshuo; Xia, Limin; Gong, Xingao; Zheng, Gengfeng

    2016-03-01

    Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in living RAW 264.7 macrophage cells and neurons. First-principles calculations further demonstrate that the enhanced sensitivity of probing H2O2 is attributed to the efficient and spontaneous H2O2 adsorption on WS2 nanosheet edge sites. The combined features of 3D WS2 nanosheet networks suggest attractive new opportunities for exploring the physiological roles of reactive oxygen species like H2O2 in living systems.Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in

  16. Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)22-OH)2(H2O)4 (P2W16O59)2]14-

    NASA Astrophysics Data System (ADS)

    Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

    2003-08-01

    Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)22-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

  17. Non-Potassic Melts In CMAS-CO2-H2O-K2O Model Peridotite

    NASA Astrophysics Data System (ADS)

    Buisman, I.; Walter, M. J.; Keshav, S.

    2009-12-01

    Volatile mediated model systems have been fundamental in shaping our knowledge about the way we view melting phase relations of peridotite at various depths in the Earth. Volatiles not only affect the melting temperatures, but the resulting liquids are, in some case, dramatically different than those witnessed in melting of dry peridotite. For example, the influence of CO2 and H2O on the melting phase relations of model peridotite shows a remarkable decrease in the solidus temperatures when compared to the dry peridotite (Gudfinnsson and Presnall, 2005). These model systems illustrate a gradational change above the solidus from carbonatites to kimberlites over several hundreds of degrees. Group-II kimberlites are ultrapotassic rocks with high water content where the mineral phlogopite is abundant. To get a better understanding of the melting phase relations related to carbonatitic and kimberlitic magmas, K2O was added to the system CMAS-CO2-H2O. In these systems, fluid and melt can co-exist in P-T space. However, from past studies, it is also known that in hydrous systems, both the fluid and melt will become indistinguishable from one another creating a singularity (second critical endpoint). Starting from the solidus located in six components (Keshav and Gudfinnsson, AGU abstract, 2009), with seven phases, melting phase relations in CMAS-CO2-H2O-K2O involving, fo-opx-cpx-garnet-carbonate-melt-fluid, are divariant. Fluid was recognized with the observation of large cavities seen in exposed capsules. Moreover, the presence of bright, needle-like grains found in large cavities in backscattered images implies the presence of solute in the fluid phase. Significantly, liquids on this divariant region have about 1000 ppm K2O, and so is the case with accompanying cpx. Hence, with this non-interesting amount of K2O in the mentioned phases, fluid must have all the potassium. At 30 kbar/1100C, with fo-opx-cpx-garnet-carbonate-phlogopite-melt-fluid, the melting phase

  18. Pd-catalytic in situ generation of H2O2 from H2 and O2 produced by water electrolysis for the efficient electro-fenton degradation of rhodamine B.

    PubMed

    Yuan, Songhu; Fan, Ye; Zhang, Yucheng; Tong, Man; Liao, Peng

    2011-10-01

    A novel electro-Fenton process was developed for wastewater treatment using a modified divided electrolytic system in which H2O2 was generated in situ from electro-generated H2 and O2 in the presence of Pd/C catalyst. Appropriate pH conditions were obtained by the excessive H+ produced at the anode. The performance of the novel process was assessed by Rhodamine B (RhB) degradation in an aqueous solution. Experimental results showed that the accumulation of H2O2 occurred when the pH decreased and time elapsed. The maximum concentration of H2O2 reached 53.1 mg/L within 120 min at pH 2 and a current of 100 mA. Upon the formation of the Fenton reagent by the addition of Fe2+, RhB degraded completely within 30 min at pH 2 with a pseudo first order rate constant of 0.109 ± 0.009 min(-1). An insignificant decline in H2O2 generation and RhB degradation was found after six repetitions. RhB degradation was achieved by the chemisorption of H2O2 on the Pd/C surface, which subsequently decomposed into •OH upon catalysis by Pd0 and Fe2+. The catalytic decomposition of H2O2 to •OH by Fe2+ was more powerful than that by Pd0, which was responsible for the high efficiency of this novel electro-Fenton process.

  19. Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

    NASA Astrophysics Data System (ADS)

    Johannes, Wilhelm

    1980-09-01

    Beginning of melting and subsolidus relationships in the system K2O-CaO-Al2O3-SiO2-H2O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt. The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K2O-CaO-Al2O3-SiO2-H2O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al2O3-SiO2-H2O. The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al2O3-SiO2-H2O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this

  20. Protective effect of hydroxytyrosol and its metabolite homovanillic alcohol on H(2)O(2) induced lipid peroxidation in renal tubular epithelial cells.

    PubMed

    Deiana, Monica; Incani, Alessandra; Rosa, Antonella; Corona, Giulia; Atzeri, Angela; Loru, Debora; Paola Melis, M; Assunta Dessì, M

    2008-09-01

    We investigated the capacity of hydroxytyrosol (HT), 3,4-dihydroxyphenylethanol, and homovanillic alcohol (HVA), 4-hydroxy-3-methoxy-phenylethanol, to inhibit H(2)O(2) induced oxidative damage in LLC-PK1, a porcine kidney epithelial cell line, studying the effect of H(2)O(2) on specific cell membrane lipid targets, unsaturated fatty acids and cholesterol. Exposure to H(2)O(2) induced a significant increase of the level of MDA together with a disruption of the membrane structure, with the loss of unsaturated fatty acids, cholesterol and alpha-tocopherol, and the formation of fatty acids hydroperoxides and 7-ketocholesterol. Pretreatment with HT protected renal cells from oxidative damage: the level of membrane lipids was preserved and there was no significant detection of oxidation products. HVA exerted a comparable activity, thus both HT and HVA were able to prevent in renal cells the lipid peroxidation process that plays a central role in tubular cell injury.

  1. Generation of H2, O2, and H2O2 from water by the use of intense femtosecond laser pulses and the possibility of laser sterilization

    NASA Astrophysics Data System (ADS)

    Chin, S. L.; Lagacé, S.

    1996-02-01

    An intense femtosecond Ti-sapphire laser pulse was focused into water, leading to self-focusing. Apart from generating a white light (supercontinuum), the intense laser field in the self-focusing regions of the laser pulse dissociated the water molecules, giving rise to hydrogen and oxygen gas as well as hydrogen peroxide. Our analysis shows that the formation of free radicals O, H, and OH preceded the formation of the stable products of H2, O2, and H2O2. Because O radicals and H2O2 are strong oxydizing agents, one can take advantage of this phenomenon to design a laser scheme for sterilization in medical and biological applications.

  2. H2O2 Synthesis Induced by Irradiation of H2O with Energetic H(+) and Ar(+) Ions at Various Temperatures

    NASA Technical Reports Server (NTRS)

    Baragiola, R. A.; Loeffler, M. J.; Raut, U.; Vidal, R. A.; Carlson, R. W.

    2004-01-01

    The detection of H2O2 on Jupiter's icy satellite Europa by the Galileo NIMS instrument presented a strong evidence for the importance of radiation effects on icy surfaces. A few experiments have investigated whether solar flux of protons incident on Europa ice could cause a significant if any H2O2 production. These published results differ as to whether H2O2 can be formed by ions impacting water at temperatures near 80 K, which are appropriate to Europa. This discrepancy may be a result of the use of different incident ion energies, different vacuum conditions, or different ways of processing the data. The latter possibility comes about from the difficulty of identifying the 3.5 m peroxide OH band on the long wavelength wing of the much stronger water 3.1 m band. The problem is aggravated by using straight line baselines to represent the water OH band with a curvature, in the region of the peroxide band, that increases with temperature. To overcome this problem, we use polynomial baselines that provide good fits to the water band and its derivative.

  3. Hydration energies and structures of alkaline earth metal ions, M2+(H2O)n, n = 5-7, M = Mg, Ca, Sr, and Ba.

    PubMed

    Rodriguez-Cruz, S E; Jockusch, R A; Williams, E R

    1999-09-29

    The evaporation of water from hydrated alkaline earth metal ions, produced by electrospray ionization, was studied in a Fourier transform mass spectrometer. Zero-pressure-limit dissociation rate constants for loss of a single water molecule from the hydrated divalent metal ions, M(2+)(H(2)O)(n) (M = Mg, Ca, and Sr for n = 5-7, and M = Ba for n = 4-7), are measured as a function of temperature using blackbody infrared radiative dissociation. From these values, zero-pressure-limit Arrhenius parameters are obtained. By modeling the dissociation kinetics using a master equation formalism, threshold dissociation energies (E(o)) are determined. These reactions should have a negligible reverse activation barrier; therefore, E(o) values should be approximately equal to the binding energy or hydration enthalpy at 0 K. For the hepta- and hexahydrated ions at low temperature, binding energies follow the trend expected on the basis of ionic radii: Mg > Ca > Sr > Ba. For the hexahydrated ions at high temperature, binding energies follow the order Ca > Mg > Sr > Ba. The same order is observed for the pentahydrated ions. Collisional dissociation experiments on the tetrahydrated species result in relative dissociation rates that directly correlate with the size of the metals. These results indicate the presence of two isomers for hexahydrated magnesium ions: a low-temperature isomer in which the six water molecules are located in the first solvation shell, and a high-temperature isomer with the most likely structure corresponding to four water molecules in the inner shell and two water molecules in the second shell. These results also indicate that the pentahydrated magnesium ions have a structure with four water molecules in the first solvation shell and one in the outer shell. The dissociation kinetics for the hexa- and pentahydrated clusters of Ca(2+), Sr(2+), and Ba(2+) are consistent with structures in which all the water molecules are located in the first solvation shell.

  4. Complexes in the Photocatalytic Reaction of CO2 and H2O: Theoretical Studies

    PubMed Central

    Luo, Dongmei; Zhang, Ning; Hong, Sanguo; Wu, Huanwen; Liu, Zhihua

    2010-01-01

    Complexes (H2O/CO2, e–(H2O/CO2) and h+–(H2O/CO2)) in the reaction system of CO2 photoreduction with H2O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H2O/CO2 captured photo-induced electron and hole produced e–(H2O/CO2) and h+–(H2O/CO2), respectively. The results revealed that CO2 and H2O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO2 and H2O, which might be attributed to the synergistic effect and which could not be captured experimentally. PMID:21152274

  5. Availability of O(2) and H(2)O(2) on pre-photosynthetic Earth.

    PubMed

    Haqq-Misra, Jacob; Kasting, James F; Lee, Sukyoung

    2011-05-01

    Old arguments that free O(2) must have been available at Earth's surface prior to the origin of photosynthesis have been revived by a new study that shows that aerobic respiration can occur at dissolved oxygen concentrations much lower than had previously been thought, perhaps as low as 0.05 nM, which corresponds to a partial pressure for O(2) of about 4 × 10(-8) bar. We used numerical models to study whether such O(2) concentrations might have been provided by atmospheric photochemistry. Results show that disproportionation of H(2)O(2) near the surface might have yielded enough O(2) to satisfy this constraint. Alternatively, poleward transport of O(2) from the equatorial stratosphere into the polar night region, followed by downward transport in the polar vortex, may have brought O(2) directly to the surface. Thus, our calculations indicate that this "early respiration" hypothesis might be physically reasonable.

  6. A novel GH10 xylanase from Penicillium sp. accelerates saccharification of alkaline-pretreated bagasse by an enzyme from recombinant Trichoderma reesei expressing Aspergillus β-glucosidase.

    PubMed

    Shibata, Nozomu; Suetsugu, Mari; Kakeshita, Hiroshi; Igarashi, Kazuaki; Hagihara, Hiroshi; Takimura, Yasushi

    2017-01-01

    Trichoderma reesei is considered a candidate fungal enzyme producer for the economic saccharification of cellulosic biomass. However, performance of the saccharifying enzymes produced by T. reesei is insufficient. Therefore, many attempts have been made to improve its performance by heterologous protein expression. In this study, to increase the conversion efficiency of alkaline-pretreated bagasse to sugars, we conducted screening of biomass-degrading enzymes that showed synergistic effects with enzyme preparations produced by recombinant T. reesei . Penicillium sp. strain KSM-F532 produced the most effective enzyme to promote the saccharification of alkaline-pretreated bagasse. Biomass-degrading enzymes from strain KSM-F532 were fractionated and analyzed, and a xylanase, named PspXyn10, was identified. The amino acid sequence of PspXyn10 was determined by cDNA analysis: the enzyme shows a modular structure consisting of glycoside hydrolase family 10 (GH10) and carbohydrate-binding module family 1 (CBM1) domains. Purified PspXyn10 was prepared from the supernatant of a recombinant T. reesei strain. The molecular weight of PspXyn10 was estimated to be 55 kDa, and its optimal temperature and pH for xylanase activity were 75 °C and pH 4.5, respectively. More than 80% of the xylanase activity was maintained at 65 °C for 10 min. With beechwood xylan as the substrate, the enzyme had a K m of 2.2 mg/mL and a V max of 332 μmol/min/mg. PspXyn10ΔCBM, which lacked the CBM1 domain, was prepared by limited proteolysis. PspXyn10ΔCBM showed increased activity against soluble xylan, but decreased saccharification efficiency of alkaline-pretreated bagasse. This result indicated that the CBM1 domain of PspXyn10 contributes to the enhancement of the saccharification efficiency of alkaline-pretreated bagasse. A recombinant T. reesei strain, named X2PX10, was constructed from strain X3AB1. X3AB1 is an Aspergillus aculeatus β-glucosidase-expressing T. reesei PC-3-7. X2PX10

  7. Xylan extraction from pretreated sugarcane bagasse using alkaline and enzymatic approaches.

    PubMed

    Sporck, Daniele; Reinoso, Felipe A M; Rencoret, Jorge; Gutiérrez, Ana; Del Rio, José C; Ferraz, André; Milagres, Adriane M F

    2017-01-01

    New biorefinery concepts are necessary to drive industrial use of lignocellulose biomass components. Xylan recovery before enzymatic hydrolysis of the glucan component is a way to add value to the hemicellulose fraction, which can be used in papermaking, pharmaceutical, and food industries. Hemicellulose removal can also facilitate subsequent cellulolytic glucan hydrolysis. Sugarcane bagasse was pretreated with an alkaline-sulfite chemithermomechanical process to facilitate subsequent extraction of xylan by enzymatic or alkaline procedures. Alkaline extraction methods yielded 53% (w/w) xylan recovery. The enzymatic approach provided a limited yield of 22% (w/w) but produced the xylan with the lowest contamination with lignin and glucan components. All extracted xylans presented arabinosyl side groups and absence of acetylation. 2D-NMR data suggested the presence of O -methyl-glucuronic acid and p -coumarates only in enzymatically extracted xylan. Xylans isolated using the enzymatic approach resulted in products with molecular weights (Mw) lower than 6 kDa. Higher Mw values were detected in the alkali-isolated xylans. Alkaline extraction of xylan provided a glucan-enriched solid readily hydrolysable with low cellulase loads, generating hydrolysates with a high glucose/xylose ratio. Hemicellulose removal before enzymatic hydrolysis of the cellulosic fraction proved to be an efficient manner to add value to sugarcane bagasse biorefining. Xylans with varied yield, purity, and structure can be obtained according to the extraction method. Enzymatic extraction procedures produce high-purity xylans at low yield, whereas alkaline extraction methods provided higher xylan yields with more lignin and glucan contamination. When xylan extraction is performed with alkaline methods, the residual glucan-enriched solid seems suitable for glucose production employing low cellulase loadings.

  8. Reductive atmospheric acid leaching of spent alkaline batteries in H2SO4/Na2SO3 solutions

    NASA Astrophysics Data System (ADS)

    Morcali, Mehmet Hakan

    2015-07-01

    This work studies the optimum reductive leaching process for manganese and zinc recovery from spent alkaline battery paste. The effects of reducing agents, acid concentration, pulp density, reaction temperature, and leaching time on the dissolution of manganese and zinc were investigated in detail. Manganese dissolution by reductive acidic media is an intermediate-controlled process with an activation energy of 12.28 kJ·mol-1. After being leached, manganese and zinc were selectively precipitated with sodium hydroxide. The zinc was entirely converted into zincate (Zn(OH){4/2-}) ions and thus did not co-precipitate with manganese hydroxide during this treatment (2.0 M NaOH, 90 min, 200 r/min, pH > 13). After the manganese was removed from the solution, the Zn(OH){4/2-} was precipitated as zinc sulfate in the presence of sulfuric acid. The results indicated that this process could be effective in recovering manganese and zinc from alkaline batteries.

  9. Solar kerosene from H2O and CO2

    NASA Astrophysics Data System (ADS)

    Furler, P.; Marxer, D.; Scheffe, J.; Reinalda, D.; Geerlings, H.; Falter, C.; Batteiger, V.; Sizmann, A.; Steinfeld, A.

    2017-06-01

    The entire production chain for renewable kerosene obtained directly from sunlight, H2O, and CO2 is experimentally demonstrated. The key component of the production process is a high-temperature solar reactor containing a reticulated porous ceramic (RPC) structure made of ceria, which enables the splitting of H2O and CO2 via a 2-step thermochemical redox cycle. In the 1st reduction step, ceria is endo-thermally reduced using concentrated solar radiation as the energy source of process heat. In the 2nd oxidation step, nonstoichiometric ceria reacts with H2O and CO2 to form H2 and CO - syngas - which is finally converted into kerosene by the Fischer-Tropsch process. The RPC featured dual-scale porosity for enhanced heat and mass transfer: mm-size pores for volumetric radiation absorption during the reduction step and μm-size pores within its struts for fast kinetics during the oxidation step. We report on the engineering design of the solar reactor and the experimental demonstration of over 290 consecutive redox cycles for producing high-quality syngas suitable for the processing of liquid hydrocarbon fuels.

  10. Adsorption of H2O, H2, O2, CO, NO, and CO2 on graphene/g-C3N4 nanocomposite investigated by density functional theory

    NASA Astrophysics Data System (ADS)

    Wu, Hong-Zhang; Bandaru, Sateesh; Liu, Jin; Li, Li-Li; Wang, Zhenling

    2018-02-01

    Motivated by the photocatalytic reactions of small molecules on g-C3N4 by these insights, we sought to explore the adsorption of H2O and CO2 molecules on the graphene side and H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side of hybrid g-C3N4/graphene nanocomposite using first-principles calculations. The atomic structure and electronic properties of hybrid g-C3N4/graphene nanocomposite is explored. The adsorption of small molecules on graphene/g-C3N4 nanocomposite is thoroughly investigated. The computational studies revels that all small molecules on graphene/g-C3N4 nanocomposite are the physisorption. The adsorption characteristics of H2O and CO2 molecules on the graphene side are similar to that on graphene. The adsorption of H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side always leads to a buckle structure of graphene/g-C3N4 nanocomposite. Graphene as a substrate can significantly relax the buckle degree of g-C3N4 in g-C3N4/graphene nanocomposite.

  11. Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

    PubMed

    Monegan, Jessie D; Bunge, Scott D

    2009-04-06

    The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

  12. Degradation of crystal violet by an FeGAC/H2O2 process.

    PubMed

    Chen, Chiing-Chang; Chen, Wen-Ching; Chiou, Mei-Rung; Chen, Sheng-Wei; Chen, Yao Yin; Fan, Huan-Jung

    2011-11-30

    Because of the growing concern over highly contaminated crystal violet (CV) wastewater, an FeGAC/H(2)O(2) process was employed in this research to treat CV-contaminated wastewater. The experimental results indicated that the presence of iron oxide-coated granular activated carbon (FeGAC) greatly improved the oxidative ability of H(2)O(2) for the removal of CV. For instance, the removal efficiencies of H(2)O(2), GAC, FeGAC, GAC/H(2)O(2) and FeGAC/H(2)O(2) processes were 10%, 44%, 40%, 43% and 71%, respectively, at test conditions of pH 3 and 7.4mM H(2)O(2). FeGAC/H(2)O(2) combined both the advantages of FeGAC and H(2)O(2). FeGAC had a good CV adsorption ability and could effectively catalyze the hydrogen peroxide oxidation reaction. Factors (including pH, FeGAC dosage and H(2)O(2) dosage) affecting the removal of CV by FeGAC/H(2)O(2) were investigated in this research as well. In addition, the reaction intermediates were separated and identified using HPLC-ESI-MS. The N-demethylation step might be the main reaction pathway for the removal of CV. The reaction mechanisms for the process proposed in this research might be useful for future application of this technology to the removal of triphenylmethane (TPM) dyes. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Bradykinin-potentiating PEPTIDE-10C, an argininosuccinate synthetase activator, protects against H2O2-induced oxidative stress in SH-SY5Y neuroblastoma cells.

    PubMed

    Querobino, Samyr Machado; Ribeiro, César Augusto João; Alberto-Silva, Carlos

    2018-05-01

    Bradykinin-potentiating peptides (BPPs - 5a, 7a, 9a, 10c, 11e, and 12b) of Bothrops jararaca (Bj) were described as argininosuccinate synthase (AsS) activators, improving l-arginine availability. Agmatine and polyamines, which are l-arginine metabolism products, have neuroprotective properties. Here, we investigated the neuroprotective effects of low molecular mass fraction from Bj venom (LMMF) and two synthetic BPPs (BPP-10c, H 2 O 2 -induced oxidative stress. The neuroprotective effects against H 2 O 2 -induced were analyzed by reactive oxygen species (ROS - DCFH) production; lipid peroxidation (TBARS); intracellular GSH; AsS, iNOS, and NF-kB expressions; nitrite levels (Griess); mitochondrial membrane potential (TMRM); and antioxidant activity (DPPH). Analysis of variance followed by Tukey's post hoc test were calculated for statistical comparisons. Pre-treatment with both BPPs significantly reduced cell death induced by H 2 O 2 , but BPP-10c showed higher protective capacity than BPP-12b. LMMF pretreatment was unable to prevent the reduction of cell viability caused by H 2 O 2 . The neuroprotective mechanism of BPP-10c against oxidative stress was investigated. BPP-10c reduced ROS generation and lipid peroxidation in relation to cells treated only with H 2 O 2 . BBP-10c increased AsS expression and was not neuroprotective in the presence of MDLA, a specific inhibitor of AsS. BPP-10c reduced iNOS expression and nitrate levels but decreased NF-kB expression. Furthermore, BPP-10c protected the mitochondrial membrane against oxidation. Overall, we demonstrated for the first time neuroprotective mechanisms of BPPs against oxidative stress, opening new perspectives to the study and application of these peptides for the treatment of neurodegenerative diseases. Copyright © 2018 Elsevier Inc. All rights reserved.

  14. H2O2 modulates the energetic metabolism of the cloud microbiome

    NASA Astrophysics Data System (ADS)

    Wirgot, Nolwenn; Vinatier, Virginie; Deguillaume, Laurent; Sancelme, Martine; Delort, Anne-Marie

    2017-12-01

    Chemical reactions in clouds lead to oxidation processes driven by radicals (mainly HO⚫, NO3⚫, or HO2⚫) or strong oxidants such as H2O2, O3, nitrate, and nitrite. Among those species, hydrogen peroxide plays a central role in the cloud chemistry by driving its oxidant capacity. In cloud droplets, H2O2 is transformed by microorganisms which are metabolically active. Biological activity can therefore impact the cloud oxidant capacity. The present article aims at highlighting the interactions between H2O2 and microorganisms within the cloud system. First, experiments were performed with selected strains studied as a reference isolated from clouds in microcosms designed to mimic the cloud chemical composition, including the presence of light and iron. Biotic and abiotic degradation rates of H2O2 were measured and results showed that biodegradation was the most efficient process together with the photo-Fenton process. H2O2 strongly impacted the microbial energetic state as shown by adenosine triphosphate (ATP) measurements in the presence and absence of H2O2. This ATP depletion was not due to the loss of cell viability. Secondly, correlation studies were performed based on real cloud measurements from 37 cloud samples collected at the PUY station (1465 m a.s.l., France). The results support a strong correlation between ATP and H2O2 concentrations and confirm that H2O2 modulates the energetic metabolism of the cloud microbiome. The modulation of microbial metabolism by H2O2 concentration could thus impact cloud chemistry, in particular the biotransformation rates of carbon compounds, and consequently can perturb the way the cloud system is modifying the global atmospheric chemistry.

  15. NASA Lewis H2-O2 MHD program

    NASA Technical Reports Server (NTRS)

    Smith, M.; Nichols, L. D.; Seikel, G. R.

    1974-01-01

    Performance and power costs of H2-O2 combustion powered steam-MHD central power systems are estimated. Hydrogen gas is assumed to be transmitted by pipe from a remote coal gasifier into the city and converted to electricity in a steam MHD plant having an integral gaseous oxygen plant. These steam MHD systems appear to offer an attractive alternative to both in-city clean fueled conventional steam power plants and to remote coal fired power plants with underground electric transmission into the city. Status and plans are outlined for an experimental evaluation of H2-O2 combustion-driven MHD power generators at NASA Lewis Research Center.

  16. Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

    PubMed

    Yang, Jingying; Xie, Zuowei

    2015-04-14

    Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

  17. Analysis of H2O in silicate glass using attenuated total reflectance (ATR) micro-FTIR spectroscopy

    USGS Publications Warehouse

    Lowenstern, Jacob B.; Pitcher, Bradley W.

    2013-01-01

    We present a calibration for attenuated total reflectance (ATR) micro-FTIR for analysis of H2O in hydrous glass. A Ge ATR accessory was used to measure evanescent wave absorption by H2O within hydrous rhyolite and other standards. Absorbance at 3450 cm−1 (representing total H2O or H2Ot) and 1630 cm−1 (molecular H2O or H2Om) showed high correlation with measured H2O in the glasses as determined by transmission FTIR spectroscopy and manometry. For rhyolite, wt%H2O=245(±9)×A3450-0.22(±0.03) and wt%H2Om=235(±11)×A1630-0.20(±0.03) where A3450 and A1630 represent the ATR absorption at the relevant infrared wavelengths. The calibration permits determination of volatiles in singly polished glass samples with spot size down to ~5 μm (for H2O-rich samples) and detection limits of ~0.1 wt% H2O. Basaltic, basaltic andesite and dacitic glasses of known H2O concentrations fall along a density-adjusted calibration, indicating that ATR is relatively insensitive to glass composition, at least for calc-alkaline glasses. The following equation allows quantification of H2O in silicate glasses that range in composition from basalt to rhyolite: wt%H2O=(ω×A3450/ρ)+b where ω = 550 ± 21, b = −0.19 ± 0.03, ρ = density, in g/cm3, and A3450 is the ATR absorbance at 3450 cm−1. The ATR micro-FTIR technique is less sensitive than transmission FTIR, but requires only a singly polished sample for quantitative results, thus minimizing time for sample preparation. Compared with specular reflectance, it is more sensitive and better suited for imaging of H2O variations in heterogeneous samples such as melt inclusions. One drawback is that the technique can damage fragile samples and we therefore recommend mounting of unknowns in epoxy prior to polishing. Our calibration should hold for any Ge ATR crystals with the same incident angle (31°). Use of a different crystal type or geometry would require measurement of several H2O-bearing standards to provide a crystal

  18. Low levels of iron enhance UV/H2O2 efficiency at neutral pH.

    PubMed

    Ulliman, Sydney L; McKay, Garrett; Rosario-Ortiz, Fernando L; Linden, Karl G

    2018-03-01

    While the presence of iron is generally not seen as favorable for UV-based treatment systems due to lamp fouling and decreased UV transmittance, we show that low levels of iron can lead to improvements in the abatement of chemicals in the UV-hydrogen peroxide advanced oxidation process. The oxidation potential of an iron-assisted UV/H 2 O 2 (UV 254  + H 2 O 2  + iron) process was evaluated at neutral pH using iron levels below USEPA secondary drinking water standards (<0.3 mg/L). Para-chlorobenzoic acid (pCBA) was used as a hydroxyl radical (HO) probe to quantify HO steady state concentrations. Compounds degraded by different mechanisms including, carbamazepine (CBZ, HO oxidation) and N-nitrosodimethylamine (NDMA, direct photolysis), were used to investigate the effect of iron on compound degradation for UV/H 2 O 2 systems. The effects of iron species (Fe 2+ and Fe 3+ ), iron concentration (0-0.3 mg/L), H 2 O 2 concentration (0-10 mg/L) and background water matrix (low-carbon tap (LCT) and well water) on HO production and compound removal were examined. Iron-assisted UV/H 2 O 2 efficiency was most influenced by the target chemical and the water matrix. Added iron to UV/H 2 O 2 was shown to increase the steady-state HO concentration by approximately 25% in all well water scenarios. While CBZ removal was unchanged by iron addition, 0.3 mg/L iron improved NDMA removal rates in both LCT and well water matrices by 15.1% and 4.6% respectively. Furthermore, the combination of UV/Fe without H 2 O 2 was also shown to enhance NDMA removal when compared to UV photolysis alone indicating the presence of degradation pathways other than HO oxidation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Correlation between pH dependence of O2 evolution and sensitivity of Mn cations in the oxygen-evolving complex to exogenous reductants.

    PubMed

    Semin, Boris K; Davletshina, Lira N; Rubin, Andrei B

    2015-08-01

    Effects of pH, Ca(2+), and Cl(-) ions on the extraction of Mn cations from oxygen-evolving complex (OEC) in Ca-depleted photosystem II (PSII(-Ca)) by exogenous reductants hydroquinone (H2Q) and H2O2 were studied. Two of 4 Mn cations are released by H2Q and H2O2 at pHs 5.7, 6.5, and 7.5, and their extraction does not depend on the presence of Ca(2+) and Cl(-) ions. One of Mn cations ("resistant" Mn cation) cannot be extracted by H2Q and H2O2 at any pH. Extraction of 4th Mn ion ("flexible" Mn cation) is sensitive to pH, Ca(2+), and Cl(-). This Mn cation is released by reductants at pH 6.5 but not at pHs 5.7 and 7.5. A pH dependence curve of the oxygen-evolving activity in PSII(-Ca) membranes (in the presence of exogenous Ca(2+)) has a bell-shaped form with the maximum at pH 6.5. Thus, the increase in the resistance of flexible Mn cation in OEC to the action of reductants at acidic and alkaline pHs coincides with the decrease in oxygen evolution activity at these pHs. Exogenous Ca(2+) protects the extraction of flexible Mn cation at pH 6.5. High concentration of Cl(-) anions (100 mM) shifts the pH optimum of oxygen evolution to alkaline region (around pH 7.5), while the pH of flexible Mn extraction is also shifted to alkaline pH. This result suggests that flexible Mn cation plays a key role in the water-splitting reaction. The obtained results also demonstrate that only one Mn cation in Mn4 cluster is under strong control of calcium. The change in the flexible Mn cation resistance to exogenous reductants in the presence of Ca(2+) suggests that Ca(2+) can control the redox potential of this cation.

  20. Radical-scavenging abilities and antioxidant properties of theaflavins and their gallate esters in H2O2-mediated oxidative damage system in the HPF-1 cells.

    PubMed

    Yang, Ziyin; Jie, Guoliang; Dong, Fang; Xu, Yi; Watanabe, Naoharu; Tu, Youying

    2008-08-01

    The antioxidant properties of theaflavins and their gallate esters, namely theaflavin (TF1), theaflavin-3(3')-gallate (TF2) and theaflavin-3,3'-digallate (TF3) were investigated by comparing with epigallocatechin gallate (EGCG). The order of hydroxyl radicals-scavenging ability was TF3>TF2>TF1>EGCG. The order of 2,2-diphenyl-1-picrylhydrazyl scavenging ability was TF3>TF2>EGCG>TF1. TF1, TF2, and TF3 showed more effective effects than EGCG in protection against H2O2-mediated damage in HPF-1 cells. TF2 was the most potent accelerant of HPF-1 cell proliferation. TF1, TF2 and TF3 suppressed the accumulation of intracellular reactive species in H2O2-mediated damage HPF-1 cells. Pre-treated for 2h and eliminated from the cells, TF1 and TF3 still showed protective effects against H2O2-mediated damage in HPF-1 cells. This suggests that the protective effects of TF1 and TF3 on oxidative damage HPF-1 cells may be responsible for other mechanisms, rather than only scavenging the already formed reactive species. It remains to be determined whether TF1 and TF3 improved the normal HPF-1 cell resistive abilities toward radical-damage in pre-treatment. Further studies of the effects of theaflavins on some enzymes or signal transduction in the normal HPF-1 cells are underway.

  1. Oxyhydroxide of metallic nanowires in a molecular H2O and H2O2 environment and their effects on mechanical properties.

    PubMed

    Aral, Gurcan; Islam, Md Mahbubul; Wang, Yun-Jiang; Ogata, Shigenobu; Duin, Adri C T van

    2018-06-14

    To avoid unexpected environmental mechanical failure, there is a strong need to fully understand the details of the oxidation process and intrinsic mechanical properties of reactive metallic iron (Fe) nanowires (NWs) under various aqueous reactive environmental conditions. Herein, we employed ReaxFF reactive molecular dynamics (MD) simulations to elucidate the oxidation of Fe NWs exposed to molecular water (H2O) and hydrogen peroxide (H2O2) environment, and the influence of the oxide shell layer on the tensile mechanical deformation properties of Fe NWs. Our structural analysis shows that oxidation of Fe NWs occurs with the formation of different iron oxide and hydroxide phases in the aqueous molecular H2O and H2O2 oxidizing environments. We observe that the resulting microstructure due to pre-oxide shell layer formation reduces the mechanical stress via increasing the initial defect sites in the vicinity of the oxide region to facilitate the onset of plastic deformation during tensile loading. Specifically, the oxide layer of Fe NWs formed in the H2O2 environment has a relatively significant effect on the deterioration of the mechanical properties of Fe NWs. The weakening of the yield stress and Young modulus of H2O2 oxidized Fe NWs indicates the important role of local oxide microstructures on mechanical deformation properties of individual Fe NWs. Notably, deformation twinning is found as the primary mechanical plastic deformation mechanism of all Fe NWs, but it is initially observed at low strain and stress level for the oxidized Fe NWs.

  2. Lignin Sulfonation and SO2 Addition Enhance the Hydrolyzability of Deacetylated and Then Steam-Pretreated Poplar with Reduced Inhibitor Formation.

    PubMed

    Tang, Yong; Dou, Xiaoli; Hu, Jinguang; Jiang, Jianxin; Saddler, Jack N

    2018-01-01

    The merit of deacetylation of corn stover prior to pretreatment is decreasing the formation of inhibitors and improving enzyme hydrolysis, proved in dilute acid pretreatment. However, few studies are done on how deacetylation would affect bioconversion process containing steam explosion. In this study, the effect of deacetylation on steam explosion was conducted using poplar as substrate. About 57 to 90% of acetyl group in poplar, depending on alkaline types and concentration, was removed by dilute alkaline deacetylation in 6 h. Deacetylation eliminated over 85% of inhibitor formation during downstream steam explosion. However, deacetylation prior to steam explosion decreased the dissolution of hemicellulose, thus reducing the cellulose accessibility of pretreated poplar, finally resulting in 5-20% decrease in glucose yield and 20-35% decrease in xylose yield. The addition of 5% SO 2 during steam explosion significantly improved the hydrolysis of deacetylated and pretreated poplar without significantly increasing the concentration of inhibitors. Incorporating 45 mmol/kg sulfoacid group in lignin fraction of deacetylated and then pretreated poplar dramatically improved the xylose yield to about 100% and increased the glucose yield by 30%.

  3. Active sites and mechanisms for H2O2 decomposition over Pd catalysts

    PubMed Central

    Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

    2016-01-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  4. Influences of H2O mass fraction and chemical kinetics mechanism on the turbulent diffusion combustion of H2-O2 in supersonic flows

    NASA Astrophysics Data System (ADS)

    Huang, Wei; Wang, Zhen-guo; Li, Shi-bin; Liu, Wei-dong

    2012-07-01

    Hydrogen is one of the most promising fuels for the airbreathing hypersonic propulsion system, and it attracts an increasing attention of the researchers worldwide. In this study, a typical hydrogen-fueled supersonic combustor was investigated numerically, and the predicted results were compared with the available experimental data in the open literature. Two different chemical reaction mechanisms were employed to evaluate their effects on the combustion of H2-O2, namely the two-step and the seven-step mechanisms, and the vitiation effect was analyzed by varying the H2O mass fraction. The obtained results show that the predicted mole fraction profiles for different components show very good agreement with the available experimental data under the supersonic mixing and combustion conditions, and the chemical reaction mechanism has only a slight impact on the overall performance of the turbulent diffusion combustion. The simple mechanism of H2-O2 can be employed to evaluate the performance of the combustor in order to reduce the computational cost. The H2O flow vitiation makes a great difference to the combustion of H2-O2, and there is an optimal H2O mass fraction existing to enhance the intensity of the turbulent combustion. In the range considered in this paper, its optimal value is 0.15. The initiated location of the reaction appears far away from the bottom wall with the increase of the H2O mass fraction, and the H2O flow vitiation quickens the transition from subsonic to supersonic mode at the exit of the combustor.

  5. Interface actions between TiO2 and porous diatomite on the structure and photocatalytic activity of TiO2-diatomite

    NASA Astrophysics Data System (ADS)

    Xia, Yue; Li, Fangfei; Jiang, Yinshan; Xia, Maosheng; Xue, Bing; Li, Yanjuan

    2014-06-01

    TiO2-diatomite photocatalysts were prepared by sol-gel process with various pre-modified diatomite. In order to obtain diatomite with different surface characteristics, two modification approaches including calcination and phosphoric acid treatment on the micro-structure of diatomite are introduced. The photocatalysts were characterized by XRD, XPS, nitrogen adsorption-desorption isotherms and micromorphology analysis. The results indicate that, compared with pure TiO2, the anatase-to-rutile phase transition temperature of TiO2 loaded on diatomite carrier is significantly increased to nearly 900 °C, depending on the different pretreatment method of diatomite. The photocatalytic activities of different samples were evaluated by their degradation rate of methyl orange (MO) dye under UV and visible-light irradiation. The samples prepared by phosphoric acid pretreatment method exhibit the highest photocatalytic activity. After 90 min of UV irradiation, about 90% of MO is decomposed by the best effective photocatalyst. And after 8 h visible-light irradiation, nearly 60% of MO is decomposed by the same sample. Further mechanism investigation reveals that the H3PO4 pretreatment process can obviously change the surface features of diatomite carrier, cause the formation of Si-O-Ti bond, increase the binding strength between TiO2 and diatomite, restrain crystal growth of loaded TiO2, and thus form thermal-stable mesoporous structure at the granular spaces. It helps to build micro-, meso- and macro-porous hierarchical porous structure in TiO2-diatomite, and improves the charge and mass transfer efficiency during catalyzing process, resulting in the significantly increased photocatalytic activity of TiO2-diatomite pretreated by phosphoric acid.

  6. Intestinal alkaline phosphatase regulates protective surface microclimate pH in rat duodenum.

    PubMed

    Mizumori, Misa; Ham, Maggie; Guth, Paul H; Engel, Eli; Kaunitz, Jonathan D; Akiba, Yasutada

    2009-07-15

    Regulation of localized extracellular pH (pH(o)) maintains normal organ function. An alkaline microclimate overlying the duodenal enterocyte brush border protects the mucosa from luminal acid. We hypothesized that intestinal alkaline phosphatase (IAP) regulates pH(o) due to pH-sensitive ATP hydrolysis as part of an ecto-purinergic pH regulatory system, comprised of cell-surface P2Y receptors and ATP-stimulated duodenal bicarbonate secretion (DBS). To test this hypothesis, we measured DBS in a perfused rat duodenal loop, examining the effect of the competitive alkaline phosphatase inhibitor glycerol phosphate (GP), the ecto-nucleoside triphosphate diphosphohydrolase inhibitor ARL67156, and exogenous nucleotides or P2 receptor agonists on DBS. Furthermore, we measured perfusate ATP concentration with a luciferin-luciferase bioassay. IAP inhibition increased DBS and luminal ATP output. Increased luminal ATP output was partially CFTR dependent, but was not due to cellular injury. Immunofluorescence localized the P2Y(1) receptor to the brush border membrane of duodenal villi. The P2Y(1) agonist 2-methylthio-ADP increased DBS, whereas the P2Y(1) antagonist MRS2179 reduced ATP- or GP-induced DBS. Acid perfusion augmented DBS and ATP release, further enhanced by the IAP inhibitor l-cysteine, and reduced by the exogenous ATPase apyrase. Furthermore, MRS2179 or the highly selective P2Y(1) antagonist MRS2500 co-perfused with acid induced epithelial injury, suggesting that IAP/ATP/P2Y signalling protects the mucosa from acid injury. Increased DBS augments IAP activity presumably by raising pH(o), increasing the rate of ATP degradation, decreasing ATP-mediated DBS, forming a negative feedback loop. The duodenal epithelial brush border IAP-P2Y-HCO(3-) surface microclimate pH regulatory system effectively protects the mucosa from acid injury.

  7. Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130°C and 2.2 GPa

    NASA Astrophysics Data System (ADS)

    Ridolfi, Filippo; Renzulli, Alberto

    2012-05-01

    The following article presents constraints of the stability of Mg-rich (Mg/(Mg + Fe2+) > 0.5) calcic amphibole in both calc-alkaline and alkaline magmas, testing of previous thermobarometers, and formulation of new empirical equations that take into consideration a large amount of literature data (e.g. more than one thousand amphibole compositions among experimental and natural crystals). Particular care has been taken in choosing a large number of natural amphiboles and selecting quality experimental data from literature. The final database of experimental data, composed of 61 amphiboles synthesized in the ranges of 800-1,130°C and 130-2,200 MPa, indicates that amphibole crystallization occurs in a horn-like P- T stability field limited by two increasing curves (i.e. the thermal stability and an upper limit), which should start to bend back to higher pressures. Among calcic amphiboles, magnesiohornblendes and tschermakitic pargasites are only found in equilibrium with calc-alkaline melts and crystallize at relatively shallow conditions ( P up to ~1 GPa). Kaersutite and pargasite are species almost exclusively found in alkaline igneous products, while magnesiohastingsite is equally distributed in calc-alkaline and alkaline rocks. The reliability of previous amphibole applications was checked using the selected experimental database. The results of this testing indicate that none of the previous thermobarometers can be successfully used to estimate the P, T and fO2 in a wide range of amphibole crystallization conditions. Multivariate least-square analyses of experimental amphibole compositions and physico-chemical parameters allowed us to achieve a new thermobarometric model that gives reasonably low uncertainties ( T ± 23.5°C, P ± 11.5%, H2Omelt ± 0.78wt%) for calc-alkaline and alkaline magmas in a wide range of P- T conditions (up to 1,130°C and 2,200 MPa) and ΔNNO values (±0.37 log units) up to 500 MPa. The AK-[4]Al relation in amphibole can be readily

  8. O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

    PubMed

    Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

    2017-10-05

    Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

  9. Acidic and alkaline pretreatments of activated carbon and their effects on the performance of air-cathodes in microbial fuel cells.

    PubMed

    Wang, Xin; Gao, Ningshengjie; Zhou, Qixing; Dong, Heng; Yu, Hongbing; Feng, Yujie

    2013-09-01

    Activated carbon (AC) is a high performing and cost effective catalyst for oxygen reduction reactions (ORRs) of air-cathodes in microbial fuel cells (MFCs). Acidic (HNO3) and alkaline (KOH) pretreatments on AC at low temperature (85°C) are conducted to enhance the performance of MFCs. The alkaline pretreatment increased the power density by 16% from 804±70 to 957±31 mW m(-2), possibly due to the decrease of ohmic resistance (from 20.58 to 19.20 Ω) and the increase of ORR activities provided by the adsorbed hydroxide ion and extra micropore area/volume after alkaline pretreatment. However, acidic pretreatment decreased the power output to 537±36 mW m(-2), which can be mainly attributed to the corrosion by adsorbed proton at the interface of AC powder and stainless steel mesh and the decreased pore area. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. GaAs micromachining in the 1 H2SO4:1 H2O2:8 H2O system. From anisotropy to simulation

    NASA Astrophysics Data System (ADS)

    Tellier, C. R.

    2011-02-01

    The bulk micromachining on (010), (110) and (111)A GaAs substrates in the 1 H2SO4:1 H2O2:8 H2O system is investigated. Focus is placed on anisotropy of 3D etching shapes with a special emphasis on convex and concave undercuts which are of prime importance in the wet micromachining of mechanical structures. Etched structures exhibit curved contours and more and less rounded sidewalls showing that the anisotropy is of type 2. This anisotropy can be conveniently described by a kinematic and tensorial model. Hence, a database composed of dissolution constants is further determined from experiments. A self-elaborated simulator which works with the proposed database is used to derive theoretical 3D shapes. Simulated shapes agree well with observed shapes of microstructures. The successful simulations open up two important applications for MEMS: CAD of mask patterns and meshing of simulated shapes for FEM simulation tools.

  11. Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols.

    PubMed

    Bi, Jianhong; Kong, Lingtao; Huang, Zixiang; Liu, Jinhuai

    2008-06-02

    Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.

  12. Transfer of a proton between H2 and O2.

    PubMed

    Kluge, Lars; Gärtner, Sabrina; Brünken, Sandra; Asvany, Oskar; Gerlich, Dieter; Schlemmer, Stephan

    2012-11-13

    The proton affinities of hydrogen and oxygen are very similar. Therefore, it has been discussed that the proton transfer from the omnipresent H(3)(+) to molecular oxygen in the near thermoneutral reaction H(3)(+) + O(2) <--> O(2)H(+) + H(2) effectively binds the interstellar oxygen in O(2)H(+). In this work, the proton transfer reaction has been investigated in a low-temperature 22-pole ion trap from almost room temperature (280 K) down to the lowest possible temperature limited by freeze out of oxygen gas (about 40 K at a low pressure). The Arrhenius behaviour of the rate coefficient for the forward reaction shows that it is subject to an activation energy of E(A)/k=113 K. Thus, the forward reaction can proceed only in higher temperature molecular clouds. Applying laser-induced reactions to the given reaction (in the backward direction), a preliminary search for spectroscopic signatures of O(2)H(+) in the infrared was unsuccessful, whereas the forward reaction has been successfully used to probe the population of the lowest ortho and para levels of H(3)(+).

  13. Ro-vibrational spectrum of H2O-Ne in the ν2 H2O bending region: A combined ab initio and experimental investigation

    NASA Astrophysics Data System (ADS)

    Liu, Xunchen; Hou, Dan; Thomas, Javix; Li, Hui; Xu, Yunjie

    2016-12-01

    High resolution ro-vibrational transitions of the H2O-Ne complex in the ν2 bending region of H2O at 6 μm have been measured using a rapid scan infrared spectrometer based on an external cavity quantum cascade laser and an astigmatic multipass optical cell. To aid the spectral assignment, a four-dimension potential energy surface of H2O-Ne which depends on the intramolecular bending coordinate of the H2O monomer and the three intermolecular vibrational coordinates has been constructed and the rovibrational transitions have been calculated. Three ortho and two para H2O-20Ne bands have been identified from the experimental spectra. Some weaker transitions belonging to H2O-22Ne have also been identified experimentally. Spectroscopic fits have been performed for both the experimental and theoretical transition frequencies using a simple pseudo-diatomic Hamiltonian including both Coriolis coupling and Fermi resonance terms. The experimental and theoretical spectroscopic constants thus obtained have been compared. Further improvements needed in the potential energy surface and the related spectral simulation have been discussed.

  14. Odin observations of H2O and O2 in comets and interstellar clouds

    NASA Astrophysics Data System (ADS)

    Hjalmarson, Åke; Odin Team

    2002-11-01

    We here report on results from single-position observations, and in some cases also mapping, of the 557 GHz ortho-H2O line in several comets and in many interstellar molecular clouds by the Odin sub-millimetre wave spectroscopy satellite. The H2O production rates have been accurately determined in four comets, C/2001 A2 (LINEAR), 19P/Borrelly, C/2000 WM1 (LINEAR), and 153P/2002 C1 (Ikeya-Zhang). In comet Ikeya-Zhang our detection at a low level of the corresponding H218O emission line verifies the H2O production rate (which depends upon the assumed radiative and collisional excitation and also upon radiative transfer modelling) and is consistent with a nearly terrestrial 16O/18O-isotope ratio. In an astrobiological context, the cometary H2O production rates are especially important as reference levels for comparison with abundances of other molecules simultaneously observed with ground-based telescopes. In interstellar clouds the observed gas-phase H2O abundances (vs H2) range from 5×10-4 in the Orion KL outflow/shock region (where essentially all oxygen is locked up in H2O) to circa 10-8 in quiescent cloud regions (where H2O) is just one of many trace molecules). From an astrobiological point of view, the molecular abundances in star forming clouds are important in terms of initial conditions for the chemistry in proto-planetary disks ("proto-solar nebulae"), the formation sites of new planetary systems. In simultaneous observations, Odin has also detected the 572 GHz ortho-NH3 line in cold and warm clouds as well as in the Orion outflow and Bar/PDR regions (an area of increased ionisation caused by the intense UV flux from newly born massive stars). In other simultaneous observations, we have performed sensitive searches for O2 at 119 GHz. Although no detection can be reported as yet, the resulting very low abundance limits (<10-7) are very intriguing when they are compared with current "standard" model expectations, which fall in the range 10-5-10-4.

  15. Theoretical studies of UO(2)(OH)(H(2)O)(n) (+), UO(2)(OH)(2)(H(2)O)(n), NpO(2)(OH)(H(2)O)(n), and PuO(2)(OH)(H(2)O)(n) (+) (n

    PubMed

    Cao, Zhiji; Balasubramanian, K

    2009-10-28

    Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO(2)(OH)(+), UO(2)(OH)(2), NpO(2)(OH), and PuO(2)(OH)(+) complexes that contain up to 21 water molecules both in first and second hydration spheres in both aqueous solution and the gas phase. The structures have been further optimized by considering long-range solvent effects through a polarizable continuum dielectric model. The hydrolysis reaction Gibbs free energy of UO(2)(H(2)O)(5) (2+) is computed to be 8.11 kcal/mol at the MP2 level in good agreement with experiments. Our results reveal that it is necessary to include water molecules bound to the complex in the first hydration sphere for proper treatment of the hydrated complex and the dielectric cavity although water molecules in the second hydration sphere do not change the coordination complex. Structural reoptimization of the complex in a dielectric cavity seems inevitable to seek subtle structural variations in the solvent and to correlate with the observed spectra and thermodynamic properties in the aqueous environment. Our computations reveal dramatically different equilibrium structures in the gas phase and solution and also confirm the observed facile exchanges between the complex and bulk solvent. Complete active space multiconfiguration self-consistent field followed by multireference singles+doubles CI (MRSDCI) computations on smaller complexes confirm predominantly single-configurational nature of these species and the validity of B3LYP and MP2 techniques for these complexes in their ground states.

  16. The effect of H2O and CO2 on planetary mantles

    NASA Technical Reports Server (NTRS)

    Wyllie, P. J.

    1978-01-01

    The peridotite-H2O-CO2 system is discussed, and it is shown that even traces of H2O and CO2, in minerals or vapor, lower mantle solidus temperatures through hundreds of degrees in comparison with the volatile-free solidus. The solidus for peridotite-H2O-CO2 is a divariant surface traversed by univariant lines that locate the intersections of subsolidus divariant surfaces for carbonation or hydration reactions occurring in the presence of H2O-CO2 mixtures. Vapor phase compositions are normally buffered to these lines, and near the buffered curve for the solidus of partly carbonated peridotite there is a temperature maximum on the peridotite-vapor solidus. Characteristics on the CO2 side of the maximum and on the H2O side of the maximum are described.

  17. [{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron.

    PubMed

    Botar, Bogdan; Kögerler, Paul; Hill, Craig L

    2005-07-07

    Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure.

  18. Defining the chemical role of H2O in mantle melts: Effect of melt composition and H2O content on the activity of SiO2

    NASA Astrophysics Data System (ADS)

    Moore, G.; Roggensack, K.

    2007-12-01

    Quantifying the influence of volatiles (H2O, CO2) on the chemistry of mantle melts is a critical aspect of understanding the petrogenesis of arc magmas. A significant amount of experimental work done on the effect of H2O on the solidii of various mantle compositions, as well as on multiple saturation points of various primitive melts, has shown that H2O stabilizes olivine with respect to orthopyroxene. Or, in other words, at constant activity of SiO2, the presence of H2O decreases the activity coefficient of SiO2 in the melt, potentially leading to mantle melts that have suprisingly high SiO2 contents (Carmichael, 2002). Quantification and modelling of this behavior in hydrous silicate melts in equilibrium with the mantle have proven problematic, due mainly to a relatively small set of experiments that allow this type of thermodynamic analysis, and because of the experimental and analytical difficulties of dealing with hydrous high P-T samples (e.g. quench to a glass, rapid melt-solid reaction on quench, electron beam sensitivity of resulting glass, volatile content determination, etc). A further complication in the existing data includes co-variance of important experimental parameters (e.g. T and H2O content), making robust statistical regression analysis difficult and potentially misleading. We present here results of high P-T experiments conducted at a single pressure and temperature (1.0 GPa, 1200 deg C) that have the specific goal of quantifying the effect of H2O, as well as other melt components, on the activity coefficient of SiO2 in mantle melts. Using a "sandwich" type experiment, basaltic melts are saturated with an olivine plus orthopyroxene mineral assemblage with varying H2O and CO2 contents. The resulting samples have their bulk solid phase and glass compositions determined using EPMA, and the volatile content of the glass is determined by FTIR. The activity of SiO2 is then calculated using the olivine and orthopyroxene compositions. This value is

  19. Potential of potassium hydroxide pretreatment of switchgrass for fermentable sugar production.

    PubMed

    Sharma, Rajat; Palled, Vijaykumar; Sharma-Shivappa, Ratna R; Osborne, Jason

    2013-02-01

    Chemical pretreatment of lignocellulosic biomass has been extensively investigated for sugar generation and subsequent fuel production. Alkaline pretreatment has emerged as one of the popular chemical pretreatment methods, but most attempts thus far have utilized NaOH for the pretreatment process. This study aimed at investigating the potential of potassium hydroxide (KOH) as a viable alternative alkaline reagent for lignocellulosic pretreatment based on its different reactivity patterns compared to NaOH. Performer switchgrass was pretreated at KOH concentrations of 0.5-2% for varying treatment times of 6-48 h, 6-24 h, and 0.25-1 h at 21, 50, and 121 °C, respectively. The pretreatments resulted in the highest percent sugar retention of 99.26% at 0.5%, 21 °C, 12 h while delignification up to 55.4% was observed with 2% KOH, 121 °C, 1 h. Six pretreatment conditions were selected for subsequent enzymatic hydrolysis with Cellic CTec2® for sugar generation. The pretreatment condition of 0.5% KOH, 24 h, 21 °C was determined to be the most effective as it utilized the least amount of KOH while generating 582.4 mg sugar/g raw biomass for a corresponding percent carbohydrate conversion of 91.8%.

  20. A V(IV) Hydroxyhydrogenomonophosphate with an Intersecting Tunnel Structure: HK 4[V 10O 10(H 2O) 2(OH) 4(PO 4) 7]·9H 2O

    NASA Astrophysics Data System (ADS)

    Berrah, F.; Guesdon, A.; Leclaire, A.; Borel, M. M.; Provost, J.; Raveau, B.

    1999-12-01

    A V(IV) hydroxyhydrogenomonophosphate HK4[V10O10(H2O)2(OH)4(PO4)7]·9H2O has been obtained, using hydrothermal conditions. Its structure, closely related to that of (CH3)2NH2K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O, differs from the latter by its I41/a space group (instead of P43). This difference corresponds to a "disordering" of the vanadium atoms, with respect to the dimethyl ammonium phase. It is shown that this disorder, which appears in the form of "V5O22" units distributed at random, does not affect the oxygen framework. The analysis of this complex structure shows that it can be described from the stacking along c of [V8P7O38(OH)4(H2O)2]∞ layers interconnected through layers of isolated VO6 octahedra. In this structure, built up of VO6, VO5OH, and VO4(OH)(H2O) octahedra, of VO4OH pyramids, and of PO4 tetrahedra, large "toffee" tunnels and smaller ones with a tulip-shape section are running along a (or b). The first ones are stuffed with H2O molecules forming aquo tubes, where protons are likely "delocalized," whereas the second ones are occupied by K+ cations.

  1. Tracking the energy flow in the hydrogen exchange reaction OH + H2OH2O + OH.

    PubMed

    Zhu, Yongfa; Ping, Leilei; Bai, Mengna; Liu, Yang; Song, Hongwei; Li, Jun; Yang, Minghui

    2018-05-09

    The prototypical hydrogen exchange reaction OH + H2OH2O + OH has attracted considerable interest due to its importance in a wide range of chemically active environments. In this work, an accurate global potential energy surface (PES) for the ground electronic state was developed based on ∼44 000 ab initio points at the level of UCCSD(T)-F12a/aug-cc-pVTZ. The PES was fitted using the fundamental invariant-neural network method with a root mean squared error of 4.37 meV. The mode specific dynamics was then studied by the quasi-classical trajectory method on the PES. Furthermore, the normal mode analysis approach was employed to calculate the final vibrational state distribution of the product H2O, in which a new scheme to acquire the Cartesian coordinates and momenta of each atom in the product molecule from the trajectories was proposed. It was found that, on one hand, excitation of either the symmetric stretching mode or the asymmetric stretching mode of the reactant H2O promotes the reaction more than the translational energy, which can be rationalized by the sudden vector projection model. On the other hand, the relatively higher efficacy of exciting the symmetric stretching mode than that of the asymmetric stretching mode is caused by the prevalence of the indirect mechanism at low collision energies and the stripping mechanism at high collision energies. In addition, the initial collision energy turns ineffectively into the vibrational energy of the products H2O and OH while a fraction of the energy transforms into the rotational energy of the product H2O. Fundamental excitation of the stretching modes of H2O results in the product H2O having the highest population in the fundamental state of the asymmetric stretching mode, followed by the ground state and the fundamental state of the symmetric stretching mode.

  2. A potential energy surface for the process H2 + H2O yielding H + H + H2O - Ab initio calculations and analytical representation

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

    1991-01-01

    Extensive ab initio calculations on the ground state potential energy surface of H2 + H2O were performed using a large contracted Gaussian basis set and a high level of correlation treatment. An analytical representation of the potential energy surface was then obtained which reproduces the calculated energies with an overall root-mean-square error of only 0.64 mEh. The analytic representation explicitly includes all nine internal degrees of freedom and is also well behaved as the H2 dissociates; it thus can be used to study collision-induced dissociation or recombination of H2. The strategy used to minimize the number of energy calculations is discussed, as well as other advantages of the present method for determining the analytical representation.

  3. IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

    NASA Astrophysics Data System (ADS)

    Vanderdeelen, Jan

    2012-06-01

    The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO3 types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO3. H2O), the hexahydrate ikaite (CaCO3.6H2O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

  4. Preparation, Characterization, and Structure of Two Layered Molybdenum(VI) Phosphates: KMo(H 2O)O 2PO 4 and NH 4Mo(H 2O)O 2PO 4

    NASA Astrophysics Data System (ADS)

    Millini, Roberto; Carati, Angela

    1995-08-01

    New layered Mo(VI) compounds, KMo(H 2O)O 2PO 4 (I) and NH 4Mo(H 2O)O 2PO 4 (II), were synthesized hydrothermally and their structures were determined from single-crystal X-ray analysis. Compounds (I) and (II) are isostructural and crystallize in the monoclinic P2 1/ n space group with a = 12.353(3), b = 8.623(2), c = 5.841(1) Å, β = 102.78(1)°, V = 606.8(2) Å 3, Z = 4, and R = 0.027 ( Rw = 0.030) for compound (I) and a = 12.435(3), b = 8.761(2), c = 6.015(1), β = 103.45(1)°, V = 637.3(2) Å 3, Z = 4, and R = 0.040 ( Rw = 0.041) for compound (II). The structure consists of layers built up of eight- and four-membered rings resulting from the alternation of corner-sharing [MoO 6] octahedra and [PO 4] tetrahedra. The layers stack along the (1¯01) direction by intercalating K and NH 4 ions.

  5. Empirical electronic polarizabilities: deviations from the additivity rule. I. M2+SO4·nH2O, blödite Na2M2+(SO4)2·4H2O, and kieserite-related minerals with sterically strained structures

    NASA Astrophysics Data System (ADS)

    Gagné, Olivier; Hawthorne, Frank; Shannon, Robert D.; Fischer, Reinhard X.

    2017-09-01

    Empirical electronic polarizabilities allow the prediction of total mineral polarizabilities and mean refractive indices of the vast majority of minerals and synthetic oxides. However, deviations from the valence-sum rule at cations in some minerals are associated with large deviations of observed from calculated total polarizabilities. We have identified several groups of minerals and compounds where deviations from the valence-sum rule at cations lead to polarizability deviations of 2-5%: M(SO4)·nH2O, n = 1-6, blödite-group minerals [Na2M2+(SO4)2·4H2O], and the kieserite-related minerals: isokite, panasqueiraite and tilasite. In these minerals, the environment of the M ions contains both O and H2O: Mg[O4(H2O)2] in kieserite, szmikite, and szomolnokite; Mg[O2(H2O)4] in starkeyite, ilesite, and rozenite, and Mg[(H2O)6] in hexahydrite. In compounds where the ligands are only H2O, deviations from the valence-sum rule at the M(H2O)6 groups are not accompanied by significant polarizability deviations. This is the case for epsomite, MgSO4·7H2O; bieberite, CoSO4·7H2O; goslarite, ZnSO4·7H2O, six silicofluorides, MSiF6·6H2O; eighteen Tutton's salts, M2M'(SO4)2·6H2O, where M = K, Rb, Cs and M' = Mg, Mn, Fe, Co, Ni, Cu, and Zn; and eleven MM'(SO4)2·12H2O alums, where M = Na, K, Rb and Cs, and M' = Al, Cr, Ga and In. This is also the case for the sulfates alunogen, Al2(SO4)3·17H2O and halotrichite, FeAl2(SO4)4·22H2O; three hydrated nitrates; one phosphate; three antimonates and two hydrated perchlorates. A possible explanation for this different behavior is that the bond-valence model treats O and H separately, whereas polarizability calculations treat the polarizability of the entire H2O molecule.

  6. Genotoxicity testing: Comparison of the γH2AX focus assay with the alkaline and neutral comet assays.

    PubMed

    Nikolova, Teodora; Marini, Federico; Kaina, Bernd

    2017-10-01

    Genotoxicity testing relies on the quantitative measurement of adverse effects, such as chromosome aberrations, micronuclei, and mutations, resulting from primary DNA damage. Ideally, assays will detect DNA damage and cellular responses with high sensitivity, reliability, and throughput. Several novel genotoxicity assays may fulfill these requirements, including the comet assay and the more recently developed γH2AX assay. Although they are thought to be specific for genotoxicants, a systematic comparison of the assays has not yet been undertaken. In the present study, we compare the γH2AX focus assay with the alkaline and neutral versions of the comet assay, as to their sensitivities and limitations for detection of genetic damage. We investigated the dose-response relationships of γH2AX foci and comet tail intensities at various times following treatment with four prototypical genotoxicants, methyl methanesulfonate (MMS), N-methyl-N'-nitro-N-nitrosoguanidine (MNNG), mitomycin C, and hydrogen peroxide (H 2 O 2 ) and we tested whether there is a correlation between the endpoints, i.e., alkali-labile sites and DNA strand breaks on the one hand and the cell's response to DNA double-strand breaks and blocked replication forks on the other. Induction of γH2AX foci gave a linear dose response and all agents tested were positive in the assay. The increase in comet tail intensity was also a function of dose; however, mitomycin C was almost completely ineffective in the comet assay, and the doses needed to achieve a significant effect were somewhat higher for some treatments in the comet assay than in the γH2AX foci assay, which was confirmed by threshold analysis. There was high correlation between tail intensity and γH2AX foci for MMS and H 2 O 2 , less for MNNG, and none for mitomycin C. From this we infer that the γH2AX foci assay is more reliable, sensitive, and robust than the comet assay for detecting genotoxicant-induced DNA damage. Copyright © 2017 Elsevier

  7. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

    We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of thesemore » interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.« less

  8. Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2).

    PubMed

    Lee, Minju; Merle, Tony; Rentsch, Daniel; Canonica, Silvio; von Gunten, Urs

    2017-01-03

    The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O 3 /H 2 O 2 and UV/H 2 O 2 ) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k O 3 ) (<0.1-7.9 × 10 3 M -1 s -1 ) or with hydroxyl radicals (k • OH ) (0.9 × 10 9 - 6.5 × 10 9 M -1 s -1 ), photon fluence-based rate constants (k') (210-2730 m 2 einstein -1 ), and quantum yields (Φ) (0.03-0.95 mol einstein -1 ). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO 3 /gDOC to ∼100% at ≥1.0 gO 3 /gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k O 3 and k • OH . The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H 2 O 2 . For a typical UV disinfection dose (400 J/m 2 ), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of H 2 O 2 addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

  9. Exploring crystalline-structural variations of cellulose during alkaline pretreatment for enhanced enzymatic hydrolysis.

    PubMed

    Ling, Zhe; Chen, Sheng; Zhang, Xun; Xu, Feng

    2017-01-01

    The study aimed to explore the crystallinity and crystalline structure of alkaline pretreated cellulose. The enzymatic hydrolysis followed by pretreatment was conducted for measuring the efficiency of sugar conversion. For cellulose Iβ dominated samples, alkaline pretreatment (<8wt%) caused increased cellulose crystallinity and depolymerized hemicelluloses, that were superimposed to affect the enzymatic conversion to glucose. Varying crystallite sizes and lattice spacings indicated the separation of cellulose crystals during mercerization (8-12wt% NaOH). Completion of mercerization was proved under higher alkaline concentration (14-18wt% NaOH), leading to distortion of crystalline cellulose to some extent. Cellulose II crystallinity showed a stimulative impact on enzymatic hydrolysis due to the weakened hydrophobic interactions within cellulose chains. The current study may provide innovative explanations for enhanced enzymatic digestibility of alkaline pretreated lignocellulosic materials. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

    PubMed

    De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

    2014-03-28

    New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

  11. Combination of alkaline and microwave pretreatment for disintegration of meat processing wastewater sludge.

    PubMed

    Erden, G

    2013-01-01

    Meat processing wastewater sludge has high organic content but it is very slow to degrade in biological processes. Anaerobic digestion may be a good alternative for this type of sludge when the hydrolysis, known to be the rate-limiting step of biological sludge anaerobic degradation, could be eliminated by disintegration. This investigation deals with disintegration of meat processing wastewater sludge. Microwave (MW) irradiation and combined alkaline pretreatment and MW irradiation were applied to sludge for disintegration purposes. Disintegration performance of the methods was evaluated with disintegration degree based on total and dissolved organic carbon calculations (DD(TOC)), and the solubilization of volatile solids (S(VS)) in the pretreated sludge. Optimum conditions were found to be 140 degrees C and 30 min for MW irradiation using response surface methodology (RSM) and pH = 13 for combined pretreatment. While DD(TOC) was observed as 24.6% and 54.9, S(VS) was determined as 8.54% and 42.5% for MW pretreated and combined pretreated sludge, respectively. The results clearly show that pre-conditioning of sludge with alkaline pretreatment played an important role in enhancing the disintegration efficiency of subsequent MW irradiation. Disintegration methods also affected the anaerobic biodegradability and dewaterability of sludge. An increase of 23.6% in biogas production in MW irradiated sludge was obtained, comparing to the raw sludge at the end of the 35 days of incubation. This increase was observed as 44.5% combined pretreatment application. While MW pretreatment led to a little improvement of the dewatering performance of sludge, in combined pretreatment NaOH deteriorates the sludge dewaterability.

  12. Quasiparticle interfacial level alignment of highly hybridized frontier levels: H2O on TiO2(110).

    PubMed

    Migani, Annapaola; Mowbray, Duncan J; Zhao, Jin; Petek, Hrvoje

    2015-01-13

    Knowledge of the frontier levels' alignment prior to photoirradiation is necessary to achieve a complete quantitative description of H2O photocatalysis on TiO2(110). Although H2O on rutile TiO2(110) has been thoroughly studied both experimentally and theoretically, a quantitative value for the energy of the highest H2O occupied levels is still lacking. For experiment, this is due to the H2O levels being obscured by hybridization with TiO2(110) levels in the difference spectra obtained via ultraviolet photoemission spectroscopy (UPS). For theory, this is due to inherent difficulties in properly describing many-body effects at the H2O-TiO2(110) interface. Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) G0W0, we disentangle the adsorbate and surface contributions to the complex UPS spectra of H2O on TiO2(110). We perform this separation as a function of H2O coverage and dissociation on stoichiometric and reduced surfaces. Due to hybridization with the TiO2(110) surface, the H2O 3a1 and 1b1 levels are broadened into several peaks between 5 and 1 eV below the TiO2(110) valence band maximum (VBM). These peaks have both intermolecular and interfacial bonding and antibonding character. We find the highest occupied levels of H2O adsorbed intact and dissociated on stoichiometric TiO2(110) are 1.1 and 0.9 eV below the VBM. We also find a similar energy of 1.1 eV for the highest occupied levels of H2O when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than those estimated from UPS difference spectra, which are inconclusive in this energy region. Finally, we apply self-consistent QPGW (scQPGW1) to obtain the ionization potential of the H2O-TiO2(110) interface.

  13. A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

    NASA Astrophysics Data System (ADS)

    Dou, Ming-Yu; Lu, Jing

    2017-12-01

    A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

  14. Reduction in central H2O2 levels prevents voluntary ethanol intake in mice: a role for the brain catalase-H2O2 system in alcohol binge drinking.

    PubMed

    Ledesma, Juan Carlos; Baliño, Pablo; Aragon, Carlos M G

    2014-01-01

    Hydrogen peroxide (H2 O2 ) is the cosubstrate used by the enzyme catalase to form Compound I (the catalase-H2 O2 system), which is the major pathway for the conversion of ethanol (EtOH) into acetaldehyde in the brain. This centrally formed acetaldehyde has been shown to be involved in some of the psychopharmacological effects induced by EtOH in rodents, including voluntary alcohol intake. It has been observed that different levels of this enzyme in the central nervous system (CNS) result in variations in the amount of EtOH consumed. This has been interpreted to mean that the brain catalase-H2 O2 system, by determining EtOH metabolism, mediates alcohol self-administration. To date, however, the role of H2 O2 in voluntary EtOH drinking has not been investigated. In the present study, we explored the consequence of a reduction in cerebral H2 O2 levels in volitional EtOH ingestion. With this end in mind, we injected mice of the C57BL/6J strain intraperitoneally with the H2 O2 scavengers alpha-lipoic acid (LA; 0 to 50 mg/kg) or ebselen (Ebs; 0 to 25 mg/kg) 15 or 60 minutes, respectively, prior to offering them an EtOH (10%) solution following a drinking-in-the-dark procedure. The same procedure was followed to assess the selectivity of these compounds in altering EtOH intake by presenting mice with a (0.1%) solution of saccharin. In addition, we indirectly tested the ability of LA and Ebs to reduce brain H2 O2 availability. The results showed that both LA and Ebs dose-dependently reduced voluntary EtOH intake, without altering saccharin consumption. Moreover, we demonstrated that these treatments decreased the central H2 O2 levels available to catalase. Therefore, we propose that the amount of H2 O2 present in the CNS, by determining brain acetaldehyde formation by the catalase-H2 O2 system, could be a factor that determines an animal's propensity to consume EtOH. Copyright © 2013 by the Research Society on Alcoholism.

  15. Vibrational spectra of Mg2KH(XO4)2·15H2O (X = P, As) containing dimer units [H(XO4)2

    NASA Astrophysics Data System (ADS)

    Stefov, V.; Koleva, V.; Najdoski, M.; Abdija, Z.; Cahil, A.; Šoptrajanov, B.

    2017-08-01

    Infrared and Raman spectra of Mg2KH(PO4)2·15H2O and Mg2KH(AsO4)2·15H2O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg2KH(XO4)2·15H2O (X = P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO4)2] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C1 crystallographic symmetry of the XO4 groups. The observation of a singlet Raman band for the ν1(XO4) mode as well as the absence of substantial splitting of the ν3(XO4) modes and IR activation of the ν1(XO4) mode suggest that the dimer units [H(XO4)2] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg2KH(AsO4)2·15H2O, both ν1(AsО4) and ν3(AsО4) modes have practically the same wavenumber around 830 cm- 1. It was also established that the ν4(PО4) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D2O librations. As a whole, the spectral picture of Mg2KH(XO4)2·15H2O (X = P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO4·6H2O (X = P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO4)2] play a relatively small part in the general spectral appearance.

  16. Reactions of hydrated electrons (H2O)n- with carbon dioxide and molecular oxygen: hydration of the CO2- and O2- ions.

    PubMed

    Balaj, O Petru; Siu, Chi-Kit; Balteanu, Iulia; Beyer, Martin K; Bondybey, Vladimir E

    2004-10-04

    The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n- because they possess low-lying empty pi* orbitals. The molecular CO2- and O2- anions are concurrently solvated and stabilized by the water ligands to form CO2(-)(H2O)n and O2(-)(H2O)n. Core exchange reactions are also observed, in which CO2(-)(H2O)n is transformed into O2(-)(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(-)(H2O)n clusters are thermodynamically favored with respect to CO2(-)(H2O)n. Electron detachment from the product species is only observed for CO2(-)(H2O)2, in agreement with the calculated electron affinities and solvation energies.

  17. Fluoresence cross section of the H2O(+) A 2A1(0,7,0) produced through photoionization of H2O

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. Robert; Hwang, M. Y.

    1988-01-01

    The cross section for the production of the H2O(+) A 2A1(0,7,0) - X 2B1(0,0,0) fluorescence through photoionization of H2O was measured in the 14.5-20.5 eV region. The maximum quantum yield is 1.4 x 10 to the -3rd at 16.5 eV.

  18. Quasiparticle Interfacial Level Alignment of Highly Hybridized Frontier Levels: H2O on TiO2(110)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Migani, Annapaola; Mowbray, Duncan J.; Zhao, Jin

    Knowledge of the frontier levels’ alignment prior to photoirradiation is necessary to achieve a complete quantitative description of H2O photocatalysis on TiO2(110). Although H2O on rutile TiO2(110) has been thoroughly studied both experimentally and theoretically, a quantitative value for the energy of the highest H2O occupied levels is still lacking. For experiment, this is due to the H2O levels being obscured by hybridization with TiO2(110) levels in the difference spectra obtained via ultraviolet photoemission spectroscopy (UPS). For theory, this is due to inherent difficulties in properly describing many-body effects at the H2O–TiO2(110) interface. Using the projected density of states (DOS)more » from state-of-the-art quasiparticle (QP) G0W0, we disentangle the adsorbate and surface contributions to the complex UPS spectra of H2O on TiO2(110). We perform this separation as a function of H2O coverage and dissociation on stoichiometric and reduced surfaces. Due to hybridization with the TiO2(110) surface, the H2O 3a1 and 1b1 levels are broadened into several peaks between 5 and 1 eV below the TiO2(110) valence band maximum (VBM). These peaks have both intermolecular and interfacial bonding and antibonding character. We find the highest occupied levels of H2O adsorbed intact and dissociated on stoichiometric TiO2(110) are 1.1 and 0.9 eV below the VBM. We also find a similar energy of 1.1 eV for the highest occupied levels of H2O when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than those estimated from UPS difference spectra, which are inconclusive in this energy region. Finally, we apply self-consistent QPGW (scQPGW1) to obtain the ionization potential of the H2O–TiO2(110) interface.« less

  19. Mechanistic analysis of water oxidation catalyst cis-[Ru(bpy) 2(H 2O) 2] 2+: Effect of dimerization

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Erdman, Darren; Pineda-Galvan, Yuliana; Pushkar, Yulia

    While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In this work, the single site Ru complex [Ru(bpy) 2(H 2O) 2] 2+ (bpy = 2,20-bipyridine)—which can exist as either a cis isomer or a trans isomer—is investigated. While a difference in the catalytic activity of these two isomers is well established, with cis-[Ru(bpy) 2(H 2O) 2] 2+ being much more active, no mechanistic explanation of this fact has been presented. The oxygen evolving capability of both isomers at multiple concentrations has been investigated,more » with cis-[Ru(bpy) 2(H 2O) 2] 2+ showing a second-order dependence of O2 evolution activity with increased catalyst concentration. Measurement of the electron paramagnetic resonance (EPR) spectrum of cis-[Ru(bpy) 2(H 2O) 2] 2+, shortly after oxidation with CeIV, showed the presence of a signal matching that of cis,cis-[Ru III(bpy) 2(H 2O)ORu IV(bpy) 2(OH)] 4+, also known as “blue dimer”. The formation of dimers is a concentration-dependent process, which could serve to explain the greater than first order increase in catalytic activity. The trans isomer showed a first-order dependence of O 2 evolution on catalyst concentration. As a result, behavior of [Ru(bpy) 2(H 2O) 2] 2+ isomers is compared with other Ru-based catalysts, in particular [Ru(tpy)(bpy)(H 2O)] 2+ (tpy = 2,20;6,20 0-terpyridine).« less

  20. Mechanistic analysis of water oxidation catalyst cis-[Ru(bpy) 2(H 2O) 2] 2+: Effect of dimerization

    DOE PAGES

    Erdman, Darren; Pineda-Galvan, Yuliana; Pushkar, Yulia

    2017-01-25

    While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In this work, the single site Ru complex [Ru(bpy) 2(H 2O) 2] 2+ (bpy = 2,20-bipyridine)—which can exist as either a cis isomer or a trans isomer—is investigated. While a difference in the catalytic activity of these two isomers is well established, with cis-[Ru(bpy) 2(H 2O) 2] 2+ being much more active, no mechanistic explanation of this fact has been presented. The oxygen evolving capability of both isomers at multiple concentrations has been investigated,more » with cis-[Ru(bpy) 2(H 2O) 2] 2+ showing a second-order dependence of O2 evolution activity with increased catalyst concentration. Measurement of the electron paramagnetic resonance (EPR) spectrum of cis-[Ru(bpy) 2(H 2O) 2] 2+, shortly after oxidation with CeIV, showed the presence of a signal matching that of cis,cis-[Ru III(bpy) 2(H 2O)ORu IV(bpy) 2(OH)] 4+, also known as “blue dimer”. The formation of dimers is a concentration-dependent process, which could serve to explain the greater than first order increase in catalytic activity. The trans isomer showed a first-order dependence of O 2 evolution on catalyst concentration. As a result, behavior of [Ru(bpy) 2(H 2O) 2] 2+ isomers is compared with other Ru-based catalysts, in particular [Ru(tpy)(bpy)(H 2O)] 2+ (tpy = 2,20;6,20 0-terpyridine).« less

  1. Selective Adsorption Resonances in the Scattering of n-H2 p-H2 n-D2 and o-D2 from Ag(111)

    NASA Astrophysics Data System (ADS)

    Yu, Chien-Fan; Whaley, K. Birgitta; Hogg, Charles S.; Sibener, Steven J.

    1983-12-01

    Diffractive and rotationally mediated selective adsorption scattering resonances are reported for n-H2 p-H2 n-D2 and o-D2 on Ag(111). Small resonance shifts and line-width differences are observed between n-H2 and p-H2 indicating a weak orientation dependence of the laterally averaged H2/Ag(111) potential. The p-H2 and o-D2 levels were used to determine the isotropic component of this potential, yielding a well depth of ~ 32 meV.

  2. UV-activated ZnO films on a flexible substrate for room temperature O2 and H2O sensing.

    PubMed

    Jacobs, Christopher B; Maksov, Artem B; Muckley, Eric S; Collins, Liam; Mahjouri-Samani, Masoud; Ievlev, Anton; Rouleau, Christopher M; Moon, Ji-Won; Graham, David E; Sumpter, Bobby G; Ivanov, Ilia N

    2017-07-20

    We demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2 O. We propose that the distinctive responses to O 2 and H 2 O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2 O adsorption energy on ZnO surfaces were performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). These simulations suggest that the adsorption mechanisms differ for O 2 and H 2 O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2 O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2 O at low temperature.

  3. Liraglutide alleviates H2O2-induced retinal ganglion cells injury by inhibiting autophagy through mitochondrial pathways.

    PubMed

    Ma, Xuefei; Lin, Wenjian; Lin, Zhenyu; Hao, Ming; Gao, Xinyuan; Zhang, Yue; Kuang, Hongyu

    2017-06-01

    Retinal ganglion cells (RGCs), which exist in the inner retina, are the retinal neurons which can be damaged in the early stage of diabetic retinopathy (DR). Liraglutide, a glucagon-like peptide-1 (GLP-1) analog, exerts biological functions by binding the receptor (GLP-1R), the expression of which in RGC-5 cells was first shown by our team in 2012. It was reported that liraglutide prevented retinal neurodegeneration in diabetic subjects. However, the involvement of mechanisms such as autophagy and mitochondrial balance in liraglutide-induced retinal protection is unknown. Here, we aimed to investigate the protective effects of liraglutide and explore the potential mechanisms of liraglutide-induced retinal RGC protection. RGC-5 cells were treated with H 2 O 2 and/or liraglutide. Cell viability was detected with the CCK-8 kit. The axon marker GAP43, autophagy and mitophagy indicators LC3A/B, Beclin-1, p62, Parkin, BCL2/Adenovirus E1B 19kDa protein-interacting protein 3-like (BNIP3L) and the key regulator of mitochondrial biogenesis PGC-1α were examined via western blot analysis. Autophagy was also evaluated using the ImageXpress Micro XLS system and transmission electron microscopy (TEM). Reactive oxygen species (ROS), mitochondrial membrane potential and fluorescent staining for mitochondria were also measured using the ImageXpress Micro XLS system. Our results showed that pretreatment with liraglutide significantly prevented H 2 O 2 -induced cell viability decline, mitochondrial morphological deterioration and induction of autophagy, which appeared as increased expression of LC3 II/I and Beclin-1, along with p62 degradation. Moreover, liraglutide suppressed the H 2 O 2 -induced decline in GAP43 expression, thus protecting cells. However, rapamycin induced autophagy and blocked the protective process. Liraglutide also provided mitochondrial protection and appeared to alleviate H 2 O 2 -induced ROS overproduction and a decline in mitochondrial membrane potential

  4. The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

    DOE PAGES

    Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

    2016-04-16

    Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

  5. The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

    Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

  6. Production optimization of a heat-tolerant alkaline pectinase from Bacillus subtilis ZGL14 and its purification and characterization.

    PubMed

    Yu, Ping; Zhang, Yishu; Gu, Donglu

    2017-09-03

    Alkaline pectinase has important applications in the pretreatment of waste water from food processing and in both the fabric and paper industries. In this study, a 2-level factorial design was used to screen significant factors that affect the activity of alkaline pectinase, and the response surface methodology (RSM) with a Box-Behnken design (BBD) was used to optimize their concentrations. Starch, peptone, KH 2 PO 4 and K 2 HPO 4 ·3H 2 O were found to significantly affect the activity of alkaline pectinase. Their optimal concentrations were as follows: 4.68% starch, 1.6% peptone, 0.26% KH 2 PO 4 and 0.68% K 2 HPO 4 ·3H 2 O. Under the above conditions, the activity of alkaline pectinase was significantly improved to 734.11 U/mL. Alkaline pectinase was purified to homogeneity with a recovery rate of 9.6% and a specific activity of 52372.52 U/mg. Its optimal temperature and pH were 50°C and 8.6, respectively. The purified enzyme showed strong thermo-stability and good alkali resistance. In addition, the activity of alkaline pectinase was improved in the presence of Mg 2+ . Cu 2+ , Mn 2+ , and Co 2+ significantly inhibited its activity. This study provides an important basis for the future development and use of a heat-tolerant alkaline pectinase from B. subtilis ZGL14.

  7. Production optimization of a heat-tolerant alkaline pectinase from Bacillus subtilis ZGL14 and its purification and characterization

    PubMed Central

    Yu, Ping; Zhang, Yishu; Gu, Donglu

    2017-01-01

    ABSTRACT Alkaline pectinase has important applications in the pretreatment of waste water from food processing and in both the fabric and paper industries. In this study, a 2-level factorial design was used to screen significant factors that affect the activity of alkaline pectinase, and the response surface methodology (RSM) with a Box-Behnken design (BBD) was used to optimize their concentrations. Starch, peptone, KH2PO4 and K2HPO4·3H2O were found to significantly affect the activity of alkaline pectinase. Their optimal concentrations were as follows: 4.68% starch, 1.6% peptone, 0.26% KH2PO4 and 0.68% K2HPO4·3H2O. Under the above conditions, the activity of alkaline pectinase was significantly improved to 734.11 U/mL. Alkaline pectinase was purified to homogeneity with a recovery rate of 9.6% and a specific activity of 52372.52 U/mg. Its optimal temperature and pH were 50°C and 8.6, respectively. The purified enzyme showed strong thermo-stability and good alkali resistance. In addition, the activity of alkaline pectinase was improved in the presence of Mg2+. Cu2+, Mn2+, and Co2+ significantly inhibited its activity. This study provides an important basis for the future development and use of a heat-tolerant alkaline pectinase from B. subtilis ZGL14. PMID:28282260

  8. Photodesorption of H2O, HDO, and D2O ice and its impact on fractionation

    NASA Astrophysics Data System (ADS)

    Arasa, Carina; Koning, Jesper; Kroes, Geert-Jan; Walsh, Catherine; van Dishoeck, Ewine F.

    2015-03-01

    The HDO/H2O ratio measured in interstellar gas is often used to draw conclusions on the formation and evolution of water in star-forming regions and, by comparison with cometary data, on the origin of water on Earth. In cold cores and in the outer regions of protoplanetary disks, an important source of gas-phase water comes from photodesorption of water ice. This research note presents fitting formulae for implementation in astrochemical models using previously computed photodesorption efficiencies for all water ice isotopologues obtained with classical molecular dynamics simulations. The results are used to investigate to what extent the gas-phase HDO/H2O ratio reflects that present in the ice or whether fractionation can occur during the photodesorption process. Probabilities for the top four monolayers are presented for photodesorption of X (X = H, D) atoms, OX radicals, and X2O and HDO molecules following photodissociation of H2O, D2O, and HDO in H2O amorphous ice at ice temperatures from 10-100 K. Significant isotope effects are found for all possible products: (1) H atom photodesorption probabilities from H2O ice are larger than those for D atom photodesorption from D2O ice by a factor of 1.1; the ratio of H and D photodesorbed upon HDO photodissociation is a factor of 2. This process will enrich the ice in deuterium atoms over time; (2) the OD/OH photodesorption ratio upon D2O and H2O photodissociation is on average a factor of 2, but the OD/OH photodesorption ratio upon HDO photodissociation is almost constant at unity for all ice temperatures; (3) D atoms are more effective in kicking out neighbouring water molecules than H atoms. However, the ratio of the photodesorbed HDO and H2O molecules is equal to the HDO/H2O ratio in the ice, therefore, there is no isotope fractionation when HDO and H2O photodesorb from the ice. Nevertheless, the enrichment of the ice in D atoms due to photodesorption can over time lead to an enhanced HDO/H2O ratio in the ice, and

  9. Special hydrogen bonds observed in two monovalent metal carboxylate-phosphinates: {NaH(Phsbnd PO2sbnd C2H4sbnd COOH)2}∞ and {[KH(Phsbnd PO2sbnd C2H4sbnd COOH)2H2O}∞

    NASA Astrophysics Data System (ADS)

    Zhao, Cui-Cui; Zhang, Jian-Wei; Zhou, Zhong-Gao; Du, Zi-Yi

    2013-02-01

    The addition of strong base such as sodium hydroxide or potassium hydroxide to the aqueous solution of (2-carboxyethyl)(phenyl)phosphinic acid afforded two novel monovalent metal carboxylate-phosphinates, namely, {NaH(Phsbnd PO2sbnd C2H4sbnd COOH)2}∞ (1) and {[KH(Phsbnd PO2sbnd C2H4sbnd COOH)2H2O}∞ (2). They represent the first examples of phosphinate containing short, symmetric or almost symmetric O⋯H⋯O hydrogen bonds.

  10. Bacterial Ice Nucleation in Monodisperse D2O and H2O-in-Oil Emulsions.

    PubMed

    Weng, Lindong; Tessier, Shannon N; Smith, Kyle; Edd, Jon F; Stott, Shannon L; Toner, Mehmet

    2016-09-13

    Ice nucleation is of fundamental significance in many areas, including atmospheric science, food technology, and cryobiology. In this study, we investigated the ice-nucleation characteristics of picoliter-sized drops consisting of different D2O and H2O mixtures with and without the ice-nucleating bacteria Pseudomonas syringae. We also studied the effects of commonly used cryoprotectants such as ethylene glycol, propylene glycol, and trehalose on the nucleation characteristics of D2O and H2O mixtures. The results show that the median freezing temperature of the suspension containing 1 mg/mL of a lyophilized preparation of P. syringae is as high as -4.6 °C for 100% D2O, compared to -8.9 °C for 100% H2O. As the D2O concentration increases every 25% (v/v), the profile of the ice-nucleation kinetics of D2O + H2O mixtures containing 1 mg/mL Snomax shifts by about 1 °C, suggesting an ideal mixing behavior of D2O and H2O. Furthermore, all of the cryoprotectants investigated in this study are found to depress the freezing phenomenon. Both the homogeneous and heterogeneous freezing temperatures of these aqueous solutions depend on the water activity and are independent of the nature of the solute. These findings enrich our fundamental knowledge of D2O-related ice nucleation and suggest that the combination of D2O and ice-nucleating agents could be a potential self-ice-nucleating formulation. The implications of self-nucleation include a higher, precisely controlled ice seeding temperature for slow freezing that would significantly improve the viability of many ice-assisted cryopreservation protocols.

  11. A new Pu(iii) coordination geometry in (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O as obtained via supramolecular assembly in aqueous, high chloride media.

    PubMed

    Surbella, Robert G; Ducati, Lucas C; Pellegrini, Kristi L; McNamara, Bruce K; Autschbach, Jochen; Schwantes, Jon M; Cahill, Christopher L

    2017-09-28

    Crystals of a hydrated Pu(iii) chloride, (C 5 H 5 NBr) 2 [PuCl 3 (H 2 O) 5 ]·2Cl·2H 2 O, were grown via slow evaporation from acidic aqueous, high chloride media. X-ray diffraction data reveals the neutral [PuCl 3 (H 2 O) 5 ] tecton is assembled via charge assisted hydrogen and halogen bonds donated by 4-bromopyridinium cations and a series of inter-tecton hydrogen bonds.

  12. Improved hydrogen storage properties of MgH2 catalyzed with TiO2

    NASA Astrophysics Data System (ADS)

    Jangir, Mukesh; Meena, Priyanka; Jain, I. P.

    2018-05-01

    In order to improve the hydrogenation properties of the MgH2, various concentration of rutile Titanium Oxide (TiO2) (X wt%= 5, 10, 15 wt %) is added to MgH2 by ball milling and the catalytic effect of TiO2 on hydriding/dehydriding properties of MgH2 has been investigated. Result shows that the TiO2 significantly reduced onset temperature of desorption. Onset temperature as low as 190 °C were observed for the MgH2-15 wt% TiO2 sample which is 60 °C and 160 °C lower than the as-milled and as-received MgH2. Fromm the Kissinger plot the activation energy of 15 wt% TiO2 added sample is calculated to be -75.48 KJ/mol. These results indicate that the hydrogenation properties of MgH2-TiO2 have been improved compared to the as-milled and as-received MgH2. Furthermore, XRD and XPS were performed to characterize the structural evolution upon milling and dehydrogenation.

  13. Cathodic Electrodeposition of Ni-Mo on Semiconducting NiFe2 O4 for Photoelectrochemical Hydrogen Evolution in Alkaline Media.

    PubMed

    Wijten, Jochem H J; Jong, Ronald P H; Mul, Guido; Weckhuysen, Bert M

    2018-04-25

    Photocathodes for hydrogen evolution from water were made by electrodeposition of Ni-Mo layers on NiFe 2 O 4 substrates, deposited by spin coating on F:SnO 2 -glass. Analysis confirmed the formation of two separate layers, without significant reduction of NiFe 2 O 4 . Bare NiFe 2 O 4 was found to be unstable under alkaline conditions during (photo)electrochemistry. To improve the stability significantly, the deposition of a bifunctional Ni-Mo layer through a facile electrodeposition process was performed and the composite electrodes showed stable operation for at least 1 h. Moreover, photocurrents up to -2.1 mA cm -2 at -0.3 V vs. RHE were obtained for Ni-Mo/NiFe 2 O 4 under ambient conditions, showing that the new combination functions as both a stabilizing and catalytic layer for the photoelectrochemical evolution of hydrogen. The photoelectrochemical response of these composite electrodes decreased with increasing NiFe 2 O 4 layer thickness. Transient absorption spectroscopy showed that the lifetime of excited states is short and on the ns timescale. An increase in lifetime was observed for NiFe 2 O 4 of large layer thickness, likely explained by decreasing the defect density in the primary layer(s), as a result of repetitive annealing at elevated temperature. The photoelectrochemical and transient absorption spectroscopy results indicated that a short charge carrier lifetime limits the performance of Ni-Mo/NiFe 2 O 4 photocathodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Morphology-defined interaction of copper phthalocyanine with O 2/H 2O

    DOE PAGES

    Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; ...

    2016-11-01

    Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but its interaction with ambient gas/vapor may lead to changes in electronic properties of the material which subsequently limits the lifetime of OPV devices. CuPc films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O 2 and H 2O vapor. Mass loading by O 2 wasmore » enhanced by a factor of 5 in films deposited at 250 C, possibly due to the ~200° C CuPc -> transition which allows higher O 2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales > 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O 2/H 2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O 2/H 2O molecules on gold, which is consistent with findings of other studies.« less

  15. Competitive Sorption of CO2 and H2O in 2:1 Layer Phyllosilicates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Schaef, Herbert T.; Loring, John S.; Glezakou, Vassiliki Alexandra

    The salting out effect, where increasing the ionic strength of aqueous solutions decreases the solubility of dissolved gases is a well-known phenomenon. Less explored is the opposite process where an initially anhydrous system containing a volatile, relatively non-polar component and inorganic ions is systematically hydrated. Expandable clays such as montmorillonite are ideal systems for exploring this scenario as they have readily accessible exchange sites containing cations that can be systematically dehydrated or hydrated, from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO2 to bothmore » mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. Here, the partitioning of CO2 and H2O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO2 (scCO2) was investigated using in situ X-ray diffraction, infrared (IR)spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H2O and CO2 concentrations as a function of %H2O saturated in scCO2. Intercalation of CO2 is favored at low H2O/CO2 ratios in the interlayer region, where CO2 can solvate the interlayer cation. As the clay becomes more hydrated and the H2O/CO2 ratio increases, H2O displaces CO2 from the solvation shell of the cation and CO2 tends to segregate. This transition decreases both the entropic and enthalpic driving force for CO2 intercalation, consistent with experimentally observed loss of intercalated CO2.« less

  16. The pH dependency of N-converting enzymatic processes, pathways and microbes: effect on net N2 O production.

    PubMed

    Blum, Jan-Michael; Su, Qingxian; Ma, Yunjie; Valverde-Pérez, Borja; Domingo-Félez, Carlos; Jensen, Marlene Mark; Smets, Barth F

    2018-05-01

    Nitrous oxide (N 2 O) is emitted during microbiological nitrogen (N) conversion processes, when N 2 O production exceeds N 2 O consumption. The magnitude of N 2 O production vs. consumption varies with pH and controlling net N 2 O production might be feasible by choice of system pH. This article reviews how pH affects enzymes, pathways and microorganisms that are involved in N-conversions in water engineering applications. At a molecular level, pH affects activity of cofactors and structural elements of relevant enzymes by protonation or deprotonation of amino acid residues or solvent ligands, thus causing steric changes in catalytic sites or proton/electron transfer routes that alter the enzymes' overall activity. Augmenting molecular information with, e.g., nitritation or denitrification rates yields explanations of changes in net N 2 O production with pH. Ammonia oxidizing bacteria are of highest relevance for N 2 O production, while heterotrophic denitrifiers are relevant for N 2 O consumption at pH > 7.5. Net N 2 O production in N-cycling water engineering systems is predicted to display a 'bell-shaped' curve in the range of pH 6.0-9.0 with a maximum at pH 7.0-7.5. Net N 2 O production at acidic pH is dominated by N 2 O production, whereas N 2 O consumption can outweigh production at alkaline pH. Thus, pH 8.0 may be a favourable pH set-point for water treatment applications regarding net N 2 O production. © 2018 Society for Applied Microbiology and John Wiley & Sons Ltd.

  17. UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.

    Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

  18. UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

    DOE PAGES

    Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.; ...

    2017-07-20

    Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

  19. Co3(PO4)2·4H2O

    PubMed Central

    Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

    2008-01-01

    Single crystals of Co3(PO4)2·4H2O, tricobalt(II) bis­[ortho­phosphate(V)] tetra­hydrate, were obtained under hydro­thermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO4)2·4H2O (mineral name hopeite) and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetra­hedral coordination, while the second, located on a mirror plane, has a distorted octa­hedral coordination environment. The tetra­hedrally coordinated Co2+ is bonded to four O atoms of four PO4 3− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water mol­ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O—H⋯O are present throughout the crystal structure. PMID:21200978

  20. Novel Process of Simultaneous Removal of Nitric Oxide and Sulfur Dioxide Using a Vacuum Ultraviolet (VUV)-Activated O2/H2O/H2O2 System in A Wet VUV-Spraying Reactor.

    PubMed

    Liu, Yangxian; Wang, Qian; Pan, Jianfeng

    2016-12-06

    A novel process for NO and SO 2 simultaneous removal using a vacuum ultraviolet (VUV, with 185 nm wavelength)-activated O 2 /H 2 O/H 2 O 2 system in a wet VUV-spraying reactor was developed. The influence of different process variables on NO and SO 2 removal was evaluated. Active species (O 3 and ·OH) and liquid products (SO 3 2- , NO 2 - , SO 4 2- , and NO 3 - ) were analyzed. The chemistry and routes of NO and SO 2 removal were investigated. The oxidation removal system exhibits excellent simultaneous removal capacity for NO and SO 2 , and a maximum removal of 96.8% for NO and complete SO 2 removal were obtained under optimized conditions. SO 2 reaches 100% removal efficiency under most of test conditions. NO removal is obviously affected by several process variables. Increasing VUV power, H 2 O 2 concentration, solution pH, liquid-to-gas ratio, and O 2 concentration greatly enhances NO removal. Increasing NO and SO 2 concentration obviously reduces NO removal. Temperature has a dual impact on NO removal, which has an optimal temperature of 318 K. Sulfuric acid and nitric acid are the main removal products of NO and SO 2 . NO removals by oxidation of O 3 , O·, and ·OH are the primary routes. NO removals by H 2 O 2 oxidation and VUV photolysis are the complementary routes. A potential scaled-up removal process was also proposed initially.

  1. Reactions of electronically excited molecular nitrogen with H2 and H2O molecules: theoretical study

    NASA Astrophysics Data System (ADS)

    Pelevkin, Alexey V.; Sharipov, Alexander S.

    2018-05-01

    Comprehensive quantum chemical analysis with the usage of the second-order perturbation multireference XMCQDPT2 approach was carried out to study the processes in the   +  H2 and   +  H2O systems. The energetically favorable reaction pathways have been revealed based on the exploration of potential energy surfaces. It has been shown that the reactions   +  H2 and   +  H2O occur with small activation barriers and, primarily, lead to the formation of N2H  +  H and N2H  +  OH products, respectively. Further, the interaction of these species could give rise to the ground state and H2 (or H2O) products, however, the estimations, based on RRKM theory and dynamic reaction coordinate calculations, exhibited that the   +  H2 and   +  H2O reactions lead to the dissociative quenching predominately. Appropriate rate constants for revealed reaction channels have been estimated by using a canonical variational theory and capture approximation. Corresponding three-parameter Arrhenius expressions for the temperature range T  =  300  ‑  3000 K were reported.

  2. Kinetics of Al + H2O reaction: theoretical study.

    PubMed

    Sharipov, Alexander; Titova, Nataliya; Starik, Alexander

    2011-05-05

    Quantum chemical calculations were carried out to study the reaction of Al atom in the ground electronic state with H(2)O molecule. Examination of the potential energy surface revealed that the Al + H(2)O → AlO + H(2) reaction must be treated as a complex process involving two steps: Al + H(2)O → AlOH + H and AlOH + H → AlO + H(2). Activation barriers for these elementary reaction channels were calculated at B3LYP/6-311+G(3df,2p), CBS-QB3, and G3 levels of theory, and appropriate rate constants were estimated by using a canonical variational theory. Theoretical analysis exhibited that the rate constant for the Al + H(2)O → products reaction measured by McClean et al. must be associated with the Al + H(2)O → AlOH + H reaction path only. The process of direct HAlOH formation was found to be negligible at a pressure smaller than 100 atm.

  3. Vibrational spectra of Mg2KH(XO4)2·15H2O (X=P, As) containing dimer units [H(XO4)2].

    PubMed

    Stefov, V; Koleva, V; Najdoski, M; Abdija, Z; Cahil, A; Šoptrajanov, B

    2017-08-05

    Infrared and Raman spectra of Mg 2 KH(PO 4 ) 2 ·15H 2 O and Mg 2 KH(AsO 4 ) 2 ·15H 2 O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO 4 ) 2 ] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO 4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C 1 crystallographic symmetry of the XO 4 groups. The observation of a singlet Raman band for the ν 1 (XO 4 ) mode as well as the absence of substantial splitting of the ν 3 (XO 4 ) modes and IR activation of the ν 1 (XO 4 ) mode suggest that the dimer units [H(XO 4 ) 2 ] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg 2 KH(AsO 4 ) 2 ·15H 2 O, both ν 1 (AsО 4 ) and ν 3 (AsО 4 ) modes have practically the same wavenumber around 830cm -1 . It was also established that the ν 4 (PО 4 ) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D 2 O librations. As a whole, the spectral picture of Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO 4 ·6H 2 O (X=P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO 4 ) 2 ] play a relatively small part in the general spectral appearance. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. N2/O2/H2 Dual-Pump Cars: Validation Experiments

    NASA Technical Reports Server (NTRS)

    OByrne, S.; Danehy, P. M.; Cutler, A. D.

    2003-01-01

    The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method is used to measure temperature and the relative species densities of N2, O2 and H2 in two experiments. Average values and root-mean-square (RMS) deviations are determined. Mean temperature measurements in a furnace containing air between 300 and 1800 K agreed with thermocouple measurements within 26 K on average, while mean mole fractions agree to within 1.6 % of the expected value. The temperature measurement standard deviation averaged 64 K while the standard deviation of the species mole fractions averaged 7.8% for O2 and 3.8% for N2, based on 200 single-shot measurements. Preliminary measurements have also been performed in a flat-flame burner for fuel-lean and fuel-rich flames. Temperature standard deviations of 77 K were measured, and the ratios of H2 to N2 and O2 to N2 respectively had standard deviations from the mean value of 12.3% and 10% of the measured ratio.

  5. Improving methane production from digested manure biofibers by mechanical and thermal alkaline pretreatment.

    PubMed

    Tsapekos, P; Kougias, Panagiotis G; Frison, A; Raga, R; Angelidaki, I

    2016-09-01

    Animal manure digestion is associated with limited methane production, due to the high content in fibers, which are hardly degradable lignocellulosic compounds. In this study, different mechanical and thermal alkaline pretreatment methods were applied to partially degradable fibers, separated from the effluent stream of biogas reactors. Batch and continuous experiments were conducted to evaluate the efficiency of these pretreatments. In batch experiments, the mechanical pretreatment improved the degradability up to 45%. Even higher efficiency was shown by applying thermal alkaline pretreatments, enhancing fibers degradability by more than 4-fold. In continuous experiments, the thermal alkaline pretreatment, using 6% NaOH at 55°C was proven to be the most efficient pretreatment method as the methane production was increased by 26%. The findings demonstrated that the methane production of the biogas plants can be increased by further exploiting the fraction of the digested manure fibers which are discarded in the post-storage tank. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Degradation of 40 selected pharmaceuticals by UV/H2O2.

    PubMed

    Wols, B A; Hofman-Caris, C H M; Harmsen, D J H; Beerendonk, E F

    2013-10-01

    The occurrence of pharmaceuticals in source waters is increasing. Although UV advanced oxidation is known to be an effective barrier against micropollutants, degradation rates are only available for limited amounts of pharmaceuticals. Therefore, the degradation of a large group of pharmaceuticals has been studied in this research for the UV/H2O2 process under different conditions, including pharmaceuticals of which the degradation by UV/H2O2 was never reported before (e.g., metformin, paroxetine, pindolol, sotalol, venlafaxine, etc.). Monochromatic low pressure (LP) and polychromatic medium pressure (MP) lamps were used for three different water matrices. In order to have well defined hydraulic conditions, all experiments were conducted in a collimated beam apparatus. Degradation rates for the pharmaceuticals were determined. For those compounds used in this research that are also reported in literature, measured degradation results are in good agreement with literature data. Pharmaceutical degradation for only photolysis with LP lamps is small, which is increased by using a MP lamp. Most of the pharmaceuticals are well removed when applying both UV (either LP or MP) and H2O2. However, differences in degradation rates between pharmaceuticals can be large. For example, ketoprofen, prednisolone, pindolol are very well removed by UV/H2O2, whereas metformin, cyclophosphamide, ifosfamide are very little removed by UV/H2O2. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Degradation mechanism of cyanide in water using a UV-LED/H2O2/Cu2+ system.

    PubMed

    Kim, Tae-Kyoung; Kim, Taeyeon; Jo, Areum; Park, Suhyun; Choi, Kyungho; Zoh, Kyung-Duk

    2018-06-01

    In this study, we developed a UV-LED/H 2 O 2 /Cu 2+ system to remove cyanide, which is typically present in metal electroplating wastewater. The results showed the synergistic effects of UV-LED, H 2 O 2 , and Cu 2+ ions on cyanide removal in comparison with UV-LED photolysis, H 2 O 2 oxidation, UV-LED/H 2 O 2 , and H 2 O 2 /Cu 2+ systems. Cyanide was removed completely in 30 min in the UV-LED/H 2 O 2 /Cu 2+ system, and its loss followed pseudo-first order kinetics. Statistically, both H 2 O 2 and Cu 2+ ions showed positive effects on cyanide removal, but Cu 2+ ions exhibited a greater effect. The highest cyanide removal rate constant (k = 0.179 min -1 ) was achieved at pH 11, but the lowest was achieved at pH 12.5 (k = 0.064 min -1 ) due to the hydrolysis of H 2 O 2 (pK a of H 2 O 2  = 11.75). The presence of dissolved organic matter (DOM) inhibited cyanide removal, and the removal rate constant exhibited a negative linear correlation with DOM (R 2  = 0.987). The removal rate of cyanide was enhanced by the addition of Zn 2+ ions (from 0.179 to 0.457 min -1 ), while the co-existence of Ni 2+ or Cr +6 ion with Cu 2+ ion reduced cyanide removal. The formation of OH radicals in the UV-LED/H 2 O 2 /Cu 2+ system was verified using an aminophenyl fluorescence (APF) probe. Cyanate ions and ammonia were detected as the byproducts of cyanide decomposition. Finally, an acute toxicity reduction of 64.6% was achieved in the system within 1 h, despite a high initial cyanide concentration (100 mg/L). In terms of removal efficiency and toxicity reduction, the UV-LED/H 2 O 2 /Cu 2+ system may be an alternative method of cyanide removal from wastewaters. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Characterization of H2 photoproduction by marine green alga Tetraselmis subcordiformis integrated with an alkaline fuel cell.

    PubMed

    Guo, Zhen; Li, Ying; Guo, Haiyan

    2016-03-01

    To investigate the feasibility of coupling carbonyl cyanide m-chlorophenylhydrazone-regulated photohydrogen production by Tetraselmis subcordiformis in a photobioreactor to an alkaline fuel cell (AFC). H2 evolution kinetics in the AFC integrated process was characterized. The duration of H2 evolution was prolonged and its yield was improved about 1.5-fold (to 78 ± 5 ml l(-1)) compared with that of the process without AFC. Improved H2 yield was possibly caused by removal of H2 feedback inhibition by H2 consumption in situ. Decreases in the H2 production rate correlated with the gradual deactivation of PSII and hydrogenase activities. The H2 yield was closely associated with catabolism of starch and protein. A marine green algal CO2-supplemented culture integrated with in situ H2-consumption by an AFC system was developed as a viable protocol for the H2 production.

  9. Facile Modification of TiO2 with Nickel Sulfide and Sulfate Species for Photoreformation of Cellulose into H2.

    PubMed

    Hao, Hongchang; Zhang, Ling; Wang, Wenzhong; Zeng, Shuwen

    2018-06-19

    Photocatalytic cellulose reformation is regarded as a potential and affordable route for sustainable H2 evolution. However, the direct photoreformation still suffers from challenges such as the limited solubility of cellulose and dependence on catalytic activity of noble-metals. Herein, we reported a novel photoreformation of cellulose into H2 over TiO2 which is synchronously modified with nickel sulfide (NixSy) and chemisorbed sulfate species (SO42-) by a one-pot approach. A significant elevation in photocatalytic hydrogen evolution rate is achieved, with the maximal value of 3.02 mmol/g/h during the first three hours, almost 76-fold higher than that of P25 and comparable to Pt-P25. Aided by systematic investigation, it is proposed that nickel sulfide and sulfate modification synergistically contribute to the remarkably raised efficiency of biomass transformation. Specifically, NixSy serves as co-catalyst for photocatalytic H2 production, while SO42- ions are inferred to promote cellulose hydrolyzation and consequent accessibility of biomass to catalysts. Further, the accumulated formate intermediates are found to have a poison effect on catalysts, desorption of which can be controlled by tuning aqueous alkalinity. Overall, our strategy for modifying TiO2 with SO42- and NixSy provides a novel perspective of concurrently accelerating cellulose hydrolyzation process and supplementing hydrogen evolution sites, for efficient photocatalytic reformation of cellulose into H2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 2Q NMR of 2H2O ordering at solid interfaces

    NASA Astrophysics Data System (ADS)

    Krivokhizhina, Tatiana V.; Wittebort, R. J.

    2014-06-01

    Solvent ordering at an interface can be studied by multiple-quantum NMR. Quantitative studies of 2H2O ordering require clean double-quantum (2Q) filtration and an analysis of 2Q buildup curves that accounts for relaxation and, if randomly oriented samples are used, the distribution of residual couplings. A pulse sequence with absorption mode detection is extended for separating coherences by order and measuring relaxation times such as the 2Q filtered T2. Coherence separation is used to verify 2Q filtration and the 2Q filtered T2 is required to extract the coupling from the 2Q buildup curve when it is unresolved. With our analysis, the coupling extracted from the buildup curve in 2H2O hydrated collagen was equivalent to the resolved coupling measured in the usual 1D experiment and the 2Q to 1Q signal ratio was in accord with theory. Application to buildup curves from 2H2O hydrated elastin, which has an unresolved coupling, revealed a large increase in the 2Q signal upon mechanical stretch that is due to an increase in the ordered water fraction while changes in the residual coupling and T2 are small.

  11. Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

    NASA Technical Reports Server (NTRS)

    Kindler, Andrew; Huang, Yuhong

    2010-01-01

    Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

  12. X-ray irradiation activates K+ channels via H2O2 signaling.

    PubMed

    Gibhardt, Christine S; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

    2015-09-09

    Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels.

  13. Phosphorus recovery from biogas slurry by ultrasound/H2O2 digestion coupled with HFO/biochar adsorption process.

    PubMed

    He, Xuemeng; Zhang, Tao; Ren, Hongqiang; Li, Guoxue; Ding, Lili; Pawlowski, Lucjan

    2017-02-01

    Phosphorus (P) recovery from biogas slurry has recently attracted considerable interest. In this work, ultrasound/H 2 O 2 digestion coupled with ferric oxide hydrate/biochar (HFO/biochar) adsorption process was performed to promote P dissolution, release, and recovery from biogas slurry. The results showed that the optimal total phosphorus release efficiency was achieved at an inorganic phosphorus/total phosphorus ratio of 95.0% at pH 4, 1mL of added H 2 O 2 , and ultrasonication for 30min. The P adsorption by the HFO/biochar followed pseudo second-order kinetics and was mainly controlled by chemical processes. The Langmuir-Freundlich model matched the experimental data best for P adsorption by HFO/biochar at 298 and 308K, whereas the Freundlich model matched best at 318K. The maximum amount of P adsorbed was 220mg/g. The process was endothermic, spontaneous, and showed an increase in disorder at the solid-liquid interface. The saturated adsorbed HFO/biochar continually releases P and is most suitable for use in an alkaline environment. The amount of P released reached 29.1mg/g after five extractions. P mass balance calculation revealed that 11.3% of the total P can be made available. Copyright © 2016. Published by Elsevier Ltd.

  14. Isotope exchange in reactions between D2O and size-selected ionic water clusters containing pyridine, H+ (pyridine)m(H2O)n.

    PubMed

    Ryding, Mauritz Johan; Zatula, Alexey S; Andersson, Patrik Urban; Uggerud, Einar

    2011-01-28

    Pyridine containing water clusters, H(+)(pyridine)(m)(H(2)O)(n), have been studied both experimentally by a quadrupole time-of-flight mass spectrometer and by quantum chemical calculations. In the experiments, H(+)(pyridine)(m)(H(2)O)(n) with m = 1-4 and n = 0-80 are observed. For the cluster distributions observed, there are no magic numbers, neither in the abundance spectra, nor in the evaporation spectra from size selected clusters. Experiments with size-selected clusters H(+)(pyridine)(m)(H(2)O)(n), with m = 0-3, reacting with D(2)O at a center-of-mass energy of 0.1 eV were also performed. The cross-sections for H/D isotope exchange depend mainly on the number of water molecules in the cluster and not on the number of pyridine molecules. Clusters having only one pyridine molecule undergo D(2)O/H(2)O ligand exchange, while H(+)(pyridine)(m)(H(2)O)(n), with m = 2, 3, exhibit significant H/D scrambling. These results are rationalized by quantum chemical calculations (B3LYP and MP2) for H(+)(pyridine)(1)(H(2)O)(n) and H(+)(pyridine)(2)(H(2)O)(n), with n = 1-6. In clusters containing one pyridine, the water molecules form an interconnected network of hydrogen bonds associated with the pyridinium ion via a single hydrogen bond. For clusters containing two pyridines, the two pyridine molecules are completely separated by the water molecules, with each pyridine being positioned diametrically opposite within the cluster. In agreement with experimental observations, these calculations suggest a "see-saw mechanism" for pendular proton transfer between the two pyridines in H(+)(pyridine)(2)(H(2)O)(n) clusters.

  15. Photogeneration of H2O2 in Water-Swollen SPEEK/PVA Polymer Films.

    PubMed

    Lockhart, PaviElle; Little, Brian K; Slaten, B L; Mills, G

    2016-06-09

    Efficient reduction of O2 took place via illumination with 350 nm photons of cross-linked films containing a blend of sulfonated poly(ether etherketone) and poly(vinyl alcohol) in contact with air-saturated aqueous solutions. Swelling of the solid macromolecular matrices in H2O enabled O2 diffusion into the films and also continuous extraction of the photogenerated H2O2, which was the basis for a method that allowed quantification of the product. Peroxide formed with similar efficiencies in films containing sulfonated polyketones prepared from different precursors and the initial photochemical process was found to be the rate-determining step. Generation of H2O2 was most proficient in the range of 4.9 ≤ pH ≤ 8 with a quantum yield of 0.2, which was 10 times higher than the efficiencies determined for solutions of the polymer blend. Increases in temperature as well as [O2] in solution were factors that enhanced the H2O2 generation. H2O2 quantum yields as high as 0.6 were achieved in H2O/CH3CN mixtures with low water concentrations, but peroxide no longer formed when film swelling was suppressed. A mechanism involving reduction of O2 by photogenerated α-hydroxy radicals from the polyketone in competition with second-order radical decay processes explains the kinetic features. Higher yields result from the films because cross-links present in them hinder diffusion of the radicals, limiting their decay and enhancing the oxygen reduction pathway.

  16. Dehydration of the Uranyl Peroxide Studtite, [UO 22-O 2)(H 2O) 22H 2O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vitova, Tonya; Pidchenko, Ivan; Biswas, Saptarshi

    The dehydration of studtite, [UO 2(2-O 2)(H 2O)22H 2O, to metastudtite, [UO 2(2-O 2)(H 2O) 2], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probesmore » f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.« less

  17. Low-Lying Energy Isomers and Global Minima of Aqueous Nanoclusters: Structures and Spectroscopic Features of the Pentagonal Dodecahedron (H2O)20 and (H3O)+(H2O)20

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xantheas, Sotiris S.

    We rely on a hierarchy of methods to identify the low-lying isomers for the pentagonal dodecahedron (H2O)20 and the H3O+(H2O)20 clusters. Initial screening of isomers was performed with classical potentials [TIP4P, TTM2-F, TTM2.1-F for (H2O)20 and ASP for H3O+(H2O)20] and the networks obtained with those potentials were subsequently reoptimized at the DFT (B3LYP) and MP2 levels of theory. For the pentagonal dodecahedron (H2O)20 it was found that DFT (B3LYP) and MP2 produced the same global minimum. However, this was not the case for the H3O+(H2O)20 cluster, for which MP2 produced a different network for the global minimum when compared tomore » DFT (B3LYP). All low-lying minima of H3O+(H2O)20 correspond to hydrogen bonding networks having 9 ''free'' OH bonds and the hydronium ion on the surface of the cluster. The fact that DFT (B3LYP) and MP2 produce different results and issues related to the use of a smaller basis set, explains the discrepancy between the current results and the structure previously suggested [Science 304, 1137 (2004)] for the global minimum of the H3O+(H2O)20 cluster. Additionally, the IR spectra of the MP2 global minimum are closer to the experimentally measured ones than the spectra of the previously suggested DFT global minimum. The latter exhibit additional bands in the most red-shifted region of the OH stretching vibrations (corresponding to the ''fingerprint'' of the underlying hydrogen bonding network), which are absent from both the experimental as well as the spectra of the new structure suggested for the global minimum of this cluster.« less

  18. Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes

    PubMed Central

    2012-01-01

    Background For cellulosic biofuels processes, suitable characterization of the lignin remaining within the cell wall and correlation of quantified properties of lignin to cell wall polysaccharide enzymatic deconstruction is underrepresented in the literature. This is particularly true for grasses which represent a number of promising bioenergy feedstocks where quantification of grass lignins is particularly problematic due to the high fraction of p-hydroxycinnamates. The main focus of this work is to use grasses with a diverse range of lignin properties, and applying multiple lignin characterization platforms, attempt to correlate the differences in these lignin properties to the susceptibility to alkaline hydrogen peroxide (AHP) pretreatment and subsequent enzymatic deconstruction. Results We were able to determine that the enzymatic hydrolysis of cellulose to to glucose (i.e. digestibility) of four grasses with relatively diverse lignin phenotypes could be correlated to total lignin content and the content of p-hydroxycinnamates, while S/G ratios did not appear to contribute to the enzymatic digestibility or delignification. The lignins of the brown midrib corn stovers tested were significantly more condensed than a typical commercial corn stover and a significant finding was that pretreatment with alkaline hydrogen peroxide increases the fraction of lignins involved in condensed linkages from 88–95% to ~99% for all the corn stovers tested, which is much more than has been reported in the literature for other pretreatments. This indicates significant scission of β-O-4 bonds by pretreatment and/or induction of lignin condensation reactions. The S/G ratios in grasses determined by analytical pyrolysis are significantly lower than values obtained using either thioacidolysis or 2DHSQC NMR due to presumed interference by ferulates. Conclusions It was found that grass cell wall polysaccharide hydrolysis by cellulolytic enzymes for grasses exhibiting a diversity of

  19. Electrochemical Quantification of Extracellular Local H2O2 Kinetics Originating from Single Cells.

    PubMed

    Bozem, Monika; Knapp, Phillip; Mirčeski, Valentin; Slowik, Ewa J; Bogeski, Ivan; Kappl, Reinhard; Heinemann, Christian; Hoth, Markus

    2017-05-15

    H 2 O 2 is produced by all eukaryotic cells under physiological and pathological conditions. Due to its enormous relevance for cell signaling at low concentrations and antipathogenic function at high concentrations, precise quantification of extracellular local H 2 O 2 concentrations ([H 2 O 2 ]) originating from single cells is required. Using a scanning electrochemical microscope and bare platinum disk ultramicroelectrodes, we established sensitive long-term measurements of extracellular [H 2 O 2 ] kinetics originating from single primary human monocytes (MCs) ex vivo. For the electrochemical techniques square wave voltammetry, cyclic and linear scan voltammetry, and chronoamperometry, detection limits for [H 2 O 2 ] were determined to be 5, 50, and 500 nM, respectively. Following phorbol ester stimulation, local [H 2 O 2 ] 5-8 μm above a single MC increased by 3.4 nM/s within the first 10 min before reaching a plateau. After extracellular addition of H 2 O 2 to an unstimulated MC, the local [H 2 O 2 ] decreased on average by 4.2 nM/s due to degradation processes of the cell. Using the scanning mode of the setup, we found that H 2 O 2 is evenly distributed around the producing cell and can still be detected up to 30 μm away from the cell. The electrochemical single-cell measurements were validated in MC populations using electron spin resonance spectroscopy and the Amplex ® UltraRed assay. Innovation and Conclusion: We demonstrate a highly sensitive, spatially, and temporally resolved electrochemical approach to monitor dynamics of production and degradation processes for H 2 O 2 separately. Local extracellular [H 2 O 2 ] kinetics originating from single cells is quantified in real time. Antioxid. Redox Signal. 00, 000-000.

  20. Global Flux Balance in the Terrestrial H2O Cycle: Reconsidering the Post-Arc Subducted H2O Flux

    NASA Astrophysics Data System (ADS)

    Parai, R.; Mukhopadhyay, S.

    2010-12-01

    Quantitative estimates of H2O fluxes between the mantle and the exosphere (i.e., the atmosphere, oceans and crust) are critical to our understanding of the chemistry and dynamics of the solid Earth: the abundance and distribution of water in the mantle has dramatic impacts upon mantle melting, degassing history, structure and style of convection. Water is outgassed from the mantle is association with volcanism at mid-ocean ridges, ocean islands and convergent margins. H2O is removed from the exosphere at subduction zones, and some fraction of the subducted flux may be recycled past the arc into the Earth’s deep interior. Estimates of the post-arc subducted H2O flux are primarily based on the stability of hydrous phases at subduction zone pressures and temperatures (e.g. Schmidt and Poli, 1998; Rüpke et al., 2004; Hacker, 2008). However, the post-arc H2O flux remains poorly quantified, in part due to large uncertainties in the water content of the subducting slab. Here we evaluate estimated post-arc subducted fluxes in the context of mantle-exosphere water cycling, using a Monte Carlo simulation of the global H2O cycle. Literature estimates of primary magmatic H2O abundances and magmatic production rates at different tectonic settings are used with estimates of the total subducted H2O flux to establish the parameter space under consideration. Random sampling of the allowed parameter space affords insight into which input and output fluxes satisfy basic constraints on global flux balance, such as a limit on sea-level change over time. The net flux of H2O between mantle and exosphere is determined by the total mantle output flux (via ridges and ocean islands, with a small contribution from mantle-derived arc output) and the input flux subducted beyond the arc. Arc and back-arc output is derived mainly from the slab, and therefore cancels out a fraction of the trench intake in an H2O subcycle. Limits on sea-level change since the end of the Archaean place

  1. A Molecular Cobalt Catalyst Architected and TiO2 Modified p-GaInP2 Photoelectrode for Hydrogen Production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gu, Jing; Yan, Yong; Young, James

    2017-05-01

    We demonstrate that by employing a hybrid molecular/semiconductor interface with atomic layer deposited (ALD) TiO2 as an intermediate layer, a robust and corrosion resistant GaInP2-TiO2-cobaltoxime-TiO2 photocathode can be operated in alkaline media (pH =13).

  2. The effect of alkaline pretreatment methods on cellulose structure and accessibility

    DOE PAGES

    Bali, Garima; Meng, Xianzhi; Deneff, Jacob I.; ...

    2014-11-24

    The effects of different alkaline pretreatments on cellulose structural features and accessibility are compared and correlated with the enzymatic hydrolysis of Populus. The pretreatments are shown to modify polysaccharides and lignin content to enhance the accessibility for cellulase enzymes. The highest increase in the cellulose accessibility was observed in dilute sodium hydroxide, followed by methods using ammonia soaking and lime (Ca(OH) 2). The biggest increase of cellulose accessibility occurs during the first 10 min of pretreatment, with further increases at a slower rate as severity increases. Low temperature ammonia soaking at longer residence times dissolved a major portion of hemicellulosemore » and exhibited higher cellulose accessibility than high temperature soaking. Moreover, the most significant reduction of degree of polymerization (DP) occurred for dilute sodium hydroxide (NaOH) and ammonia pretreated Populus samples. The study thus identifies important cellulose structural features and relevant parameters related to biomass recalcitrance.« less

  3. Overlap corrections for emissivity calculations of H2O-CO2-CO-N2 mixtures

    NASA Astrophysics Data System (ADS)

    Alberti, Michael; Weber, Roman; Mancini, Marco

    2018-01-01

    Calculations of total gas emissivities of gas mixtures containing several radiatively active species require corrections for band overlapping. In this paper, we generate such overlap correction charts for H2O-CO2-N2, H2O-CO-N2, and CO2-CO-N2 mixtures. These charts are applicable in the 0.1-40 bar total pressure range and in the 500 K-2500 K temperature range. For H2O-CO2-N2 mixtures, differences between our charts and Hottel's graphs as well as models of Leckner and Modak are highlighted and analyzed.

  4. Phase and Physicochemical Properties Diagrams of Quaternary System Li2B4O7 + Na2B4O7 + Mg2B6O11 + H2O

    NASA Astrophysics Data System (ADS)

    Wang, Shi-qiang; Du, Xue-min; Jing, Yan; Guo, Ya-fei; Deng, Tian-long

    2017-12-01

    The phase and physicochemical properties diagrams of the quaternary system (Li2B4O7 + Na2B4O7 + Mg2B6O11) at 288.15 K and 0.1 MPa were constructed using the solubilities, densities, and refractive indices measured. In the phase diagrams of the system there are one invariant point, three univariant isothermic dissolution curves, and three crystallization regions corresponding to Li2B4O7 · 3H2O, Na2B4O7 · 10H2O, and Mg2B6O11 · 15H2O, respectively. The solution density, refractive index of the quaternary system changes regularly with the increasing of Li2B4O7 concentration. The calculated values of density and refractive index using empirical equations of the quaternary system are in good agreement with the experimental values.

  5. Electricity generation from banana peels in an alkaline fuel cell with a Cu2O-Cu modified activated carbon cathode.

    PubMed

    Liu, Peng; Liu, Xianhua; Dong, Feng; Lin, Qingxia; Tong, Yindong; Li, Yang; Zhang, Pingping

    2018-08-01

    Low-cost and highly active catalyst for oxygen reduction reaction is of great importance in the design of alkaline fuel cells. In this work, Cu 2 O-Cu composite catalyst has been fabricated by a facile laser-irradiation method. The addition of Cu 2 O-Cu composite in activated carbon air-cathode greatly improves the performance of the cathode. Our results indicate the enhanced performance is likely attributed to the synergistic effect of high conductivity of Cu and the catalytic activity of Cu 2 O towards the oxygen reduction reaction. Furthermore, an alkaline fuel cell equipped with the composite air-cathode has been built to turn banana peels into electricity. Peak power density of 16.12Wm -2 is obtained under the condition of 3M KOH and 22.04gL -1 reducing sugar, which is higher than other reported low-temperature direct biomass alkaline fuel cells. HPLC results indicate the main oxidation products in the alkaline fuel cell were small organic acids. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Laboratory IR Detection of H2O, CO2 in Ion-Irradiated Ices Relevant to Europa

    NASA Technical Reports Server (NTRS)

    Moore, Marla H.; Hudson, R. L.

    1999-01-01

    Hydrogen peroxide has been identified on Europa (Carlson et al. 1999) based in part on the 3.50 micron absorption feature observed in Galileo NIMS spectra. The observed feature was fitted with laboratory reflectance spectra of H2O + H2O2. Since condensed phase molecules on Europa (H2O, CO2, SO2, and H2O2) are bombarded with a significant flux of energetic particles (H(+), O(n+), S(n+) and e-), we examined the proton irradiation of H2O at 80 K and the conditions for the IR detection of H2O2 near 3.5 microns. Contrary to expectations, H2O2 was not detected if pure H2O ice was irradiated at 80 K. This was an unexpected result since, H2O2 was detected if pure H2O was irradiated at 18 K. We find, however, that if H2O ice contains either O2 or CO2 then H2O2 is detected after irradiation at 80 K (Moore and Hudson, 1999). The source of O2 for the H2O ice on Europa could come from surface interactions with the tenuous oxygen atmosphere, or from the bombardment of the surface by O(n+).

  7. Improvement of radio frequency (RF) heating-assisted alkaline pretreatment on four categories of lignocellulosic biomass.

    PubMed

    Wang, Xiaofei; Taylor, Steven; Wang, Yifen

    2016-10-01

    Pretreatment plays an important role in making the cellulose accessible for enzyme hydrolysis and subsequent conversion because it destroys more or less resistance and recalcitrance of biomass. Radio frequency (RF)-assisted dielectric heating was utilized in the alkaline pretreatment on agricultural residues (corn stover), herbaceous crops (switchgrass), hardwood (sweetgum) and softwood (loblolly pine). Pretreatment was performed at 90 °C with either RF or traditional water bath (WB) heating for 1 h after overnight soaking in NaOH solution (0.2 g NaOH/g Biomass). Pretreated materials were characterized by chemical compositional analysis, enzyme hydrolysis, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The glucan yields of RF-heated four categories of hydrolysates were 89.6, 72.6, 21.7, and 9.9 %. Interestingly, RF heating raised glucan yield on switchgrass and sweetgum but not on corn stover or loblolly pine. The SEM images and FTIR spectra agreed with results of composition analysis and hydrolysis. GC-MS detected some compounds only from RF-heated switchgrass. These compounds were found by other researchers only in high-temperature (150-600 °C) and high-pressure pyrolysis processes.

  8. Probing the Release and Uptake of Water in α-MnO 2 · xH 2O

    DOE PAGES

    Yang, Zhenzhen; Ford, Denise C.; Park, Joong Sun; ...

    2016-12-27

    Alpha-MnO 2 is of interest as a cathode material for 3 V lithium batteries and as an electrode/electrocatalyst for higher energy, hybrid Li-ion/Li–O 2 systems. It has a structure with large tunnels that contain stabilizing cations such as Ba 2+, K + , NH 4 + , and H3O + (or water, H 2O). When stabilized by H 3O + /H 2O, the protons can be ion-exchanged with lithium to produce a Li 2O-stabilized α-MnO 2 structure. It has been speculated that the electrocatalytic process in Li–O 2 cells may be linked to the removal of lithium and oxygen frommore » the host α-MnO 2 structure during charge, and their reintroduction during discharge. In this investigation, hydrated α-MnO 2 was used, as a first step, to study the release and uptake of oxygen in α-MnO 2. Temperature-resolved in situ synchrotron X-ray diffraction (XRD) revealed a nonlinear, two-stage, volume change profile, which with the aide of X-ray absorption near-edge spectroscopy (XANES), redox titration, and density functional theory (DFT) calculations, is interpreted as the release of water from the α-MnO 2 tunnels. The two stages correspond to H 2O release from intercalated H 2O species at lower temperatures and H 3O + species at higher temperature. Thermogravimetric analysis confirmed the release of oxygen from α-MnO 2 in several stages during heating–including surface water, occluded water, and structural oxygen–and in situ UV resonance Raman spectroscopy corroborated the uptake and release of tunnel water by revealing small shifts in frequencies during the heating and cooling of α-MnO 2. Lastly, DFT calculations revealed the likelihood of disordered water species in binding sites in α-MnO 2 tunnels and a facile diffusion process.« less

  9. Degradation mechanism of alachlor during direct ozonation and O(3)/H(2)O(2) advanced oxidation process.

    PubMed

    Qiang, Zhimin; Liu, Chao; Dong, Bingzhi; Zhang, Yalei

    2010-01-01

    The degradation of alachlor by direct ozonation and advanced oxidation process O(3)/H(2)O(2) was investigated in this study with focus on identification of degradation byproducts. The second-order reaction rate constant between ozone and alachlor was determined to be 2.5+/-0.1M(-1)s(-1) at pH 7.0 and 20 degrees C. Twelve and eight high-molecular-weight byproducts (with the benzene ring intact) from alachlor degradation were identified during direct ozonation and O(3)/H(2)O(2), respectively. The common degradation byproducts included N-(2,6-diethylphenyl)-methyleneamine, 8-ethyl-3,4-dihydro-quinoline, 8-ethyl-quinoline, 1-chloroacetyl-2-hydro-3-ketone-7-acetyl-indole, 2-chloro-2',6'-diacetyl-N-(methoxymethyl)acetanilide, 2-chloro-2'-acetyl-6'-ethyl-N-(methoxymethyl)-acetanilide, and two hydroxylated alachlor isomers. In direct ozonation, four more byproducts were also identified including 1-chloroacetyl-2,3-dihydro-7-ethyl-indole, 2-chloro-2',6'-ethyl-acetanilide, 2-chloro-2',6'-acetyl-acetanilide and 2-chloro-2'-ethyl-6'-acetyl-N-(methoxymethyl)-acetanilide. Degradation of alachlor by O(3) and O(3)/H(2)O(2) also led to the formation of low-molecular-weight byproducts including formic, acetic, propionic, monochloroacetic and oxalic acids as well as chloride ion (only detected in O(3)/H(2)O(2)). Nitrite and nitrate formation was negligible. Alachlor degradation occurred via oxidation of the arylethyl group, N-dealkylation, cyclization and cleavage of benzene ring. After O(3) or O(3)/H(2)O(2) treatment, the toxicity of alachlor solution examined by the Daphnia magna bioassay was slightly reduced. 2009 Elsevier Ltd. All rights reserved.

  10. Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst.

    PubMed

    Fang, Guo-Yong; Xu, Li-Na; Wang, Lai-Guo; Cao, Yan-Qiang; Wu, Di; Li, Ai-Dong

    2015-01-01

    Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

  11. Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst

    NASA Astrophysics Data System (ADS)

    Fang, Guo-Yong; Xu, Li-Na; Wang, Lai-Guo; Cao, Yan-Qiang; Wu, Di; Li, Ai-Dong

    2015-02-01

    Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

  12. Reduction Mechanisms of Cu2+-Doped Na2O-Al2O3-SiO2 Glasses during Heating in H2 Gas.

    PubMed

    Nogami, Masayuki; Quang, Vu Xuan; Ohki, Shinobu; Deguchi, Kenzo; Shimizu, Tadashi

    2018-01-25

    Controlling valence state of metal ions that are doped in materials has been widely applied for turning optical properties. Even though hydrogen has been proven effective to reduce metal ions because of its strong reducing capability, few comprehensive studies focus on practical applications because of the low diffusion rate of hydrogen in solids and the limited reaction near sample surfaces. Here, we investigated the reactions of hydrogen with Cu 2+ -doped Na 2 O-Al 2 O 3 -SiO 2 glass and found that a completely different reduction from results reported so far occurs, which is dominated by the Al/Na concentration ratio. For Al/Na < 1, Cu 2+ ions were reduced via hydrogen to metallic Cu, distributing in glass body. For Al/Na > 1, on the other hand, the reduction of Cu 2+ ions occurred simultaneously with the formation of OH bonds, whereas the reduced Cu metal moved outward and formed a metallic film on glass surface. The NMR and Fourier transform infrared results indicated that the Cu 2+ ions were surrounded by Al 3+ ions that formed AlO 4 , distorted AlO 4 , and AlO 5 units. The diffused H 2 gas reacted with the Al-O - ···Cu + units, forming Al-OH and metallic Cu, the latter of which moved freely toward glass surface and in return enhanced H 2 diffusion.

  13. Reactivity of alkaline lignite fly ashes towards CO{sub 2} in water

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Martin Back; Michael Kuehn; Helge Stanjek

    2008-06-15

    The reaction kinetics between alkaline lignite fly ashes and CO{sub 2} (pCO{sub 2} = 0.01-0.03 MPa) were studied in a laboratory CO{sub 2} flow-through reactor at 25-75{sup o}C. The reaction is characterized by three phases that can be separated according to the predominating buffering systems and the rates of CO{sub 2} uptake. Phase I (pH > 12, < 30 min) is characterized by the dissolution of lime, the onset of calcite precipitation and a maximum uptake, the rate of which seems to be limited by dissolution of CO{sub 2}. Phase II (pH < 10.5, 10-60 min) is dominated by themore » carbonation reaction. CO{sub 2} uptake in phase III (pH < 8.3) is controlled by the dissolution of periclase (MgO) leading to the formation of dissolved magnesium-bicarbonate. Phase I could be significantly extended by increasing the solid-liquid ratios and temperature, respectively. At 75{sup o}C the rate of calcite precipitation was doubled leading to the neutralization of approximately 0.23 kg CO{sub 2} per kg fly ash within 4.5 h, which corresponds to nearly 90% of the total acid neutralizing capacity. 21 refs., 5 figs., 1 tab.« less

  14. X-ray irradiation activates K+ channels via H2O2 signaling

    PubMed Central

    Gibhardt, Christine S.; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

    2015-01-01

    Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels. PMID:26350345

  15. Evaluation of H2O2 and pH in exhaled breath condensate samples: methodical and physiological aspects.

    PubMed

    Knobloch, Henri; Becher, Gunther; Decker, Manfred; Reinhold, Petra

    2008-05-01

    This veterinary study is aimed at further standardization of H(2)O(2) and pH measurements in exhaled breath condensate (EBC). Data obtained in the study provide valuable information for many mammalian species including humans, and may help to avoid general pitfalls in interpretation of EBC data. EBC was sampled via the 'ECoScreen' in healthy calves (body weight 63-98 kg). Serum samples and condensates of ambient (indoor) air were collected in parallel. In the study on H(2)O(2), concentrations of H(2)O(2) in EBC, blood and ambient air were determined with the biosensor system 'ECoCheck'. In EBC, the concentration of H(2)O(2) was found to be dependent on food intake and increased significantly in the course of the day. Physiologically, lowest H(2)O(2) concentrations at 06:00 varied within the range 138-624 nmol l(-1) EBC or 0.10-0.94 nmol per 100 l exhaled breath and individual concentrations were significantly different indicating a remarkable intersubject variability. Highly reproducible results were seen within each subject (three different days within 4 weeks). No correlation existed between H(2)O(2) concentrations in EBC and blood, and EBC-H(2)O(2) was not influenced by variables of spontaneous breathing. Further results confirmed that standardization of H(2)O(2) measurements in EBC requires (1) the re-calculation of the concentration exhaled per 100 l exhaled breath (because the analyzed concentration in the liquid condensate underlies multiple methodological sources of variability given by the collection process), and (2) subtracting the concentration of inspired indoor H(2)O(2). In the study on pH use of the ISFET electrode (Sentron, the Netherlands) and a blood gas analyzer ABL 550 (Radiometer, Denmark) led to comparable results for EBC-pH (r=0.89, R(2)=79.3%, pH data in non-degassed EBC samples varied between 5.3 and 6.5, and were not significantly different between subjects, but were significantly higher in the evening compared

  16. Influence of H2O2 on LPG fuel performance evaluation

    NASA Astrophysics Data System (ADS)

    Khan, Muhammad Saad; Ahmed, Iqbal; Mutalib, Mohammad Ibrahim bin Abdul; Nadeem, Saad; Ali, Shahid

    2014-10-01

    The objective of this mode of combustion is to insertion of hydrogen peroxide (H2O2) to the Liquefied Petroleum Gas (LPG) combustion on spark plug ignition engines. The addition of hydrogen peroxide may probably decrease the formation of NOx, COx and unburned hydrocarbons. Hypothetically, Studies have shown that addition of hydrogen peroxide to examine the performance of LPG/H2O2 mixture in numerous volumetric compositions starting from lean LPG until obtaining a better composition can reduce the LPG fuel consumption. The theory behind this idea is that, the addition of H2O2 can cover the lean operation limit, increase the lean burn ability, diminution the burn duration along with controlling the exhaust emission by significantly reducing the greenhouse gaseous.

  17. Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

    PubMed

    Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

    2015-01-01

    The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the

  18. IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    De Visscher, Alex; Vanderdeelen, Jan; Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University, B-9000 Ghent

    The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO{sub 3} types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO{sub 3}{center_dot} H{sub 2}O), the hexahydrate ikaite (CaCO{sub 3}{center_dot}6H{submore » 2}O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.« less

  19. Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O, beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2).

    PubMed

    Almond, Philip M; Albrecht-Schmitt, Thomas E

    2002-10-21

    The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta

  20. Curcumin-induced heme oxygenase-1 expression prevents H2O2-induced cell death in wild type and heme oxygenase-2 knockout adipose-derived mesenchymal stem cells.

    PubMed

    Cremers, Niels A J; Lundvig, Ditte M S; van Dalen, Stephanie C M; Schelbergen, Rik F; van Lent, Peter L E M; Szarek, Walter A; Regan, Raymond F; Carels, Carine E; Wagener, Frank A D T G

    2014-10-08

    Mesenchymal stem cell (MSC) administration is a promising adjuvant therapy to treat tissue injury. However, MSC survival after administration is often hampered by oxidative stress at the site of injury. Heme oxygenase (HO) generates the cytoprotective effector molecules biliverdin/bilirubin, carbon monoxide (CO) and iron/ferritin by breaking down heme. Since HO-activity mediates anti-apoptotic, anti-inflammatory, and anti-oxidative effects, we hypothesized that modulation of the HO-system affects MSC survival. Adipose-derived MSCs (ASCs) from wild type (WT) and HO-2 knockout (KO) mice were isolated and characterized with respect to ASC marker expression. In order to analyze potential modulatory effects of the HO-system on ASC survival, WT and HO-2 KO ASCs were pre-treated with HO-activity modulators, or downstream effector molecules biliverdin, bilirubin, and CO before co-exposure of ASCs to a toxic dose of H2O2. Surprisingly, sensitivity to H2O2-mediated cell death was similar in WT and HO-2 KO ASCs. However, pre-induction of HO-1 expression using curcumin increased ASC survival after H2O2 exposure in both WT and HO-2 KO ASCs. Simultaneous inhibition of HO-activity resulted in loss of curcumin-mediated protection. Co-treatment with glutathione precursor N-Acetylcysteine promoted ASC survival. However, co-incubation with HO-effector molecules bilirubin and biliverdin did not rescue from H2O2-mediated cell death, whereas co-exposure to CO-releasing molecules-2 (CORM-2) significantly increased cell survival, independently from HO-2 expression. Summarizing, our results show that curcumin protects via an HO-1 dependent mechanism against H2O2-mediated apoptosis, and likely through the generation of CO. HO-1 pre-induction or administration of CORMs may thus form an attractive strategy to improve MSC therapy.

  1. Photochemical Generation of H_{2}NCNX, H_{2}NNCX, H_{2}NC(NX) (x = O, s) in Low-Temperature Matrices

    NASA Astrophysics Data System (ADS)

    Voros, Tamas; Lajgut, Gyozo Gyorgy; Magyarfalvi, Gabor; Tarczay, Gyorgy

    2017-06-01

    The [NH_{2}, C, N, O] and the [NH_{2}, C, N, S] systems were investigated by quantum-chemical computations and matrix-isolation spectroscopic methods. The equilibrium structures of the isomers and their relative energies were determined by CCSD(T) method. This was followed by the computation of the harmonic and anharmonic vibrational wavenumbers, infrared intensities, relative Raman activities and UV excitation energies. These computed data were used to assist the identification of products obtained by UV laser photolysis of 3,4-diaminofurazan, 3,4-diaminothiadiazole and 1,2,4-thiadiazole-3,5-diamine in low-temperature Ar and Kr matrices. Experimentally, first the precursors were studied by matrix-isolation IR and UV spectroscopic methods. Based on these UV spectra, different wavelengths were selected for photolysis. The irradiations, carried out by a tunable UV laser-light source, resulted in the decomposition of the precursors, and in the appearance of new bands in the IR spectra. Some of these bands were assigned to cyanamide (H_{2}NCN) and its isomer, the carbodiimide molecule (HNCNH), generated from H_{2}NCN. By the analysis of the relative absorbance vs. photolysis time curves, the other bands were grouped to three different species both for the O- and the S-containing systems. In the case of the O-containing isomers, these bands were assigned to the H_{2}NNCO:H_{2}NCN, and H_{2}NCNO:H_{2}NCN complexes, and to the ring-structure H_{2}NC(NO) isomer. In a similar way, the complexes of H_{2}NNCS and H_{2}NCNS with the H_{2}NCN, and H_{2}NC(NS) were also identified. 1,2,4-thiadiazole-3,5-diamine was also investigated in similar way like the above mentioned precursors. The results of this study also support the identification of the new S-containing isomers. Except for H_{2}NNCO and H_{2}NCNS, these molecules were not identified previously. It is expected that at least some of these species, like the methyl isocyanate (CH_{3}CNO) isomer, are present and could be

  2. Spectral and thermal studies of MgI2·8H2O

    NASA Astrophysics Data System (ADS)

    Koleva, Violeta; Stefov, Viktor; Najdoski, Metodija; Ilievski, Zlatko; Cahil, Adnan

    2017-10-01

    In the present contribution special attention is paid to the spectroscopic and thermal characterization of MgI2·8H2O which is the stable hydrated form at room temperature. The infrared spectra of MgI2·8H2O and its deuterated analogues recorded at room and liquid nitrogen temperature are presented and interpreted. In the low-temperature diference infrared spectrum of the slightly deuterated analogue (≈5% D) at least four bands are found out of the expected five (at 2595, 2550, 2538 and 2495 cm-1) as a result of the uncoupled O-D oscillators in the isotopically isolated HOD molecules. Multiple bands are observed in the water bending region and only two bands of the HOH librational modes are found. For more precise and deep description of the processes occurring upon heating of MgI2·8H2O we have applied simultaneous TG/DTA/Mass spectrometry technique identifying the gases evolved during the thermal transformations. We have established that the thermal decomposition of MgI2·8H2O is a complex process that takes place in two main stages. In the first stage (between 120 and 275 °C) the salt undergoes a partial stepwise dehydration to MgI2·2H2O followed by a hydrolytic decomposition with formation of magnesium hydroxyiodide Mg(OH)1.44I0.56 accompanied with simultaneous release of H2O and HI. In the second stage Mg(OH)1.44I0.56 is completely decomposed to MgO with elimination of gaseous H2O, HI, I2 and H2. Infrared spectra of the annealed samples heated between 190 and 270 °C confirmed the formation of magnesium hydroxyiodide.

  3. Suppression of N2O and NO from denitrification by biochar: the role of pH

    NASA Astrophysics Data System (ADS)

    Obia, Alfred; Cornelissen, Gerard; Mulder, Jan; Dörsch, Peter

    2015-04-01

    Denitrification reduces NO3- to N2 and returns excess nitrogen to the atmosphere. NO and N2O are gaseous intermediates of denitrification which, once escaped to the atmosphere, have adverse effects on chemistry and radiative forcing in the atmosphere. We studied the effect of biochar on denitrification and its gaseous intermediates in two acidic soils and tried to distinguish between the alkalizing effect of biochars on soil pH, and other, unknown effects of biochar on denitrification. Anoxic soil slurries were incubated with untreated biochars or biochars from which part of the alkalinity had been removed by water- and acid leaching. Soils amended with NaOH and uncharred cacao shell were used as controls. Biochar addition stimulated overall denitrification depending on biochar and soil type. This stimulation was not strictly coupled to pH increase, suggesting that biochar fueled respiration processes by contributing microbially available C. High resolution gas kinetics of NO, N2O and N2 showed that biochar amended soils induced denitrification enzymes earlier and with higher activity, resulting in less NO and N2O accumulation relative to N2 production. The extent to which biochar suppressed NO and N2O was dose-dependent and clearly related to the effective pH increase during incubation. Acid leaching of BC reduced or eliminated its ability to suppress N2O and NO net production. Comparison of BC with NaOH-amended soils showed that the reduction of N2O and NO net production was mainly an effect of increase in soil pH. Even though other factors supporting N2O reductase activity could not be excluded, our results indicate that soil pH increase might be an important driver behind the often-reported suppression of N2O emissions after biochar addition.

  4. CO Diffusion into Amorphous H2O Ices

    NASA Astrophysics Data System (ADS)

    Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

    2015-03-01

    The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

  5. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

  6. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

    PubMed

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-27

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

  7. Tamarix gallica phenolics protect IEC-6 cells against H2O2 induced stress by restricting oxidative injuries and MAPKs signaling pathways.

    PubMed

    Bettaib, Jamila; Talarmin, Hélène; Droguet, Mickaël; Magné, Christian; Boulaaba, Mondher; Giroux-Metges, Marie-Agnès; Ksouri, Riadh

    2017-05-01

    Polyphenolic compounds gained interest in the pharmaceutical research area due to their beneficial properties. Herein, antioxidant and cytoprotective capacities of T. gallica extract on H 2 O 2 -challenged rat small intestine epithelial cells were investigated. To set stress conditions, IEC-6 cultures were challenged with numerous H 2 O 2 doses and durations. Then, 40μM H 2 O 2 during 4h were selected to assess the cytoprotective effect of different T. gallica extract concentrations. Oxidative parameters, measured through CAT and SOD activities as well as MDA quantification were assessed. In addition, the expression of possibly involved MAPKs was also valued. Main results reported that T. gallica was rich in polyphenols and exhibited an important antioxidant activity (DPPH Assay, IC 50 =6μgmL -1 ; ABTS + test, IC 50 =50μgmL -1 ; Fe-reducing power, EC 50 =100μgmL -1 ). The exposure of IEC-6 cultures to 40μM H 2 O 2 during 4h caused oxidative stress manifested by (i) over 70% cell mortality, (ii) over-activity of CAT (246%), (iii) excess in MDA content (18.4nmolmg -1 ) and (iiii) a trigger of JNK phosphorylation. Pretreatment with T. gallica extract, especially when used at 0.25μgmL -1 , restored cell viability to 122%, and normal cell morphology in H 2 O 2 -chalenged cells. In addition, this extract normalized CAT activity and MDA content (100% and 14.7nmolmg -1 , respectively) to their basal levels as compared to control cells. Furthermore, stopping cell death seems to be due to dephosphorylated JNK MAPK exerted by T. gallica bioactive compounds. In all, T. gallica components provided a cross-talk between regulatory pathways leading to an efficient cytoprotection against harmful oxidative stimulus. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  8. Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe3)(CO)2H, CpMo(PMe3)2(CO)H, [CpMo(μ-O)(μ-O2CH)]2, and [Cp*Mo(μ-O)(μ-O2CH)]2.

    PubMed

    Neary, Michelle C; Parkin, Gerard

    2017-02-06

    The molecular structures of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H-Mo-CO moiety are displaced towards the hydride ligand. While Cp R Mo(PMe 3 ) 3-x (CO) x H (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H 2 from formic acid, the carbonyl derivatives, Cp R Mo(CO) 3 H, are also observed to form dinuclear formate compounds, namely, [Cp R Mo(μ-O)(μ-O 2 CH)] 2 . The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2 CH)] 2 and [Cp*Mo(μ-O)(μ-O 2 CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2 CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO-1) orbitals. The σ 2 δ* 2 configuration thus corresponds to a formal direct Mo-Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo-Mo bond, whereas a Mo═Mo double bond is required in the absence of lone-pair donation.

  9. Conductivity measurements on H 2O-bearing CO 2-rich fluids

    DOE PAGES

    Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; ...

    2014-09-10

    Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H 2O to CO 2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO 2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H 2O concentrationsmore » up to ~1600 ppmw (xH 2O ≈ 3.9 x 10 -3), corresponding to the H 2O solubility limit in liquid CO 2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO 2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

  10. Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

    PubMed

    Zhao, Hai-Qian; Wang, Zhong-Hua; Gao, Xing-Cun; Liu, Cheng-Hao; Qi, Han-Bing

    2018-01-01

    H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

  11. Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures

    PubMed Central

    Wang, Zhong-hua; Gao, Xing-cun; Liu, Cheng-hao; Qi, Han-bing

    2018-01-01

    H2O2 was adopted to oxidize NO in simulated flue gas at 100–500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300–500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption. PMID:29668672

  12. Effects of ultrasound and ultrasound assisted alkaline pretreatments on the enzymolysis and structural characteristics of rice protein.

    PubMed

    Li, Suyun; Yang, Xue; Zhang, Yanyan; Ma, Haile; Liang, Qiufang; Qu, Wenjuan; He, Ronghai; Zhou, Cunshan; Mahunu, Gustav Komla

    2016-07-01

    The objectives of this study were to investigate the effects of multi-frequency energy-gathered ultrasound (MFEGU) and MFEGU assisted alkaline pretreatments on the enzymolysis and the mechanism of two pretreatments accelerating the rice protein (RP) proteolysis process. The results showed that MFEGU and MFEGU assisted alkaline pretreatments improved significantly (P<0.05) the degree of hydrolysis (DH) and the protein elution amount of RP. Furthermore under the same DH conditions, ultrasound and ultrasound assisted alkaline pretreatments were more save the enzymolysis time than the unpretreatment. The changes in UV-vis spectra, fluorescence emission spectra indicated unfolding and destruction of RP by MFEGU and MFEGU assisted alkaline pretreatments. The circular dichroism analysis showed that both pretreatments decreased α-helix but increased β-sheet and random coil of RP. Amino acid composition revealed that MFEGU and MFEGU assisted alkaline pretreatments could increase the protein elution amount and the ratio of hydrophobic amino acids. Atomic force microscopy (AFM) indicated that both pretreatments destroyed the microstructures and reduced the particle size of RP. Therefore, MFEGU and MFEGU assisted alkaline pretreatments are beneficial to improving the degree of hydrolysis due to its sonochemistry effect on the molecular conformation as well as on the microstructure of protein. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Mesospheric H2O Concentrations Retrieved from SABER/TIMED Measurements

    NASA Technical Reports Server (NTRS)

    Feofilov, A. G.; Marshall, B. T.; Garcia-Comas, M.; Kutepov, A. A.; Lopez-Puertas, M.; Manuilova, R. O.; Yankovsky, V.A.; Goldberg, R. A.; Gordley, L. L.; Petelin, S.; hide

    2008-01-01

    The SABER instrument on board the TIMED Satellite is a limb scanning infrared radiometer designed to measure temperature and minor constituent vertical profiles and energetics parameters in the mesosphere and lower thermosphere (MLT). The H2O concentrations are retrieved from 6.3 micron band radiances. The populations of H2O(v2) vibrational levels are in non-Local Thermodynamic Equilibrium (non-LTE) above approximately 55 km altitude and the interpretation of 6.3 micron radiance requires utilizing non-LTE H2O model that includes various energy exchange processes in the system of H2O vibrational levels coupled with O2, N2, and CO2 vibrational levels. We incorporated these processes including kinetics of O2/O3 photolysis products to our research non-LTE H2O model and applied it for the development and optimization of SABER operational model. The latter has been validated using simultaneous SCISAT1/ACE occultation measurements. This helped us to estimate CO2(020)-O2(X,v=I), O2(X,v=I)- H2O(010), and O2(X,v=1) O rates at mesopause temperatures that is critical for an adequate interpretation of non-LTE H2O radiances in the MLT. The first distributions of seasonal and meridional H2O concentrations retrieved from SABER 6.3 micron radiances applying an updated non-LTE H2O model are demonstrated and discussed.

  14. Phosphinodi(benzylsilane) PhP{(o-C6H4CH2)SiMe2H}2: a versatile "PSi2Hx" pincer-type ligand at ruthenium.

    PubMed

    Montiel-Palma, Virginia; Muñoz-Hernández, Miguel A; Cuevas-Chávez, Cynthia A; Vendier, Laure; Grellier, Mary; Sabo-Etienne, Sylviane

    2013-09-03

    The synthesis of the new phosphinodi(benzylsilane) compound PhP{(o-C6H4CH2)SiMe2H}2 (1) is achieved in a one-pot reaction from the corresponding phenylbis(o-tolylphosphine). Compound 1 acts as a pincer-type ligand capable of adopting different coordination modes at Ru through different extents of Si-H bond activation as demonstrated by a combination of X-ray diffraction analysis, density functional theory calculations, and multinuclear NMR spectroscopy. Reaction of 1 with RuH2(H2)2(PCy3)2 (2) yields quantitatively [RuH2{[η(2)-(HSiMe2)-CH2-o-C6H4]2PPh}(PCy3)] (3), a complex stabilized by two rare high order ε-agostic Si-H bonds and involved in terminal hydride/η(2)-Si-H exchange processes. A small free energy of reaction (ΔrG298 = +16.9 kJ mol(-1)) was computed for dihydrogen loss from 3 with concomitant formation of the 16-electron species [RuH{[η(2)-(HSiMe2)-CH2-o-C6H4]PPh[CH2-o-C6H4SiMe2]}(PCy3)] (4). Complex 4 features an unprecedented (29)Si NMR decoalescence process. The dehydrogenation process is fully reversible under standard conditions (1 bar, 298 K).

  15. Do aerosols influence the diurnal variation of H2O2 in the atmosphere?

    NASA Astrophysics Data System (ADS)

    Liang, H.; Chen, Z.; Wu, Q.; Huang, D.; Zhao, Y.

    2013-12-01

    Hydrogen peroxide (H2O2) and organic peroxides are crucial reactive species that are involved in the cycling of HOx (OH and HO2) radicals and the formation of secondary inorganic and organic aerosols in the atmosphere. Despite the importance of peroxides, their formation and removal mechanisms with the coexistence of aerosols are as yet less well known. From June 10 to July 15 2013, summertime surface measurements for atmospheric peroxides were simultaneously obtained in urban Beijing (UB) and Gucheng (GC). The UB site is located in the northern downtown of Beijing city, while the GC site is a rural site located in the North China Plain and ~100 km southwest of Beijing. In both sites, the major peroxides were determined to be H2O2, methyl hydroperoxide (MHP), peroxyformic acid (PFA) and peroxyacetic acid (PAA). By comparing the concentrations of PFA and PAA in the gas phase and rainwater, for the first time, we estimated the Henry's law constant for PFA as ~210 M atm-1 at 298 K, a quarter of that for PAA. Interestingly, we observed different H2O2 profiles in the two sites as follows: (i) the average concentration of H2O2 in UB was 50% higher than that in GC; (ii) H2O2 in GC reached its peak concentration at around 15:30, whereas the peak concentration in UB appeared at as late as 21:00; and (iii) the daily variation of H2O2 in GC generally kept consistent with that of O3 and organic peroxides while it was not always the case in UB. These differences indicate a hitherto unrecognized storage-release mechanism for H2O2 in UB, that is, an extra sink in the noontime and an extra source in the early evening. The extra source of H2O2 would enhance the aerosol phase OH radical in the early evening by the Fenton reaction. A box model analysis shows that the impacts of aerosols were majorly responsible to this unrecognized mechanism, although NOx, regional transport and planet boundary layer height also contributed a minor part. Aerosols participated in the storage

  16. The reactions of HO2 with CO and NO and the reaction of O(1D) with H2O

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Heicklen, J.

    1973-01-01

    HO2 radicals were generated by the photolysis of N2O at 2139 A in the presence of excess H2O or H2 and smaller amounts of CO and O2. The O(1D) atoms produced from the photolysis of N2O to give HO radicals or H2 to give HO + H. With H2O two HO radicals are produced for each O(1D) removed low pressures (i.e. approximately 20 torr H2O), but the HO yield drops as the pressure is raised. This drop is attributed to the insertion reaction: O(1D) + H2O + M yields H2O2 +M. The HO radicals generated can react with either CO or H2 to produce H atoms which then add to O2 to produce HO2. Two reactions are given for the reactions of the HO radicals, in the absence of NO.

  17. CO2 splitting by H2O to CO and O2 under UV light in TiMCM-41silicate sieve

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lin, Wenyong; Han, Hongxian; Frei, Heinz

    2004-04-06

    The 266 nm light-induced reaction of CO{sub 2} and H{sub 2}O gas mixtures (including isotopic modifications {sup 13}CO{sub 2}, C{sup 18}O{sub 2}, and D{sub 2}O) in framework TiMCM-41 silicate sieve was monitored by in-situ FT-IR spectroscopy at room temperature. Carbon monoxide gas was observed as the sole product by infrared, and the growth was found to depend linearly on the photolysis laser power. H{sub 2}O was confirmed as stoichiometric electron donor. The work establishes CO as the single photon, 2-electron transfer product of CO{sub 2} photoreduction by H{sub 2}O at framework Ti centers for the first time. O{sub 2} wasmore » detected as co-product by mass spectrometric analysis of the photolysis gas mixture. These results are explained by single UV photon-induced splitting of CO{sub 2} by H{sub 2}O to CO and surface OH radical.« less

  18. Etude des mécanismes d'ionisation de H{2}O par interaction He^{*}(2 ^1S, 2 ^3S)/Ne^{*}(^3P{0}, ^3P{2})+H{2}O

    NASA Astrophysics Data System (ADS)

    Le Nadan, André; Sinou, Guillaume; Tuffin, Firmin

    1993-06-01

    Experimental observations of Penning ionisation of H{2}O by the helium metastables 21S and 23S and by the neon metastables ^3P{0} and ^3P{2} are reported. The kinetic energies of the ions created during the collision process (both parent and fragment) are analysed. Certain particularities of the experimental results are explained by involving the hypothesis of transfers of vibrational energy to kinetic energy. Furthermore, the forms of the energy distributions of the fragment ions are explained by th predissociation of the ^2B{2} state of H{2}O+. Nous avons étudié l'ionisation Penning de H{2}O par des métastables 21S et 23S de l'hélium, ainsi que ^3P{0} et ^3P{2} du néon. Nous avons analysé l'énergie cinétique des ions créés au cours de la collision (parents et fragments). Afin d'interpréter certaines particularités expérimentales, l'hypothèse de transferts d'énergie de vibration en énergie cinétique est proposées. Par ailleurs, les caractéristiques des distributions en énergie des ions fragments sont expliquées par la prédissociation de l'état ^2B{2} de H{2}O+.

  19. Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Yu-Heng; Pegis, Michael L.; Mayer, James M.

    A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2more » was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.« less

  20. Synthesis and physicochemical characterization of carbon backbone modified [Gd(TTDA)(H2O)]2- derivatives.

    PubMed

    Chang, Ya-Hui; Chen, Chiao-Yun; Singh, Gyan; Chen, Hsing-Yin; Liu, Gin-Chung; Goan, Yih-Gang; Aime, Silvio; Wang, Yun-Ming

    2011-02-21

    The present study was designed to exploit optimum lipophilicity and high water-exchange rate (k(ex)) on low molecular weight Gd(III) complexes to generate high bound relaxivity (r(1)(b)), upon binding to the lipophilic site of human serum albumin (HSA). Two new carbon backbone modified TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triazadodecanedioic acid) derivatives, CB-TTDA and Bz-CB-TTDA, were synthesized. The complexes [Gd(CB-TTDA)(H(2)O)](2-) and [Gd(Bz-CB-TTDA)(H(2)O)](2-) both display high stability constant (log K(GdL) = 20.28 and 20.09, respectively). Furthermore, CB-TTDA (log K(Gd/Zn) = 4.22) and Bz-CB-TTDA (log K(Gd/Zn) = 4.12) exhibit superior selectivity of Gd(III) against Zn(II) than those of TTDA (log K(Gd/Zn) = 2.93), EPTPA-bz-NO(2) (log K(Gd/Zn) = 3.19), and DTPA (log K(Gd/Zn) = 3.76). However, the stability constant values of [Gd(CB-TTDA)(H(2)O)](2-) and [Gd(Bz-CB-TTDA)(H(2)O)](2-) are lower than that of MS-325. The parameters that affect proton relaxivity have been determined in a combined variable temperature (17)O NMR and NMRD study. The water exchange rates are comparable for the two complexes, 232 × 10(6) s(-1) for [Gd(CB-TTDA)(H(2)O)](2-) and 271 × 10(6) s(-1) for [Gd(Bz-CB-TTDA)(H(2)O)](2-). They are higher than those of [Gd(TTDA)(H(2)O)](2-) (146 × 10(6) s(-1)), [Gd(DTPA)(H(2)O)](2-) (4.1 × 10(6) s(-1)), and MS-325 (6.1 × 10(6) s(-1)). Elevated stability and water exchange rate indicate that the presence of cyclobutyl on the carbon backbone imparts rigidity and steric constraint to [Gd(CB-TTDA)(H(2)O)](2-)and [Gd(Bz-CB-TTDA)(H(2)O)](2-). In addition, the major objective for selecting the cyclobutyl is to tune the lipophilicity of [Gd(Bz-CB-TTDA)(H(2)O)](2-). The binding affinity of [Gd(Bz-CB-TTDA)(H(2)O)](2-) to HSA was evaluated by ultrafiltration study across a membrane with a 30 kDa MW cutoff, and the first three stepwise binding constants were determined by fitting the data to a stoichiometric model. The binding association constants (K

  1. O2 reduction to H2O by the multicopper oxidases.

    PubMed

    Solomon, Edward I; Augustine, Anthony J; Yoon, Jungjoo

    2008-08-14

    In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in nature.

  2. O2 Reduction to H2O by the Multicopper Oxidases

    PubMed Central

    Solomon, Edward I.; Augustine, Anthony J.; Yoon, Jungjoo

    2010-01-01

    In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c Oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in Nature. PMID:18648693

  3. H2/O2 three-body rates at high temperatures

    NASA Technical Reports Server (NTRS)

    Marinelli, William J.; Kessler, William J.; Piper, Lawrence G.; Rawlins, W. Terry

    1990-01-01

    The extraction of thrust from air breathing hypersonic propulsion systems is critically dependent on the degree to which chemical equilibrium is reached in the combustion process. In the combustion of H2/Air mixtures, slow three-body chemical reactions involving H-atoms, O-atoms, and the OH radical play an important role in energy extraction. A first-generation high temperature and pressure flash-photolysis/laser-induced fluorescence reactor was designed and constructed to measure these important three-body rates. The system employs a high power excimer laser to produce these radicals via the photolysis of stable precursors. A novel two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical thickness or O2 absorption problems. To demonstrate the feasibility of the technique the apparatus in the program is designed to perform preliminary measurements on the H + O2 + M reaction at temperatures from 300 to 835 K.

  4. Fungal pretreatment of willow sawdust and its combination with alkaline treatment for enhancing biogas production.

    PubMed

    Alexandropoulou, Maria; Antonopoulou, Georgia; Fragkou, Efsevia; Ntaikou, Ioanna; Lyberatos, Gerasimos

    2017-12-01

    In this study fungal pretreatment of willow sawdust (WSD) via the white rot fungi Leiotrametes menziesii and Abortiporus biennis was studied and the effect on fractionation of lignocellulosic biomass and biochemical methane potential (BMP), was evaluated. Scanning electron microscopy (SEM) and IR spectroscopy were used to investigate the changes in the structural characteristics of the pretreated WSD. Fungal pretreatment results revealed that A. biennis is more attractive, since it resulted in higher lignin degradation and lower holocellulose uptake. Samples of the 14th and 30th d of cultivation (i.e. the middle and the end of the pretreatment experiment) with both fungi were used for BMP tests and the effect of pretreatment duration was also evaluated. BMP increase by 31 and 43% was obtained due to the cultivation of WSD with A. biennis, for 14 and 30 d, respectively. In addition, combination of biological (after 30 d of cultivation) with alkaline (NaOH 20 g/100 gTS) pretreatment was performed, in order to assess the effect of the chemical agent on biologically pretreated WSD, in terms of lignocellulosic content and BMP. Combination of alkaline with fungal pretreatment led to high lignin degradation for both fungi, while the cellulose and hemicellulose removal efficiencies were higher for combined alkaline and L. menziesii pretreatment. The maximum BMP was observed for the combined alkaline and A. biennis pretreatment and was 12.5 and 50.1% higher than the respective alkaline and fungal pretreatment alone and 115% higher than the respective BMP of raw WSD. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Detection of pH and Enzyme-Free H2O2 Sensing Mechanism by Using GdO x Membrane in Electrolyte-Insulator-Semiconductor Structure.

    PubMed

    Kumar, Pankaj; Maikap, Siddheswar; Qiu, Jian-Tai; Jana, Surajit; Roy, Anisha; Singh, Kanishk; Cheng, Hsin-Ming; Chang, Mu-Tung; Mahapatra, Rajat; Chiu, Hsien-Chin; Yang, Jer-Ren

    2016-12-01

    A 15-nm-thick GdO x membrane in an electrolyte-insulator-semiconductor (EIS) structure shows a higher pH sensitivity of 54.2 mV/pH and enzyme-free hydrogen peroxide (H2O2) detection than those of the bare SiO2 and 3-nm-thick GdO x membranes for the first time. Polycrystalline grain and higher Gd content of the thicker GdO x films are confirmed by transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS), respectively. In a thicker GdO x membrane, polycrystalline grain has lower energy gap and Gd(2+) oxidation states lead to change Gd(3+) states in the presence of H2O2, which are confirmed by electron energy loss spectroscopy (EELS). The oxidation/reduction (redox) properties of thicker GdO x membrane with higher Gd content are responsible for detecting H2O2 whereas both bare SiO2 and thinner GdO x membranes do not show sensing. A low detection limit of 1 μM is obtained due to strong catalytic activity of Gd. The reference voltage shift increases with increase of the H2O2 concentration from 1 to 200 μM owing to more generation of Gd(3+) ions, and the H2O2 sensing mechanism has been explained as well.

  6. Bleaching of cotton fabric with tetraacetylhydrazine as bleach activator for H2O2.

    PubMed

    Liu, Kai; Zhang, Xuan; Yan, Kelu

    2018-05-15

    Tetraacetylhydrazine (TH) as bleach activator for H 2 O 2 cotton bleaching was synthesized and characterized by 1 H NMR, 13 C NMR and MS spectra. TH has better solubility than that of TAED. The CIE whiteness index (WI), H 2 O 2 decomposition rate and bursting strength were employed to investigate the performance of H 2 O 2 /TH bleaching system. By addition of TH, WI and H 2 O 2 decomposition rate increased significantly at 70 °C. Bleaching temperature, NaHCO 3 concentration and bleaching time were also discussed in detail and the loss of bursting strength is not clear. By using benzenepentacarboxylic acid (BA) as a fluorescent probe for hydroxyl radical detection, the bleaching process of H 2 O 2 /TH system was investigated. Acetylhydrazine and diacetylhydrazine were also utilized to further confirm the process. In addition, bimolecular decomposition was investigated by using 9,10-dimethylanthracene (DMA) as fluorescent probe of 1 O 2 . Based on these experimental results, the bleaching mechanism of H 2 O 2 /TH system was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Isotopic separation of D.sub.2 O from H.sub.2 O using ruthenium adsorbent

    DOEpatents

    Thiel, Patricia A.

    1990-04-10

    A method of enrichment of D.sub.2 O in solutions of D.sub.2 O in H.sub.2 O by contacting said solutions in the steam phase with hexagonal crystalline to produce enriched D.sub.2 O. The passages may be repeated to achieve a desired amount of D.sub.2 O.

  8. Neuroprotective Effect of CeO2@PAA-LXW7 Against H2O2-Induced Cytotoxicity in NGF-Differentiated PC12 Cells.

    PubMed

    Jia, Jingjing; Zhang, Ting; Chi, Jieshan; Liu, Xiaoma; Sun, Jingjing; Xie, Qizhi; Peng, Sijia; Li, Changyan; Yi, Li

    2018-06-07

    CeO 2 nanoparticles (nanoceria) have been used in many studies as a powerful free radical scavenger, and LXW7, a small-molecule peptide, can specifically target the integrin αvβ3, whose neuroprotective effects have also been demonstrated. The objective of this study is to observe the neuroprotective effect and potential mechanism of CeO 2 @PAA-LXW7, a new compound that couples CeO 2 @PAA (nanoceria modified with the functional group of polyacrylic acid) with LXW7 via a series of chemical reactions, in H 2 O 2 -induced NGF-differentiated PC12 cells. We examined the effects of LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 on the viability of primary hippocampal neurons and found that there was no significant difference under control conditions, but increased cellular viability was observed in the case of H 2 O 2 -induced injury. We used H 2 O 2 -induced NGF-differentiated PC12 cells as the classical injury model to investigate the neuroprotective effect of CeO 2 @PAA-LXW7. In this study, LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 inhibit H 2 O 2 -induced oxidative stress by reducing the production of reactive oxygen species (ROS) and regulating Bax/Bcl-2, cleaved caspase-3 and mitochondrial cytochrome C (cyto C) in the apoptotic signaling pathways. We found that the levels of phosphorylation of focal adhesion kinase (FAK) and of signal transducer and activator of transcription 3 (STAT3) increased significantly in H 2 O 2 -induced NGF-differentiated PC12 cells, whereas LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 suppressed the increase to different degrees. Among the abovementioned changes, the inhibitory effect of CeO 2 @PAA-LXW7 on H 2 O 2 -induced changes, including the increases in the levels of p-FAK and p-STAT3, is more obvious than that of LXW7 or CeO 2 @PAA alone. In summary, these results suggest that integrin signaling participates in the regulation of apoptosis via the regulation of ROS and of the apoptosis pathway in H 2 O 2 -induced NGF-differentiated PC12 cells. LXW7, CeO

  9. Diode laser measurements of linestrength and temperature-dependent lineshape parameters of H2O-, CO2-, and N2-perturbed H2O transitions near 2474 and 2482 nm

    NASA Astrophysics Data System (ADS)

    Goldenstein, Christopher S.; Jeffries, Jay B.; Hanson, Ronald K.

    2013-11-01

    Absorption lineshapes for two unresolved H2O doublets near 4029.52 and 4041.92 cm-1 were measured at high-resolution in a heated static cell using two distributed-feedback diode lasers. Measurements were acquired for H2O, CO2, and N2 perturbers over a temperature and pressure range of 650-1325 K and 2-760 Torr, respectively. Strong collisional narrowing effects were observed in CO2 and N2, but not in pure H2O. The Galatry profile was used to infer collisional-broadening and -narrowing coefficients and their respective temperature dependence for CO2 and N2 perturbers. The collisional-broadening and -narrowing coefficients for CO2 perturbers were found to decrease with increasing temperature in a similar manner. For N2 perturbers, the collisional-broadening coefficients increased with temperature while the collisional-narrowing coefficients decreased with increasing temperature. Self-broadening coefficients were inferred from Voigt profile fits and are compared with HITEMP 2010. The linestrengths of 17 H2O transitions are also reported.

  10. Antioxidant activity against H2O2-induced cytotoxicity of the ethanol extract and compounds from Pyrola decorate leaves.

    PubMed

    Yang, Xiliang; Peng, Qingyun; Liu, Qian; Hu, Jie; Tang, Zhipeng; Cui, Lianjie; Lin, Zonghao; Xu, Bing; Lu, Kuojian; Yang, Fang; Sheng, Zhizheng; Yuan, Qiong; Liu, Song; Zhang, Jiuliang; Zhou, Xuefeng

    2017-12-01

    The leaves of Pyrola decorate H. Andr (Pyrolaceae), known as Luxiancao, have long been used for treating kidney deficiency, gastric haemorrhage and rheumatic arthritic diseases in traditional Chinese medicine. The phytochemicals and antioxidant capacities in vitro of P. decorate leaves were investigated. Ethanol, petroleum ether, acetidin, n-butyl alcohol and aqueous extracts of Pyrola decorate leaves were prepared by solvent sequential process, and then isolated and purified to obtain phytochemicals. Cell viability was measured by MTT assay. PC12 cells were pretreated for 24 h with different extractions of P. decorate leaves at concentrations of 0.1, 0.5, 1, 5 and 10 mg/mL, then H 2 O 2 of 0.4 mM was added in all samples for an additional 2h. The antioxidant capacities of betulin, ursolic acid and monotropein were determined in PC12 cells against H 2 O 2 induced cytotoxicity in vitro as well. Nine compounds (1-9) were isolated and structurally determined by spectroscopic methods, especially 2D NMR analyses. Ethanol extract treated groups showed inhibitory activity with IC 50 value of 10.83 mg/mL. Betulin, ursolic acid and monotropein were isolated from P. decorate, and demonstrated with IC 50 values of 6.88, 6.15 and 6.13 μg/mL, respectively. In conclusion, Pyrola decorate is a potential antioxidative natural plant and worth testing for further pharmacological investigation in the treatment of oxidative stress related neurological disease.

  11. Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Neary, Michelle C.; Parkin, Gerard

    Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

  12. Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

    DOE PAGES

    Neary, Michelle C.; Parkin, Gerard

    2017-01-19

    Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

  13. Poisoning of Ni-Based anode for proton conducting SOFC by H2S, CO2, and H2O as fuel contaminants

    NASA Astrophysics Data System (ADS)

    Sun, Shichen; Awadallah, Osama; Cheng, Zhe

    2018-02-01

    It is well known that conventional solid oxide fuel cells (SOFCs) based on oxide ion conducting electrolyte (e.g., yttria-stabilized zirconia, YSZ) and nickel (Ni) - ceramic cermet anodes are susceptible to poisoning by trace amount of hydrogen sulfide (H2S) while not significantly impacted by the presence of carbon dioxide (CO2) and moisture (H2O) in the fuel stream unless under extreme operating conditions. In comparison, the impacts of H2S, CO2, and H2O on proton-conducting SOFCs remain largely unexplored. This study aims at revealing the poisoning behaviors caused by H2S, CO2, and H2O for proton-conducting SOFCs. Anode-supported proton-conducting SOFCs with BaZe0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb) electrolyte and Ni-BZCYYb anode and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode as well as Ni-BZCYYb/BZCYYb/Ni-BZCYYb anode symmetrical cells were subjected to low ppm-level H2S or low percentage-level CO2 or H2O in the hydrogen fuel, and the responses in cell electrochemical behaviors were recorded. The results suggest that, contrary to conventional SOFCs that show sulfur poisoning and CO2 and H2O tolerance, such proton-conducting SOFCs with Ni-BZCYYb cermet anode seem to be poisoned by all three types of "contaminants". Beyond that, the implications of the experimental observations on understanding the fundamental mechanism of anode hydrogen electrochemical oxidation reaction in proton conducting SOFCs are also discussed.

  14. Heterogeneous Ag-TiO2-SiO2 composite materials as novel catalytic systems for selective epoxidation of cyclohexene by H2O2

    PubMed Central

    Wang, Xin; Xue, Jianyue; Wang, Xinyun; Liu, Xiaoheng

    2017-01-01

    TiO2-SiO2 composites were synthesized using cetyl trimethyl ammonium bromide (CTAB) as the structure directing template. Self-assembly hexadecyltrimethyl- ammonium bromide TiO2-SiO2/(CTAB) were soaked into silver nitrate (AgNO3) aqueous solution. The Ag-TiO2-SiO2(Ag-TS) composite were prepared via a precipitation of AgBr in soaking process and its decomposition at calcination stage. Structural characterization of the materials was carried out by various techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption and ultraviolet visible spectroscopy (UV-Vis). Characterization results revealed that Ag particles were incorporated into hierarchical TiO2-SiO2 without significantly affecting the structures of the supports. Further heating-treatment at 723 K was more favorable for enhancing the stability of the Ag-TS composite. The cyclohexene oxide was the major product in the epoxidation using H2O2 as the oxidant over the Ag-TS catalysts. Besides, the optimum catalytic activity and stability of Ag-TS catalysts were obtained under operational conditions of calcined at 723 K for 2 h, reaction time of 120 min, reaction temperature of 353 K, catalyst amount of 80 mg, aqueous H2O2 (30 wt.%) as oxidant and chloroform as solvent. High catalytic activity with conversion rate up to 99.2% of cyclohexene oxide could be obtainable in water-bathing. The catalyst was found to be stable and could be reused three times without significant loss of catalytic activity under the optimized reaction conditions. PMID:28493879

  15. H2O Megamasers toward Radio-bright Seyfert 2 Nuclei

    NASA Astrophysics Data System (ADS)

    Zhang, J. S.; Liu, Z. W.; Henkel, C.; Wang, J. Z.; Coldwell, G. V.

    2017-02-01

    Using the Effelsberg-100 m telescope, we perform a successful pilot survey on H2O maser emission toward a small sample of radio-bright Seyfert 2 galaxies with a redshift larger than 0.04. The targets were selected from a large Seyfert 2 sample derived from the spectroscopic Sloan Digital Sky Survey Data Release 7 (SDSS-DR7). One source, SDSS J102802.9+104630.4 (z ˜ 0.0448), was detected four times during our observations, with a typical maser flux density of ˜30 mJy and a corresponding (very large) luminosity of ˜1135 L ⊙. The successful detection of this radio-bright Seyfert 2 and an additional tentative detection support our previous statistical results that H2O megamasers tend to arise from Seyfert 2 galaxies with large radio luminosity. The finding provides further motivation for an upcoming larger H2O megamaser survey toward Seyfert 2s with particularly radio-bright nuclei with the basic goal to improve our understanding of the nuclear environment of active megamaser host galaxies. Based on observations with the 100 m telescope of the MPIfR (Max-Planck-Institut für Radioastronomie) at Effelsberg.

  16. Image-Based Measurement of H2O2 Reaction-Diffusion in Wounded Zebrafish Larvae.

    PubMed

    Jelcic, Mark; Enyedi, Balázs; Xavier, João B; Niethammer, Philipp

    2017-05-09

    Epithelial injury induces rapid recruitment of antimicrobial leukocytes to the wound site. In zebrafish larvae, activation of the epithelial NADPH oxidase Duox at the wound margin is required early during this response. Before injury, leukocytes are near the vascular region, that is, ∼100-300 μm away from the injury site. How Duox establishes long-range signaling to leukocytes is unclear. We conceived that extracellular hydrogen peroxide (H 2 O 2 ) generated by Duox diffuses through the tissue to directly regulate chemotactic signaling in these cells. But before it can oxidize cellular proteins, H 2 O 2 must get past the antioxidant barriers that protect the cellular proteome. To test whether, or on which length scales this occurs during physiological wound signaling, we developed a computational method based on reaction-diffusion principles that infers H 2 O 2 degradation rates from intravital H 2 O 2 -biosensor imaging data. Our results indicate that at high tissue H 2 O 2 levels the peroxiredoxin-thioredoxin antioxidant chain becomes overwhelmed, and H 2 O 2 degradation stalls or ceases. Although the wound H 2 O 2 gradient reaches deep into the tissue, it likely overcomes antioxidant barriers only within ∼30 μm of the wound margin. Thus, Duox-mediated long-range signaling may require other spatial relay mechanisms besides extracellular H 2 O 2 diffusion. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  17. Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere.

    PubMed

    Webster, Chris R; Mahaffy, Paul R; Flesch, Gregory J; Niles, Paul B; Jones, John H; Leshin, Laurie A; Atreya, Sushil K; Stern, Jennifer C; Christensen, Lance E; Owen, Tobias; Franz, Heather; Pepin, Robert O; Steele, Andrew; Achilles, Cherie; Agard, Christophe; Alves Verdasca, José Alexandre; Anderson, Robert; Anderson, Ryan; Archer, Doug; Armiens-Aparicio, Carlos; Arvidson, Ray; Atlaskin, Evgeny; Aubrey, Andrew; Baker, Burt; Baker, Michael; Balic-Zunic, Tonci; Baratoux, David; Baroukh, Julien; Barraclough, Bruce; Bean, Keri; Beegle, Luther; Behar, Alberto; Bell, James; Bender, Steve; Benna, Mehdi; Bentz, Jennifer; Berger, Gilles; Berger, Jeff; Berman, Daniel; Bish, David; Blake, David F; Blanco Avalos, Juan J; Blaney, Diana; Blank, Jen; Blau, Hannah; Bleacher, Lora; Boehm, Eckart; Botta, Oliver; Böttcher, Stephan; Boucher, Thomas; Bower, Hannah; Boyd, Nick; Boynton, Bill; Breves, Elly; Bridges, John; Bridges, Nathan; Brinckerhoff, William; Brinza, David; Bristow, Thomas; Brunet, Claude; Brunner, Anna; Brunner, Will; Buch, Arnaud; Bullock, Mark; Burmeister, Sönke; Cabane, Michel; Calef, Fred; Cameron, James; Campbell, John; Cantor, Bruce; Caplinger, Michael; Caride Rodríguez, Javier; Carmosino, Marco; Carrasco Blázquez, Isaías; Charpentier, Antoine; Chipera, Steve; Choi, David; Clark, Benton; Clegg, Sam; Cleghorn, Timothy; Cloutis, Ed; Cody, George; Coll, Patrice; Conrad, Pamela; Coscia, David; Cousin, Agnès; Cremers, David; Crisp, Joy; Cros, Alain; Cucinotta, Frank; d'Uston, Claude; Davis, Scott; Day, Mackenzie; de la Torre Juarez, Manuel; DeFlores, Lauren; DeLapp, Dorothea; DeMarines, Julia; DesMarais, David; Dietrich, William; Dingler, Robert; Donny, Christophe; Downs, Bob; Drake, Darrell; Dromart, Gilles; Dupont, Audrey; Duston, Brian; Dworkin, Jason; Dyar, M Darby; Edgar, Lauren; Edgett, Kenneth; Edwards, Christopher; Edwards, Laurence; Ehlmann, Bethany; Ehresmann, Bent; Eigenbrode, Jen; Elliott, Beverley; Elliott, Harvey; Ewing, Ryan; Fabre, Cécile; Fairén, Alberto; Farley, Ken; Farmer, Jack; Fassett, Caleb; Favot, Laurent; Fay, Donald; Fedosov, Fedor; Feldman, Jason; Feldman, Sabrina; Fisk, Marty; Fitzgibbon, Mike; Floyd, Melissa; Flückiger, Lorenzo; Forni, Olivier; Fraeman, Abby; Francis, Raymond; François, Pascaline; Freissinet, Caroline; French, Katherine Louise; Frydenvang, Jens; Gaboriaud, Alain; Gailhanou, Marc; Garvin, James; Gasnault, Olivier; Geffroy, Claude; Gellert, Ralf; Genzer, Maria; Glavin, Daniel; Godber, Austin; Goesmann, Fred; Goetz, Walter; Golovin, Dmitry; Gómez Gómez, Felipe; Gómez-Elvira, Javier; Gondet, Brigitte; Gordon, Suzanne; Gorevan, Stephen; Grant, John; Griffes, Jennifer; Grinspoon, David; Grotzinger, John; Guillemot, Philippe; Guo, Jingnan; Gupta, Sanjeev; Guzewich, Scott; Haberle, Robert; Halleaux, Douglas; Hallet, Bernard; Hamilton, Vicky; Hardgrove, Craig; Harker, David; Harpold, Daniel; Harri, Ari-Matti; Harshman, Karl; Hassler, Donald; Haukka, Harri; Hayes, Alex; Herkenhoff, Ken; Herrera, Paul; Hettrich, Sebastian; Heydari, Ezat; Hipkin, Victoria; Hoehler, Tori; Hollingsworth, Jeff; Hudgins, Judy; Huntress, Wesley; Hurowitz, Joel; Hviid, Stubbe; Iagnemma, Karl; Indyk, Steve; Israël, Guy; Jackson, Ryan; Jacob, Samantha; Jakosky, Bruce; Jensen, Elsa; Jensen, Jaqueline Kløvgaard; Johnson, Jeffrey; Johnson, Micah; Johnstone, Steve; Jones, Andrea; Joseph, Jonathan; Jun, Insoo; Kah, Linda; Kahanpää, Henrik; Kahre, Melinda; Karpushkina, Natalya; Kasprzak, Wayne; Kauhanen, Janne; Keely, Leslie; Kemppinen, Osku; Keymeulen, Didier; Kim, Myung-Hee; Kinch, Kjartan; King, Penny; Kirkland, Laurel; Kocurek, Gary; Koefoed, Asmus; Köhler, Jan; Kortmann, Onno; Kozyrev, Alexander; Krezoski, Jill; Krysak, Daniel; Kuzmin, Ruslan; Lacour, Jean Luc; Lafaille, Vivian; Langevin, Yves; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Lee, Ella Mae; Lee, Qiu-Mei; Lees, David; Lefavor, Matthew; Lemmon, Mark; Lepinette Malvitte, Alain; Léveillé, Richard; Lewin-Carpintier, Éric; Lewis, Kevin; Li, Shuai; Lipkaman, Leslie; Little, Cynthia; Litvak, Maxim; Lorigny, Eric; Lugmair, Guenter; Lundberg, Angela; Lyness, Eric; Madsen, Morten; Maki, Justin; Malakhov, Alexey; Malespin, Charles; Malin, Michael; Mangold, Nicolas; Manhes, Gérard; Manning, Heidi; Marchand, Geneviève; Marín Jiménez, Mercedes; Martín García, César; Martin, Dave; Martin, Mildred; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F Javier; Mauchien, Patrick; Maurice, Sylvestre; McAdam, Amy; McCartney, Elaina; McConnochie, Timothy; McCullough, Emily; McEwan, Ian; McKay, Christopher; McLennan, Scott; McNair, Sean; Melikechi, Noureddine; Meslin, Pierre-Yves; Meyer, Michael; Mezzacappa, Alissa; Miller, Hayden; Miller, Kristen; Milliken, Ralph; Ming, Douglas; Minitti, Michelle; Mischna, Michael; Mitrofanov, Igor; Moersch, Jeff; Mokrousov, Maxim; Molina Jurado, Antonio; Moores, John; Mora-Sotomayor, Luis; Morookian, John Michael; Morris, Richard; Morrison, Shaunna; Mueller-Mellin, Reinhold; Muller, Jan-Peter; Muñoz Caro, Guillermo; Nachon, Marion; Navarro López, Sara; Navarro-González, Rafael; Nealson, Kenneth; Nefian, Ara; Nelson, Tony; Newcombe, Megan; Newman, Claire; Newsom, Horton; Nikiforov, Sergey; Nixon, Brian; Noe Dobrea, Eldar; Nolan, Thomas; Oehler, Dorothy; Ollila, Ann; Olson, Timothy; de Pablo Hernández, Miguel Ángel; Paillet, Alexis; Pallier, Etienne; Palucis, Marisa; Parker, Timothy; Parot, Yann; Patel, Kiran; Paton, Mark; Paulsen, Gale; Pavlov, Alex; Pavri, Betina; Peinado-González, Verónica; Peret, Laurent; Perez, Rene; Perrett, Glynis; Peterson, Joe; Pilorget, Cedric; Pinet, Patrick; Pla-García, Jorge; Plante, Ianik; Poitrasson, Franck; Polkko, Jouni; Popa, Radu; Posiolova, Liliya; Posner, Arik; Pradler, Irina; Prats, Benito; Prokhorov, Vasily; Purdy, Sharon Wilson; Raaen, Eric; Radziemski, Leon; Rafkin, Scot; Ramos, Miguel; Rampe, Elizabeth; Raulin, François; Ravine, Michael; Reitz, Günther; Rennó, Nilton; Rice, Melissa; Richardson, Mark; Robert, François; Robertson, Kevin; Rodriguez Manfredi, José Antonio; Romeral-Planelló, Julio J; Rowland, Scott; Rubin, David; Saccoccio, Muriel; Salamon, Andrew; Sandoval, Jennifer; Sanin, Anton; Sans Fuentes, Sara Alejandra; Saper, Lee; Sarrazin, Philippe; Sautter, Violaine; Savijärvi, Hannu; Schieber, Juergen; Schmidt, Mariek; Schmidt, Walter; Scholes, Daniel; Schoppers, Marcel; Schröder, Susanne; Schwenzer, Susanne; Sebastian Martinez, Eduardo; Sengstacken, Aaron; Shterts, Ruslan; Siebach, Kirsten; Siili, Tero; Simmonds, Jeff; Sirven, Jean-Baptiste; Slavney, Susie; Sletten, Ronald; Smith, Michael; Sobrón Sánchez, Pablo; Spanovich, Nicole; Spray, John; Squyres, Steven; Stack, Katie; Stalport, Fabien; Stein, Thomas; Stewart, Noel; Stipp, Susan Louise Svane; Stoiber, Kevin; Stolper, Ed; Sucharski, Bob; Sullivan, Rob; Summons, Roger; Sumner, Dawn; Sun, Vivian; Supulver, Kimberley; Sutter, Brad; Szopa, Cyril; Tan, Florence; Tate, Christopher; Teinturier, Samuel; ten Kate, Inge; Thomas, Peter; Thompson, Lucy; Tokar, Robert; Toplis, Mike; Torres Redondo, Josefina; Trainer, Melissa; Treiman, Allan; Tretyakov, Vladislav; Urqui-O'Callaghan, Roser; Van Beek, Jason; Van Beek, Tessa; VanBommel, Scott; Vaniman, David; Varenikov, Alexey; Vasavada, Ashwin; Vasconcelos, Paulo; Vicenzi, Edward; Vostrukhin, Andrey; Voytek, Mary; Wadhwa, Meenakshi; Ward, Jennifer; Weigle, Eddie; Wellington, Danika; Westall, Frances; Wiens, Roger Craig; Wilhelm, Mary Beth; Williams, Amy; Williams, Joshua; Williams, Rebecca; Williams, Richard B; Wilson, Mike; Wimmer-Schweingruber, Robert; Wolff, Mike; Wong, Mike; Wray, James; Wu, Megan; Yana, Charles; Yen, Albert; Yingst, Aileen; Zeitlin, Cary; Zimdar, Robert; Zorzano Mier, María-Paz

    2013-07-19

    Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

  18. Possible sources of H2 to H2O enrichment at evaporation of parent chondritic material

    NASA Technical Reports Server (NTRS)

    Makalkin, A. B.; Dorofeyeva, V. A.; Vityazev, A. V.

    1993-01-01

    One of the results obtained from thermodynamic simulation of recondensation of the source chondritic material is that at 1500-1800 K it's possible to form iron-rich olivine by reaction between enstatite, metallic iron and water vapor in the case of (H2O)/(H2) approximately equal to 0.1. This could be reached if the gas depletion in hydrogen is 200-300 times relative to solar abundance. To get this range of depletion one needs some source material more rich in hydrogen than the carbonaceous CI material which is the richest in volatiles among chondrites. In the case of recondensation at impact heating and evaporation of colliding planetesimals composed of CI material, we obtain insufficiently high value of (H2)/(H2O) ratio. In the present paper we consider some possible source materials and physical conditions necessary to reach gas composition with (H2)/(H2O) approximately 10 at high temperature.

  19. The fluxes of H2O2 and O2 can be used to evaluate seed germination and vigor of Caragana korshinskii.

    PubMed

    Li, Jiaguo; Wang, Yu; Pritchard, Hugh W; Wang, Xiaofeng

    2014-06-01

    Seed deterioration is detrimental to plant germplasm conservation, and predicting seed germination and vigor with reliability and sensitivity means is urgently needed for practical problems. We investigated the link between hydrogen peroxide (H2O2) flux, oxygen influx and seed vigor of Caragana korshinskii by the non-invasive micro-test technique (NMT). Some related physiological and biochemical changes in seeds were also determined to further explain the changes in the molecular fluxes. The results showed that there was a good linear relationship between germination and H2O2 flux, and that O2 influx was more suitable for assessing seed vigor. H2O2 flux changed relatively little initially, mainly affected by antioxidants (APX, CAT and GSH) and H2O2 content; afterward, the efflux increased more and more rapidly due to high membrane permeability. With the damage of mitochondrial respiration and membrane integrity, O2 influx was gradually reduced. We propose that monitoring H2O2 and O2 fluxes by NMT may be a reliable and sensitive method to evaluate seed germination and vigor.

  20. Middendorfite, K3Na2Mn5Si12(O,OH)36 · 2H2O, a new mineral species from the Khibiny pluton, Kola Peninsula

    NASA Astrophysics Data System (ADS)

    Pekov, I. V.; Chukanov, N. V.; Dubinchuk, V. T.; Zadov, A. E.

    2007-12-01

    Middendorfite, a new mineral species, has been found in a hydrothermal assemblage in Hilairite hyperperalkaline pegmatite at the Kirovsky Mine, Mount Kukisvumchorr apatite deposit, Khibiny alkaline pluton, Kola Peninsula, Russia. Microcline, sodalite, cancrisilite, aegirine, calcite, natrolite, fluorite, narsarsukite, labuntsovite-Mn, mangan-neptunite, and donnayite are associated minerals. Middendorfite occurs as rhombshaped lamellar and tabular crystals up to 0.1 × 0.2 × 0.4 mm in size, which are combined in worm-and fanlike segregations up to 1 mm in size. The color is dark to bright orange, with a yellowish streak and vitreous luster. The mineral is transparent. The cleavage (001) is perfect, micalike; the fracture is scaly; flakes are flexible but not elastic. The Mohs hardness is 3 to 3.5. Density is 2.60 g/cm3 (meas.) and 2.65 g/cm3 (calc.). Middendorfite is biaxial (-), α = 1.534, β = 1.562, and γ = 1.563; 2 V (meas.) = 10°. The mineral is pleochroic strongly from yellowish to colorless on X through brown on Y and to deep brown on Z. Optical orientation: X = c. The chemical composition (electron microprobe, H2O determined with Penfield method) is as follows (wt %): 4.55 Na2O, 10.16 K2O, 0.11 CaO, 0.18 MgO, 24.88 MnO, 0.68 FeO, 0.15 ZnO, 0.20 Al2O3, 50.87 SiO2, 0.17 TiO2, 0.23 F, 7.73 H2O; -O=F2-0.10, total is 99.81. The empirical formula calculated on the basis of (Si,Al)12(O,OH,F)36 is K3.04(Na2.07Ca0.03)Σ2.10(Mn4.95Fe0.13Mg0.06Ti0.03Zn0.03)Σ5.20(Si11.94Al0.06)Σ12O27.57(OH)8.26F0.17 · 1.92H2O. The simplified formula is K3Na2Mn5Si12(O,OH)36 · 2H2O. Middenforite is monoclinic, space group: P21/ m or P21. The unit cell dimensions are a = 12.55, b = 5.721, c = 26.86 Å; β = 114.04°, V = 1761 Å3, Z = 2. The strongest lines in the X-ray powder pattern [ d, Å, ( I)( hkl)] are: 12.28(100)(002), 4.31(81)(11overline 4 ), 3.555(62)(301, 212), 3.063(52)(008, 31overline 6 ), 2.840(90)(312, 021, 30overline 9 ), 2.634(88)(21overline 9 , 1.0.overline 1 0

  1. Gold nanowire assembling architecture for H2O2 electrochemical sensor.

    PubMed

    Guo, Shaojun; Wen, Dan; Dong, Shaojun; Wang, Erkang

    2009-02-15

    Morphological control of nanomaterials is of great interest due to their size and shape-dependent chemical and physical properties and very important applications in many fields such as biomedicine, sensors, electronics and others. In this paper, we reported a simple strategy for synthesizing gold nanowire assembling architecture at room temperature. It is found that two important factors, the proper volume ratio of ethanol to water and poly(vinyl pyrrolidone) (PVP), will play important roles in synthesizing flower-like short gold nanowire assembling spheres. Furthermore, the obtained flower-like gold assembling spheres with high surface-to-volume ratio have been employed as enhancing materials for electrochemical sensing H(2)O(2). The present electrochemical sensing platform exhibited good electrocatalytic activity towards the reduction of H(2)O(2). The detection limit for H(2)O(2) was found to be 1.2 microM, which was lower than certain enzyme-based biosensors.

  2. Effect of hydrogen peroxide pretreatment on ZnO-based metal–semiconductor–metal ultraviolet photodetectors deposited using plasma-enhanced atomic layer deposition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lin, Yu-Chang; Lee, Hsin-Ying, E-mail: hylee@ee.ncku.edu.tw; Lee, Tsung-Hsin

    2016-01-15

    In this study, zinc oxide (ZnO) films were deposited on sapphire substrates using a plasma-enhanced atomic layer deposition system. Prior to deposition, the substrates were treated with hydrogen peroxide (H{sub 2}O{sub 2}) in order to increase nucleation on the initial sapphire surface and, thus, enhance the quality of deposited ZnO films. Furthermore, x-ray diffraction spectroscopy measurements indicated that the crystallinity of ZnO films was considerably enhanced by H{sub 2}O{sub 2} pretreatment, with the strongest (002) diffraction peak occurring for the film pretreated with H{sub 2}O{sub 2} for 60 min. X-ray photoelectron spectroscopy also was used, and the results indicated that amore » high number of Zn–O bonds was generated in ZnO films pretreated appropriately with H{sub 2}O{sub 2}. The ZnO film deposited on a sapphire substrate with H{sub 2}O{sub 2} pretreatment for 60 min was applied to metal–semiconductor–metal ultraviolet photodetectors (MSM-UPDs) as an active layer. The fabricated ZnO MSM-UPDs showed improvements in dark current and ultraviolet–visible rejection ratios (0.27 μA and 1.06 × 10{sup 3}, respectively) compared to traditional devices.« less

  3. A new approach for bioethanol production from sugarcane bagasse using hydrodynamic cavitation assisted-pretreatment and column reactors.

    PubMed

    Terán Hilares, Ruly; Kamoei, Douglas Viana; Ahmed, Muhammad Ajaz; da Silva, Silvio Silvério; Han, Jong-In; Santos, Júlio César Dos

    2018-05-01

    Hydrodynamic cavitation (HC) was adopted to assist alkaline-hydrogen peroxide pretreatment of sugarcane bagasse (SCB). In the following condition: 0.29 M of NaOH, 0.78% (v/v) of H 2 O 2 , 9.95 min of process time and 3 bar of inlet pressure, 95.4% of digestibility of cellulosic fraction was achieved. To take the best use of the pretreated biomass, the overall process was intensified by way of employing a packed bed flow-through column reactor and thus enabling to handle a high solid loading of 20%, thereby leading to cellulose and hemicellulose conversions to 74.7% and 75%, respectively. In the fermentation step, a bubble column reactor was introduced to maximize ethanol production from the pretreated SCB by Scheffersomyces stipitis NRRL-Y7124, resulting in 31.50 g/L of ethanol, 0.49 g/g of ethanol yield and 0.68 g/L.h of productivity. All this showed that our HC-assisted NaOH-H 2 O 2 pretreatment strategy along with the process intensification approach might offer an option for SCB-based biorefineries. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X=empty, H2O, NH3, H3O+: The importance of O-topology

    NASA Astrophysics Data System (ADS)

    Anick, David J.

    2010-04-01

    For (H2O)20X water clusters consisting of X enclosed by the 512 dodecahedral cage, X=empty, H2O, NH3, and H3O+, databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G∗∗. Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; |M|2, where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus |M| show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X=H3O+, one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H2O)20(NH4+) and (H2O)20(NH4+)(OH-) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H2O)20(NH4+) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low-energy water cluster geometries that may have wide applicability.

  5. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X = empty, H2O, NH3, H3O+: the importance of O-topology.

    PubMed

    Anick, David J

    2010-04-28

    For (H(2)O)(20)X water clusters consisting of X enclosed by the 5(12) dodecahedral cage, X = empty, H(2)O, NH(3), and H(3)O(+), databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G(**). Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; absolute value(M)(2), where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus absolute value(M) show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X = H(3)O(+), one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H(2)O)(20)(NH(4)(+)) and (H(2)O)(20)(NH(4)(+))(OH(-)) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H(2)O)(20)(NH(4)(+)) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low

  6. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells.

    PubMed

    Sim, Junyoung; An, Junyeong; Elbeshbishy, Elsayed; Ryu, Hodon; Lee, Hyung-Sool

    2015-11-01

    Cathode potential and O2 supply methods were investigated to improve H2O2 synthesis in an electrochemical cell, and optimal cathode conditions were applied for microbial electrochemical cells (MECs). Using aqueous O2 for the cathode significantly improved current density, but H2O2 conversion efficiency was negligible at 0.3-12%. Current density decreased for passive O2 diffusion to the cathode, but H2O2 conversion efficiency increased by 65%. An MEC equipped with a gas diffusion cathode was operated with acetate medium and domestic wastewater, which presented relatively high H2O2 conversion efficiency from 36% to 47%, although cathode overpotential was fluctuated. Due to different current densities, the maximum H2O2 production rate was 141 mg H2O2/L-h in the MEC fed with acetate medium, but it became low at 6 mg H2O2/L-h in the MEC fed with the wastewater. Our study clearly indicates that improving anodic current density and mitigating membrane fouling would be key parameters for large-scale H2O2-MECs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Attikaite, Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O, a new mineral species

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Pekov, I. V.; Zadov, A. E.

    2007-12-01

    Attikaite, a new mineral species, has been found together with arsenocrandalite, arsenogoyazite, conichalcite, olivenite, philipsbornite, azurite, malachite, carminite, beudantite, goethite, quartz, and allophane at the Christina Mine No. 132, Kamareza, Lavrion District, Attiki Prefecture (Attika), Greece. The mineral is named after the type locality. It forms spheroidal segregations (up to 0.3 mm in diameter) consisting of thin flexible crystals up to 3 × 20 × 80 μm in size. Its color is light blue to greenish blue, with a pale blue streak. The Mohs’ hardness is 2 to 2.5. The cleavage is eminent mica-like parallel to {001}. The density is 3.2(2) g/cm3 (measured in heavy liquids) and 3.356 g/cm3 (calculated). The wave numbers of the absorption bands in the infrared spectrum of attikaite are (cm-1; sh is shoulder; w is a weak band): 3525 sh, 3425, 3180, 1642, 1120 w, 1070 w, 1035 w, 900 sh, 874, 833, 820, 690 w, 645 w, 600 sh, 555, 486, 458, and 397. Attikaite is optically biaxial, negative, α = 1.642(2), β = γ = 1.644(2) ( X = c) 2 V means = 10(8)°, and 2 V calc = 0°. The new mineral is microscopically colorless and nonpleochroic. The chemical composition (electron microprobe, average over 4 point analyses, wt %) is: 0.17 MgO, 17.48 CaO, 0.12 FeO, 16.28 CuO, 10.61 Al2O3, 0.89 P2O5, 45.45 As2O5, 1.39 SO3, and H2O (by difference) 7.61, where the total is 100.00. The empirical formula calculated on the basis of (O,OH,H2O)22 is: Ca2.94Cu{1.93/2+} Al1.97Mg0.04Fe{0.02/2+} [(As3.74S0.16P0.12)Σ4.02O16.08](OH)3.87 · 2.05H2 O. The simplified formula is Ca3Cu2Al2(AsO4)4(OH)4 · 2H2O. Attikaite is orthorhombic, space group Pban, Pbam or Pba2; the unit-cell dimensions are a = 10.01(1), b = 8.199(5), c = 22.78(1) Å, V = 1870(3) Å3, and Z = 4. In the result of the ignition of attikaite for 30 to 35 min at 128 140°, the H2O bands in the IR spectrum disappear, while the OH-group band is not modified; the weight loss is 4.3%, which approximately corresponds to two H2O

  8. H-TiO2/C/MnO2 nanocomposite materials for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Di, Jing; Fu, Xincui; Zheng, Huajun; Jia, Yi

    2015-06-01

    Functionalized TiO2 nanotube arrays with decoration of MnO2 nanoparticles (denoted as H-TiO2/C/MnO2) have been synthesized in the application of electrochemical capacitors. To improve both areal and gravimetric capacitance, hydrogen treatment and carbon coating process were conducted on TiO2 nanotube arrays. By scanning electron microscopy and X-ray photoelectron spectroscopy, it is confirmed that the nanostructure is formed by the uniform incorporation of MnO2 nanoparticles growing round the surface of the TiO2 nanotube arrays. Impedance analysis proves that the enhanced capacitive is due to the decrease of charge transfer resistance and diffusion resistance. Electrochemical measurements performed on this H-TiO2/C/MnO2 nanocomposite when used as an electrode material for an electrochemical pseudocapacitor presents quasi-rectangular shaped cyclic voltammetry curves up to 100 mV/s, with a large specific capacitance (SC) of 299.8 F g-1 at the current density of 0.5 A g-1 in 1 M Na2SO4 electrolyte. More importantly, the electrode also exhibits long-term cycling stability, only 13 % of SC loss after 2000 continuous charge-discharge cycles. Based on the concept of integrating active materials on highly ordered nanostructure framework, this method can be widely applied to the synthesis of high-performance electrode materials for energy storage.

  9. Infrared spectra and radiation stability of H2O2 ices relevant to Europa.

    PubMed

    Hudson, Reggie L; Moore, Marla H

    2006-06-01

    In this paper we present spectra of H2O2-containing ices in the near- and mid-infrared (IR) regions. Spectral changes on warming are shown, as is a comparison of near-IR bands of H2O and H2O2-containing ices. An estimate of the A-value (absolute intensity) for the largest near- IR feature of H2O2 is given. Radiation-decay half-lives are reported for 19 K and 80 K, and are related to the surface radiation doses on Europa. The radiation data show that H2O2 destruction is slower at 80 K than 19 K, and are consistent with the claim that icy material in the outermost micrometer of Europa's surface has been heavily processed by radiation.

  10. Tinnunculite, C5H4N4O3 · 2H2O: Occurrences on the Kola Peninsula and Redefinition and Validation as a Mineral Species

    NASA Astrophysics Data System (ADS)

    Pekov, I. V.; Chukanov, N. V.; Yapaskurt, V. O.; Belakovskiy, D. I.; Lykova, I. S.; Zubkova, N. V.; Shcherbakova, E. P.; Britvin, S. N.; Chervonnyi, A. D.

    2017-12-01

    Based on a study of samples found in the Khibiny (Mt. Rasvumchorr: the holotype) and Lovozero (Mts Alluaiv and Vavnbed) alkaline complexes on the Kola Peninsula, Russia, tinnunculite was approved by the IMA Commission on New Minerals, Nomenclature, and Classification as a valid mineral species (IMA no. 2015-02la) and, taking into account a revisory examination of the original material from burnt dumps of coal mines in the southern Urals, it was redefined as crystalline uric acid dihydrate (UAD), C5H4N4O3 · 2H2O. Tinnunculite is poultry manure mineralized in biogeochemical systems, which could be defined as "guano microdeposits." The mineral occurs as prismatic or tabular crystals up to 0.01 × 0.1 × 0.2 mm in size and clusters of them, as well as crystalline or microglobular crusts. Tinnunculite is transparent or translucent, colorless, white, yellowish, reddish or pale lilac. Crystals show vitreous luster. The mineral is soft and brittle, with a distinct (010) cleavage. D calc = 1.68 g/cm3 (holotype). Tinnunculite is optically biaxial (-), α = 1.503(3), β = 1.712(3), γ = 1.74(1), 2 V obs = 40(10)°. The IR spectrum is given. The chemical composition of the holotype sample (electron microprobe data, content of H is calculated by UAD stoichiometry) is as follows, wt %: 37.5 O, 28.4 C, 27.0 N, 3.8 Hcalc, total 96.7. The empirical formula calculated on the basis of (C + N+ O) = 14 apfu is: C4.99H8N4.07O4.94. Tinnunculite is monoclinic, space group (by analogy with synthetic UAD) P21/ c. The unit cell parameters of the holotype sample (single crystal XRD data) are a = 7.37(4), b = 6.326(16), c = 17.59(4) Å, β = 90(1)°, V = 820(5) Å3, Z = 4. The strongest reflections in the XRD pattern ( d, Å- I[ hkl]) are 8.82-84[002], 5.97-15[011], 5.63-24[102̅, 102], 4.22-22[112], 3.24-27[114̅,114], 3.18-100[210], 3.12-44[211̅, 211], 2.576-14[024].

  11. Spectroscopic properties of morin in various CH3OH-H2O and CH3CN-H2O mixed solvents.

    PubMed

    Park, Hyoung-Ryun; Im, Seo-Eun; Seo, Jung-Ja; Kim, Bong-Gon; Yoon, Jin Ah; Bark, Ki-Min

    2015-01-01

    The specific fluorescence properties of morin (3,2',4',5,7-pentahydroxyflavone) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. Although the dihedral angle is large in the S0 state, morin has an almost planar molecular structure in the S1 state owing to the very low rotational energy barrier around the interring bond between B and the A, C ring. The excited state intramolecular proton transfer (ESIPT) at the S1 state cannot occur immediately after excitation, S1 → S0 fluorescence can be observed. Two conformers, Morin A and B have been known. At the CH3OH-H2O, Morin B will be the principal species but at the CH3CN-H2O, Morin A is the principal species. At the CH3OH-H2O, owing to the large Franck-Condon (FC) factor for S2 → S1 internal convernal (IC) and flexible molecular structure, only S1 → S0 fluorescence was exhibited. At the CH3CN-H2O, as the FC factor for S2 → S1 IC is small and molecular structure is rigid, S2 → S0 and S1 → S0 dual fluorescence was observed. This abnormal fluorescence property was further supported by the small pK1 value, effective delocalization of the lone pair electrons of C(2')-OH to the A, C ring, and a theoretical calculation. © 2014 The American Society of Photobiology.

  12. Dual-Enzyme Characteristics of Polyvinylpyrrolidone-Capped Iridium Nanoparticles and Their Cellular Protective Effect against H2O2-Induced Oxidative Damage.

    PubMed

    Su, Hua; Liu, Dan-Dan; Zhao, Meng; Hu, Wei-Liang; Xue, Shan-Shan; Cao, Qian; Le, Xue-Yi; Ji, Liang-Nian; Mao, Zong-Wan

    2015-04-22

    Polyvinylpyrrolidone-stabilized iridium nanoparticles (PVP-IrNPs), synthesized by the facile alcoholic reduction method using abundantly available PVP as protecting agents, were first reported as enzyme mimics showing intrinsic catalase- and peroxidase-like activities. The preparation procedure was much easier and more importantly, kinetic studies found that the catalytic activity of PVP-IrNPs was comparable to previously reported platinum nanoparticles. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) characterization indicated that PVP-IrNPs had the average size of approximately 1.5 nm and mainly consisted of Ir(0) chemical state. The mechanism of PVP-IrNPs' dual-enzyme activities was investigated using XPS, Electron spin resonance (ESR) and cytochrome C-based electron transfer methods. The catalase-like activity was related to the formation of oxidized species Ir(0)@IrO2 upon reaction with H2O2. The peroxidase-like activity originated from their ability acting as electron transfer mediators during the catalysis cycle, without the production of hydroxyl radicals. Interestingly, the protective effect of PVP-IrNPs against H2O2-induced cellular oxidative damage was investigated in an A549 lung cancer cell model and PVP-IrNPs displayed excellent biocompatibility and antioxidant activity. Upon pretreatment of cells with PVP-IrNPs, the intracellular reactive oxygen species (ROS) level in response to H2O2 was decreased and the cell viability increased. This work will facilitate studies on the mechanism and biomedical application of nanomaterials-based enzyme mimic.

  13. NO and H2O2 contribute to SO2 toxicity via Ca2+ signaling in Vicia faba guard cells.

    PubMed

    Yi, Min; Bai, Heli; Xue, Meizhao; Yi, Huilan

    2017-04-01

    NO and H 2 O 2 have been implicated as important signals in biotic and abiotic stress responses of plants to the environment. Previously, we have shown that SO 2 exposure increased the levels of NO and H 2 O 2 in plant cells. We hypothesize that, as signaling molecules, NO and H 2 O 2 mediate SO 2 -caused toxicity. In this paper, we show that SO 2 hydrates caused guard cell death in a concentration-dependent manner in the concentration range of 0.25 to 6 mmol L -1 , which was associated with elevation of intracellular NO, H 2 O 2 , and Ca 2+ levels in Vicia faba guard cells. NO donor SNP enhanced SO 2 toxicity, while NO scavenger c-PTIO and NO synthesis inhibitors L-NAME and tungstate significantly prevented SO 2 toxicity. ROS scavenger ascorbic acid (AsA) and catalase (CAT), Ca 2+ chelating agent EGTA, and Ca 2+ channel inhibitor LaCl 3 also markedly blocked SO 2 toxicity. In addition, both c-PTIO and AsA could completely block SO 2 -induced elevation of intracellular Ca 2+ level. Moreover, c-PTIO efficiently blocked SO 2 -induced H 2 O 2 elevation, and AsA significantly blocked SO 2 -induced NO elevation. These results indicate that extra NO and H 2 O 2 are produced and accumulated in SO 2 -treated guard cells, which further activate Ca 2+ signaling to mediate SO 2 toxicity. Our findings suggest that both NO and H 2 O 2 contribute to SO 2 toxicity via Ca 2+ signaling.

  14. Glucose Acutely Reduces Cytosolic and Mitochondrial H2O2 in Rat Pancreatic Beta Cells.

    PubMed

    Deglasse, Jean-Philippe; Roma, Leticia Prates; Pastor-Flores, Daniel; Gilon, Patrick; Dick, Tobias P; Jonas, Jean-Christophe

    2018-06-14

    Whether H 2 O 2 contributes to the glucose-dependent stimulation of insulin secretion (GSIS) by pancreatic β cells is highly controversial. We used two H 2 O 2 -sensitive probes, roGFP2-Orp1 (reduction/oxidation-sensitive enhanced green fluorescent protein fused to oxidant receptor peroxidase 1) and HyPer (hydrogen peroxide sensor) with its pH-control SypHer, to test the acute effects of glucose, monomethyl succinate, leucine with glutamine, and α-ketoisocaproate on β cell cytosolic and mitochondrial H 2 O 2 concentrations. We then tested the effects of low H 2 O 2 and menadione concentrations on insulin secretion. RoGFP2-Orp1 was more sensitive than HyPer to H 2 O 2 (response at 2-5 vs. 10 μM) and less pH-sensitive. Under control conditions, stimulation with glucose reduced mitochondrial roGFP2-Orp1 oxidation without affecting cytosolic roGFP2-Orp1 and HyPer fluorescence ratios, except for the pH-dependent effects on HyPer. However, stimulation with glucose decreased the oxidation of both cytosolic probes by 15 μM exogenous H 2 O 2 . The glucose effects were not affected by overexpression of catalase, mitochondrial catalase, or superoxide dismutase 1 and 2. They followed the increase in NAD(P)H autofluorescence, were maximal at 5 mM glucose in the cytosol and 10 mM glucose in the mitochondria, and were partly mimicked by the other nutrients. Exogenous H 2 O 2 (1-15 μM) did not affect insulin secretion. By contrast, menadione (1-5 μM) did not increase basal insulin secretion but reduced the stimulation of insulin secretion by 20 mM glucose. Subcellular changes in β cell H 2 O 2 levels are better monitored with roGFP2-Orp1 than HyPer/SypHer. Nutrients acutely lower mitochondrial H 2 O 2 levels in β cells and promote degradation of exogenously supplied H 2 O 2 in both cytosolic and mitochondrial compartments. The GSIS occurs independently of a detectable increase in β cell cytosolic or mitochondrial H 2 O 2 levels. Antioxid. Redox Signal. 00

  15. FoxO proteins restrain osteoclastogenesis and bone resorption by attenuating H2O2 accumulation

    PubMed Central

    Bartell, Shoshana M.; Kim, Ha-Neui; Ambrogini, Elena; Han, Li; Iyer, Srividhya; Serra Ucer, S.; Rabinovitch, Peter; Jilka, Robert L.; Weinstein, Robert S.; Zhao, Haibo; O’Brien, Charles A.; Manolagas, Stavros C.; Almeida, Maria

    2014-01-01

    Besides their cell-damaging effects in the setting of oxidative stress, reactive oxygen species (ROS) play an important role in physiological intracellular signalling by triggering proliferation and survival. FoxO transcription factors counteract ROS generation by upregulating antioxidant enzymes. Here we show that intracellular H2O2 accumulation is a critical and purposeful adaptation for the differentiation and survival of osteoclasts, the bone cells responsible for the resorption of mineralized bone matrix. Using mice with conditional loss or gain of FoxO transcription factor function, or mitochondria-targeted catalase in osteoclasts, we demonstrate this is achieved, at least in part, by downregulating the H2O2-inactivating enzyme catalase. Catalase downregulation results from the repression of the transcriptional activity of FoxO1, 3 and 4 by RANKL, the indispensable signal for the generation of osteoclasts, via an Akt-mediated mechanism. Notably, mitochondria-targeted catalase prevented the loss of bone caused by loss of oestrogens, suggesting that decreasing H2O2 production in mitochondria may represent a rational pharmacotherapeutic approach to diseases with increased bone resorption. PMID:24781012

  16. Comparisons of multilayer H2O adsorption onto the (110) surfaces of alpha-TiO2 and SnO2 as calculated with density functional theory.

    PubMed

    Bandura, Andrei V; Kubicki, James D; Sofo, Jorge O

    2008-09-18

    Mono- and bilayer adsorption of H2O molecules on TiO2 and SnO 2 (110) surfaces has been investigated using static planewave density functional theory (PW DFT) simulations. Potential energies and structures were calculated for the associative, mixed, and dissociative adsorption states. The DOS of the bare and hydrated surfaces has been used for the analysis of the difference between the H2O interaction with TiO2 and SnO 2 surfaces. The important role of the bridging oxygen in the H2O dissociation process is discussed. The influence of the second layer of H2O molecules on relaxation of the surface atoms was estimated.

  17. Decreased N2O reduction by low soil pH causes high N2O emissions in a riparian ecosystem.

    PubMed

    Van den Heuvel, R N; Bakker, S E; Jetten, M S M; Hefting, M M

    2011-05-01

    Quantification of harmful nitrous oxide (N(2)O) emissions from soils is essential for mitigation measures. An important N(2)O producing and reducing process in soils is denitrification, which shows deceased rates at low pH. No clear relationship between N(2)O emissions and soil pH has yet been established because also the relative contribution of N(2)O as the denitrification end product decreases with pH. Our aim was to show the net effect of soil pH on N(2)O production and emission. Therefore, experiments were designed to investigate the effects of pH on NO(3)(-) reduction, N(2)O production and reduction and N(2) production in incubations with pH values set between 4 and 7. Furthermore, field measurements of soil pH and N(2)O emissions were carried out. In incubations, NO(3)(-) reduction and N(2) production rates increased with pH and net N(2)O production rate was highest at pH 5. N(2)O reduction to N(2) was halted until NO(3)(-) was depleted at low pH values, resulting in a built up of N(2)O. As a consequence, N(2)O:N(2) production ratio decreased exponentially with pH. N(2)O reduction appeared therefore more important than N(2)O production in explaining net N(2)O production rates. In the field, a negative exponential relationship for soil pH against N(2)O emissions was observed. Soil pH could therefore be used as a predictive tool for average N(2)O emissions in the studied ecosystem. The occurrence of low pH spots may explain N(2)O emission hotspot occurrence. Future studies should focus on the mechanism behind small scale soil pH variability and the effect of manipulating the pH of soils. © 2011 Blackwell Publishing Ltd.

  18. 2-Oxoglutarate dehydrogenase is a more significant source of O2(·-)/H2O2 than pyruvate dehydrogenase in cardiac and liver tissue.

    PubMed

    Mailloux, Ryan J; Gardiner, Danielle; O'Brien, Marisa

    2016-08-01

    Pyruvate dehydrogenase (Pdh) and 2-oxoglutarate dehydrogenase (Ogdh) are vital for Krebs cycle metabolism and sources of reactive oxygen species (ROS). O2(·-)/H2O2 formation by Pdh and Ogdh from porcine heart were compared when operating under forward or reverse electron transfer conditions. Comparisons were also conducted with liver and cardiac mitochondria. During reverse electron transfer (RET) from NADH, purified Ogdh generated ~3-3.5× more O2(·-)/H2O2 in comparison to Pdh when metabolizing 0.5-10µM NADH. Under forward electron transfer (FET) conditions Ogdh generated ~2-4× more O2(·-)/H2O2 than Pdh. In both liver and cardiac mitochondria, Ogdh displayed significantly higher rates of ROS formation when compared to Pdh. Ogdh was also a significant source of ROS in liver mitochondria metabolizing 50µM and 500µM pyruvate or succinate. Finally, we also observed that DTT directly stimulated O2(·-)/H2O2 formation by purified Pdh and Ogdh and in cardiac or liver mitochondria in the absence of substrates and cofactors. Taken together, Ogdh is a more potent source of ROS than Pdh in liver and cardiac tissue. Ogdh is also an important ROS generator regardless of whether pyruvate or succinate serve as the sole source of carbon. Our observations provide insight into the ROS generating capacity of either complex in cardiac and liver tissue. The evidence presented herein also indicates DTT, a reductant that is routinely added to biological samples, should be avoided when assessing mitochondrial O2(·-)/H2O2 production. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Surface properties of SiO2 with and without H2O2 treatment as gate dielectrics for pentacene thin-film transistor applications

    NASA Astrophysics Data System (ADS)

    Hung, Cheng-Chun; Lin, Yow-Jon

    2018-01-01

    The effect of H2O2 treatment on the surface properties of SiO2 is studied. H2O2 treatment leads to the formation of Si(sbnd OH)x at the SiO2 surface that serves to reduce the number of trap states, inducing the shift of the Fermi level toward the conduction band minimum. H2O2 treatment also leads to a noticeable reduction in the value of the SiO2 capacitance per unit area. The effect of SiO2 layers with H2O2 treatment on the behavior of carrier transports for the pentacene/SiO2-based organic thin-film transistor (OTFT) is also studied. Experimental identification confirms that the shift of the threshold voltage towards negative gate-source voltages is due to the reduced number of trap states in SiO2 near the pentacene/SiO2 interface. The existence of a hydrogenated layer between pentacene and SiO2 leads to a change in the pentacene-SiO2 interaction, increasing the value of the carrier mobility.

  20. NADPH Oxidase-Derived H2O2 Contributes to Angiotensin II-Induced Aldosterone Synthesis in Human and Rat Adrenal Cortical Cells

    PubMed Central

    Rajamohan, Senthilkumar B.; Raghuraman, Gayatri; Prabhakar, Nanduri R.

    2012-01-01

    Abstract Background The Renin-Angiotensin-Aldosterone-System plays a pivotal role in hypertension. Angiotensin II (Ang II) is a major regulator of aldosterone synthesis and secretion, and it is known to facilitate reactive oxygen species (ROS) generation in many cell types. Aims: Here, we assessed the role of ROS signaling in Ang II-induced aldosterone synthesis by focusing on the regulation of aldosterone synthase (CYP11B2), a cytochrome P450 oxidase that catalyzes the final step in aldosterone biosynthetic pathway. Results: Ang II increased CYP11B2 activity, mRNA and protein with a concomitant elevation of 6-Carboxy- 2′,7′-dichlorodihydrofluorescein diacetate fluorescence, malondialdehyde and protein carbonyl levels (indices of ROS), NADPH oxidase (Nox) activity, and H2O2 levels in human and rat adrenal cortical cells. The expression of nuclear receptor related 1 protein, a transcription factor known to regulate CYP11B2 expression, was also augmented by Ang II. These Ang II-evoked effects were either abolished or attenuated by pretreatment of cells with either Ang II type I receptor (AT1R) antagonist, or antioxidants or Nox inhibitor or siRNA silencing of Nox1, 2 and 4, or inhibitors of phospholipase C and protein kinase C. Exogenous H2O2 mimicked the facilitatory effects of Ang II on CYP11B2 activity, mRNA, and protein expression, and these changes were significantly reduced by PEG-catalase. Innovation: ROS, particularly H2O2, is identified as a key regulator of aldosterone production. Conclusion: Our results suggest that Ang II facilitates CYP11B2 activity and the ensuing aldosterone production via activation of AT1R-Nox-H2O2 signaling pathway. Antioxid. Redox Signal. 17, 445–459. PMID:22214405

  1. Optimization of intermolecular potential parameters for the CO2/H2O mixture.

    PubMed

    Orozco, Gustavo A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2014-10-02

    Monte Carlo simulations in the Gibbs ensemble were used to obtain optimized intermolecular potential parameters to describe the phase behavior of the mixture CO2/H2O, over a range of temperatures and pressures relevant for carbon capture and sequestration processes. Commonly used fixed-point-charge force fields that include Lennard-Jones 12-6 (LJ) or exponential-6 (Exp-6) terms were used to describe CO2 and H2O intermolecular interactions. For force fields based on the LJ functional form, changes of the unlike interactions produced higher variations in the H2O-rich phase than in the CO2-rich phase. A major finding of the present study is that for these potentials, no combination of unlike interaction parameters is able to adequately represent properties of both phases. Changes to the partial charges of H2O were found to produce significant variations in both phases and are able to fit experimental data in both phases, at the cost of inaccuracies for the pure H2O properties. By contrast, for the Exp-6 case, optimization of a single parameter, the oxygen-oxygen unlike-pair interaction, was found sufficient to give accurate predictions of the solubilities in both phases while preserving accuracy in the pure component properties. These models are thus recommended for future molecular simulation studies of CO2/H2O mixtures.

  2. Are H and O Being Lost From the Mars Atmosphere in the H2O Stoichiometric Ratio of 2:1?

    NASA Astrophysics Data System (ADS)

    Jakosky, B. M.; Chaffin, M.; Deighan, J.; Brain, D.; Halekas, J. S.

    2017-12-01

    Loss of gas from the Mars upper atmosphere to space has been a significant process in the evolution of the Mars atmosphere through time. H is derived from photodissociation of H2O, and is lost by Jeans (thermal) escape. O comes from photodissociation of either H2O or CO2, and is lost by non-thermal processes including dissociative recombination, ion pickup, or sputtering by pick-up ions impacting the atmosphere (in order of importance today). McElroy (1972) proposed that H and O are lost in the ratio of 2:1 that comes from photodissociation of H2O; any imbalance would result in build-up of the lesser-escaping atom that increases its loss rate until the rates were in balance. For the Mars year observed by MAVEN, the large seasonal variation in H loss rate makes this hypothesis difficult to evaluate; however, current best estimates of loss rates suggest that they could be in balance, given the observational uncertainties and seasonal variations (both of which are significant). Even if they are in balance over longer timescales, they still might not be during the "MAVEN" year due to: (i) complications resulting from the interplay between multiple loss processes for O beyond only photochemical loss as considered by McElroy, (ii) interannual and longer-term variations in the lower-atmosphere dust and water cycles that can change the escape rate, (iii) the variation in loss rate expected throughout the 11-year solar cycle, (iv) changes in lower-atmosphere forcing due to the changing orbital elements, or (v) loss of C, H, or O to the crust via reaction with surface minerals. The higher (and unequal) loss rates for all species early in history are likely to have kept H and O from being in balance over the 4-billion-year timescale.

  3. Comparative study of diethyl phthalate degradation by UV/H2O2 and UV/TiO2: kinetics, mechanism, and effects of operational parameters.

    PubMed

    Song, Chengjie; Wang, Liping; Ren, Jie; Lv, Bo; Sun, Zhonghao; Yan, Jing; Li, Xinying; Liu, Jingjing

    2016-02-01

    The photodegradation of diethyl phthalate (DEP) by UV/H2O2 and UV/TiO2 is studied. The DEP degradation kinetics and multiple crucial factors effecting the clearance of DEP are investigated, including initial DEP concentration ([DEP]0), initial pH values (pH0), UV light intensity, anions (Cl(-), NO(3-), SO4 (2-), HCO3 (-), and CO3 (2-)), cations (Mg(2+), Ca(2+), Mn(2+), and Fe(3+)), and humic acid (HA). Total organic carbon (TOC) removal is tested by two treatments. And, cytotoxicity evolution of DEP degradation intermediates is detected. The relationship between molar ratio ([H2O2]/[DEP] or [TiO2]/[DEP]) and degradation kinetic constant (K) is also studied. And, the cytotoxicity tests of DEP and its degradation intermediates in UV/H2O2 and UV/TiO2 treatments are researched. The DEP removal efficiency of UV/H2O2 treatment is higher than UV/TiO2 treatment. The DEP degradation fitted a pseudo-first-order kinetic pattern under experimental conditions. The K linearly related with molar ratio in UV/H2O2 treatment while nature exponential relationship is observed in the case of UV/TiO2. However, K fitted corresponding trends better in H2O2 treatment than in TiO2 treatment. The Cl(-) is in favor of the DEP degradation in UV/H2O2 treatment; in contrast, it is disadvantageous to the DEP degradation in UV/TiO2 treatment. Other anions are all disadvantageous to the DEP degradation in two treatments. Fe(3+) promotes the degradation rates significantly. And, all other cations in question inhibit the degradation of DEP. HA hinders DEP degradation in two treatments. The intermediates of DEP degradation in UV/TiO2 treatment are less toxic to biological cell than that in UV/H2O2 treatment.

  4. Simultaneous Online Measurement of H2O and CO2 in the Humid CO2 Adsorption/Desorption Process.

    PubMed

    Yu, Qingni; Ye, Sha; Zhu, Jingke; Lei, Lecheng; Yang, Bin

    2015-01-01

    A dew point meter (DP) and an infrared (IR) CO2 analyzer were assembled in a humid CO2 adsorption/desorption system in series for simultaneous online measurements of H2O and CO2, respectively. The humidifier, by using surface-flushing on a saturated brine solution was self-made for the generation of humid air flow. It was found that by this method it became relatively easy to obtain a low H2O content in air flow and that its fluctuation could be reduced compared to the bubbling method. Water calibration for the DP-IR detector is necessary to be conducted for minimizing the measurement error of H2O. It demonstrated that the relative error (RA) for simultaneous online measurements H2O and CO2 in the desorption process is lower than 0.1%. The high RA in the adsorption of H2O is attributed to H2O adsorption on the transfer pipe and amplification of the measurement error. The high accuracy of simultaneous online measurements of H2O and CO2 is promising for investigating their co-adsorption/desorption behaviors, especially for direct CO2 capture from ambient air.

  5. Short belt-like Ca 2 B 2 O 5 ·H 2 O nanostructures: Hydrothermal formation, FT-IR, thermal decomposition, and optical properties

    NASA Astrophysics Data System (ADS)

    Zhu, Wancheng; Zhang, Xiao; Wang, Xiaoli; Zhang, Heng; Zhang, Qiang; Xiang, Lan

    2011-10-01

    Uniform high crystallinity short belt-like Ca 2B 2OH 2O nanostructures (nanobelts) were facilely synthesized through a room temperature coprecipitation of CaCl 2, H 3BO 3, and NaOH solutions, followed by a mild hydrothermal treatment (180 °C, 12.0 h). By a preferential growth parallel to the (1 0 0) planes, Ca 2B 2OH 2O nanobelts with a length of 1-5 μm, a width of 100-400 nm, and a thickness of 55-90 nm were obtained. The calcination of the nanobelts at 500 °C for 2.0 h led to short Ca 2B 2O 5 nanobelts with well preserved 1D morphology. Calcination at 800 °C led to a mixture of Ca 2B 2O 5 and Ca 3B 2O 6. The products were with belt-like and quasi-polyhedron morphology, while they turned into pore-free micro-rod like and polyhedron morphology when the calcination was taken in the presence of NaCl. NaCl assisted high temperature calcination at 900 °C promoted the formation of Ca 3B 2O 6 in the products. When dispersed in deionized water or absolute ethanol, the Ca 2B 2OH 2O nanobelts and Ca 2B 2O 5 nanobelts showed good transparency from the ultraviolet to the visible region. The as-synthesized Ca 2B 2OH 2O and Ca 2B 2O 5 nanobelts can be employed as novel metal borate nanomaterials for further potential applications in the area of glass fibers, antiwear additive, ceramic coatings, and so on.

  6. H2O2 levels in rainwater collected in south Florida and the Bahama Islands

    NASA Technical Reports Server (NTRS)

    Zika, R.; Saltzman, E.; Chameides, W. L.; Davis, D. D.

    1982-01-01

    Measurements of H2O2 in rainwater collected in Miami, Florida, and the Bahama Islands area indicate the presence of H2O2 concentration levels ranging from 100,000 to 700,000 M. No systematic trends in H2O2 concentration were observed during an individual storm, in marked contrast to the behavior of other anions for example, NO3(-), SO4(-2), and Cl(-). The data suggest that a substantial fraction of the H2O2 found in precipitation is generated by aqueous-phase reactions within the cloudwater rather than via rainout and washout of gaseous H2O2.

  7. Thermal Reactions of H2O2 on Icy Satellites and Small Bodies: Descent with Modification?

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Loeffler, Mark J.

    2012-01-01

    Magnetospheric radiation drives surface and near-surface chemistry on Europa, but below a few meters Europa's chemistry is hidden from direct observation . As an example, surface radiation chemistry converts H2O and SO2 into H2O2 and (SO4)(sup 2-), respectively, and these species will be transported downward for possible thermally-driven reactions. However, while the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, this molecule's thermally-induced solid-phase chemistry has seldom been studied. Here we report new results on thermal reactions in H2O + H2O2 + SO2 ices at 50 - 130 K. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to (SO4)(sup 2-). These results have implications for the survival of H2O2 as it descends, with modification, towards a subsurface ocean on Europa. We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

  8. Helicity in Supercritical O2/H2 and C7H16/N2 Mixing Layers

    NASA Technical Reports Server (NTRS)

    Okongo, Nora; Bellan, Josette

    2004-01-01

    This report describes a study of databases produced by direct numerical simulation of mixing layers developing between opposing flows of two fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence, with emphasis on helicity. The simulations were performed for two different fluid pairs -- O2/H2 and C7H16/N2 -- at similar values of reduced pressure.

  9. Effect of surface pretreatment of TiO2 films on interfacial processes leading to bacterial inactivation in the dark and under light irradiation.

    PubMed

    Rtimi, Sami; Nesic, Jelena; Pulgarin, Cesar; Sanjines, Rosendo; Bensimon, Michael; Kiwi, John

    2015-02-06

    Evidence is presented for radio-frequency plasma pretreatment enhancing the amount and adhesion of TiO2 sputtered on polyester (PES) and on polyethylene (PE) films. Pretreatment is necessary to attain a suitable TiO2 loading leading to an acceptable Escherichia coli reduction kinetics in the dark or under light irradiation for PES-TiO2 and PE-TiO2 samples. The amount of TiO2 on the films was monitored by diffuse reflectance spectroscopy and X-ray fluorescence. X-ray electron spectroscopy shows the lack of accumulation of bacterial residues such as C, N and S during bacterial inactivation since they seem to be rapidly destroyed by TiO2 photocatalysis. Evidence was found for Ti(4+)/Ti(3+) redox catalysis occurring on PES-TiO2 and PE-TiO2 during the bacterial inactivation process. On PE-TiO2 surfaces, Fourier transform infrared spectroscopy (ATR-FTIR) provides evidence for a systematic shift of the na(CH2) stretching vibrations preceding bacterial inactivation within 60 min. The discontinuous IR-peak shifts reflect the increase in the C-H inter-bond distance leading to bond scission. The mechanism leading to E. coli loss of viability on PES-TiO2 was investigated in the dark up to complete bacterial inactivation by monitoring the damage in the bacterial outer cell by transmission electron microscopy. After 30 min, the critical step during the E. coli inactivation commences for dark disinfection on 0.1-5% wt PES-TiO2 samples. The interactions between the TiO2 aggregates and the outer lipopolysaccharide cell wall involve electrostatic effects competing with the van der Waals forces.

  10. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

    PubMed Central

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C–O–H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

  11. Effective potentials for H2O-He and H2O-Ar systems. Isotropic induction-dispersion potentials

    NASA Astrophysics Data System (ADS)

    Starikov, Vitali I.; Petrova, Tatiana M.; Solodov, Alexander M.; Solodov, Alexander A.; Deichuli, Vladimir M.

    2017-05-01

    The vibrational and rotational dependence of the effective isotropic interaction potential of H2O-He and H2O-Ar systems, taken in the form of Lennard-Jones 6-12 potential has been analyzed. The analysis is based on the experimental line broadening (γ) and line shift (δ) coefficients obtained for different vibrational bands of H2O molecule perturbed by He and Ar. The first and second derivatives of the function C(1)(q) for the long-range part of the induction-dispersion potential with respect to the dimensionless normal coordinates q were calculated using literature information for the dipole moment and mean polarizability functions μ(q) and α(q), respectively. These derivatives have been used in the calculations of the quantities which determine the vibrational and rotational dependence of the long-range part of the effective isotropic potential. The optimal set of the derivatives for the function C(1)(q) is proposed. The comparison with the experimental data has been performed.

  12. Decoloration Kinetics of Waste Cooking Oil by 60Co γ-ray/H2O2

    NASA Astrophysics Data System (ADS)

    Xiang, Yulin; Xiang, Yuxiu; Wang, Lipeng

    2016-03-01

    In order to decolorize, waste cooking oil, a dark red close to black solution from homes and restaurants, was subjected to 60Co γ-ray/H2O2 treatment. By virtue of UV/Vis spectrophotometric method, the influence of Gamma irradiation to decoloration kinetics and rate constants of the waste cooking oil in the presence of H2O2 was researched. In addition, the influence of different factors such as H2O2 concentration and irradiation dose on the decoloration rate of waste cooking oil was investigated. Results indicated that the decoloration kinetics of waste cooking oil conformed to the first-order reaction. The decoloration rate increased with the increase of irradiation dose and H2O2 concentration. Saponification analysis and sensory evaluation showed that the sample by 60Co γ-ray/H2O2 treatment presented better saponification performance and sensory score. Furthermore, according to cost estimate, the cost of the 60Co γ-ray/H2O2 was lower and more feasible than the H2O2 alone for decoloration of waste cooking oil.

  13. An integrated microbial electrolysis-anaerobic digestion process combined with pretreatment of wastewater solids to improve hydrogen production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Beegle, Jeff R.; Borole, Abhijeet P.

    A combined anaerobic digestion (AD) and microbial electrolysis cell (MEC) system, named here as ADMEC, was investigated in this paper to evaluate the energy recovery from pretreated wastewater solids. Alkaline and thermal hydrolysis pretreatment methods increased the solubility of organic compounds present in the raw solids by 25% and 20%, respectively. The soluble phase from pretreatment was separated and used for microbial electrolysis, whereas the insoluble fraction was fed into semi-continuous digesters. The digester effluent was later utilized as a second MEC substrate. The pretreatment had variable effects on AD and MEC performance. The methane content in AD biogas wasmore » higher in pretreated groups, 78.29 ± 2.89% and 73.2 ± 1.79%, for alkaline and thermal, than the control, 50.26 ± 0.53%, but the overall biogas production rates were lower than the control, 20 and 30 mL CH 4 gCOD -1 d -1 for alkaline and thermal compared to 80 mL CH 4 gCOD -1 d -1. The effluent streams from thermally pretreated digesters were the best substrate for microbial electrolysis, in terms of hydrogen production and efficiency. The MECs produced 1.7 ± 0.2 L-H 2 per L per day, 0.3 ± 0.1 L-H 2 per L per day, and 0.29 ± 0.1 L-H 2 per L per day, for thermal, alkaline, and control reactors. The productivity was lower compared to acetate and propionate controls, which yielded 5.79 ± 0.03 L-H 2 per L per day and 3.49 ± 0.10 L-H 2 per L per day, respectively. The pretreatment solubilized fractions were not ideal substrates for microbial electrolysis. Finally, a chemical oxygen demand (COD) mass balance showed that pretreatment shifts the electron flux away from methane and biomass sinks towards hydrogen production.« less

  14. An integrated microbial electrolysis-anaerobic digestion process combined with pretreatment of wastewater solids to improve hydrogen production

    DOE PAGES

    Beegle, Jeff R.; Borole, Abhijeet P.

    2017-08-17

    A combined anaerobic digestion (AD) and microbial electrolysis cell (MEC) system, named here as ADMEC, was investigated in this paper to evaluate the energy recovery from pretreated wastewater solids. Alkaline and thermal hydrolysis pretreatment methods increased the solubility of organic compounds present in the raw solids by 25% and 20%, respectively. The soluble phase from pretreatment was separated and used for microbial electrolysis, whereas the insoluble fraction was fed into semi-continuous digesters. The digester effluent was later utilized as a second MEC substrate. The pretreatment had variable effects on AD and MEC performance. The methane content in AD biogas wasmore » higher in pretreated groups, 78.29 ± 2.89% and 73.2 ± 1.79%, for alkaline and thermal, than the control, 50.26 ± 0.53%, but the overall biogas production rates were lower than the control, 20 and 30 mL CH 4 gCOD -1 d -1 for alkaline and thermal compared to 80 mL CH 4 gCOD -1 d -1. The effluent streams from thermally pretreated digesters were the best substrate for microbial electrolysis, in terms of hydrogen production and efficiency. The MECs produced 1.7 ± 0.2 L-H 2 per L per day, 0.3 ± 0.1 L-H 2 per L per day, and 0.29 ± 0.1 L-H 2 per L per day, for thermal, alkaline, and control reactors. The productivity was lower compared to acetate and propionate controls, which yielded 5.79 ± 0.03 L-H 2 per L per day and 3.49 ± 0.10 L-H 2 per L per day, respectively. The pretreatment solubilized fractions were not ideal substrates for microbial electrolysis. Finally, a chemical oxygen demand (COD) mass balance showed that pretreatment shifts the electron flux away from methane and biomass sinks towards hydrogen production.« less

  15. Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

    PubMed

    Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

    2015-01-07

    Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

  16. Sensitive and real-time determination of H2O2 release from intact peroxisomes.

    PubMed Central

    Mueller, Sebastian; Weber, Angelika; Fritz, Reiner; Mütze, Sabine; Rost, Daniel; Walczak, Henning; Völkl, Alfred; Stremmel, Wolfgang

    2002-01-01

    Peroxisomes are essential and ubiquitous cell organelles having a key role in mammalian lipid and oxygen metabolism. The presence of flavine oxidases makes them an important intracellular source of H(2)O(2): an obligate product of peroxisomal redox reactions and a key reactive oxygen species. Peroxisomes proliferate in response to external signals triggered by peroxisome-proliferator-activated receptor signalling pathways. Peroxisome-derived oxidative stress as a consequence of this proliferation is increasingly recognized to participate in pathologies ranging from carcinogenesis in rodents to alcoholic and non-alcoholic steatosis hepatitis in humans. To date, no sensitive approach exists to record H(2)O(2) turnover of peroxisomes in real time. Here, we introduce a sensitive chemiluminescence method that allows the monitoring of H(2)O(2) generation and degradation in real time in suspensions of intact peroxisomes. Importantly, removal, as well as release of, H(2)O(2) can be assessed at nanomolar, non-toxic concentrations in the same sample. Owing to the kinetic properties of catalase and oxidases, H(2)O(2) forms fast steady-state concentrations in the presence of various peroxisomal substrates. Substrate screening suggests that urate, glycolate and activated fatty acids are the most important sources for H(2)O(2) in rodents. Kinetic studies imply further that peroxisomes contribute significantly to the beta-oxidation of medium-chain fatty acids, in addition to their essential role in the breakdown of long and very long ones. These observations establish a direct quantitative release of H(2)O(2) from intact peroxisomes. The experimental approach offers new possibilities for functionally studying H(2)O(2) metabolism, substrate transport and turnover in peroxisomes of eukaryotic cells. PMID:11964148

  17. Determination of the ortho to para ratio of H2Cl+ and H2O+ from submillimeter observations.

    PubMed

    Gerin, Maryvonne; de Luca, Massimo; Lis, Dariusz C; Kramer, Carsten; Navarro, Santiago; Neufeld, David; Indriolo, Nick; Godard, Benjamin; Le Petit, Franck; Peng, Ruisheng; Phillips, Thomas G; Roueff, Evelyne

    2013-10-03

    The opening of the submillimeter sky with the Herschel Space Observatory has led to the detection of new interstellar molecular ions, H2O(+), H2Cl(+), and HCl(+), which are important intermediates in the synthesis of water vapor and hydrogen chloride. In this paper, we report new observations of H2O(+) and H2Cl(+) performed with both Herschel and ground-based telescopes, to determine the abundances of their ortho and para forms separately and derive the ortho-to-para ratio. At the achieved signal-to-noise ratio, the observations are consistent with an ortho-to-para ratios of 3 for both H2O(+) and H2Cl(+), in all velocity components detected along the lines-of-sight to the massive star-forming regions W31C and W49N. We discuss the mechanisms that contribute to establishing the observed ortho-to-para ratio and point to the need for a better understanding of chemical reactions, which are important for establishing the H2O(+) and H2Cl(+) ortho-to-para ratios.

  18. Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

    PubMed

    Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

    2014-02-28

    The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

  19. D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

    NASA Astrophysics Data System (ADS)

    Foustoukos, D.; Mysen, B. O.

    2011-12-01

    Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium

  20. [Zn(phen)(O,N,O)(H2O)] and [Zn(phen)(O,N)(H2O)] with O,N,O is 2,6-dipicolinate and N,O is L-threoninate: synthesis, characterization, and biomedical properties.

    PubMed

    Chin, Lee-Fang; Kong, Siew-Ming; Seng, Hoi-Ling; Tiong, Yee-Lian; Neo, Kian-Eang; Maah, Mohd Jamil; Khoo, Alan Soo-Beng; Ahmad, Munirah; Hor, Tzi-Sum Andy; Lee, Hong-Boon; San, Swee-Lan; Chye, Soi-Moi; Ng, Chew-Hee

    2012-10-01

    Two ternary Zn(II) complexes, with 1,10-phenanthroline (phen) as the main ligand and a carboxylate-containing ligand [dipicolinate (dipico) or L-threoninate (L-Thr)] as the subsidiary ligand, were prepared and characterized by elemental analysis, Fourier transform IR, UV, and fluorescence spectroscopy, X-ray diffraction, molar conductivity, and electrospray ionization mass spectrometry. X-ray structure analysis shows that both [Zn(phen)(dipico)(H(2)O)]·H(2)O (1) and [Zn(phen)(L-Thr)(H(2)O)Cl]·2H(2)O (2) have octahedral geometry about the Zn(II) atom. Both complexes can inhibit topoisomerase I, and have better anticancer activity than cisplatin against nasopharyngeal cancer cell lines, HK1 and HONE-1, with concentrations causing 50 % inhibition of cell proliferation (IC(50)) in the low micromolar range. Complex 2 has the highest therapeutic index for HK1. Both Zn(II) complexes can induce cell death by apoptosis. Changing the subsidiary ligand in the Zn(II) complexes affects the UV-fluorescence spectral properties of the coordinated phen ligand, the binding affinity for some DNA sequences, nucleobase sequence-selective binding, the phase at which cell cycle progression was arrested for treated cancer cells, and their therapeutic index.

  1. Single-component and binary CO2 and H2O adsorption of amine-functionalized cellulose.

    PubMed

    Gebald, Christoph; Wurzbacher, Jan A; Borgschulte, Andreas; Zimmermann, Tanja; Steinfeld, Aldo

    2014-02-18

    A fundamental analysis of single-component and binary CO2 and H2O adsorption of amine-functionalized nanofibrillated cellulose is carried out in the temperature range of 283-353 K and at CO2 partial pressures in the range of 0.02-105 kPa, where the ultralow partial pressure range is relevant for the direct capture of CO2 from atmospheric air. Single-component CO2 and H2O adsorption experimental data are fitted to the Toth and Guggenheim-Anderson-de Boer models, respectively. Corresponding heats of adsorption, derived from explicit solutions of the van't Hoff equation, are -50 kJ/mol CO2 and -48.8 kJ/mol H2O. Binary CO2/H2O adsorption measurements for humid air reveal that the presence of H2O at 2.55 kPa enhances CO2 adsorption, while the presence of CO2 at 0.045 kPa does not influence H2O adsorption. The energy demand of the temperature-vacuum-swing adsorption/desorption cycle for delivering pure CO2 from air increases significantly with H2O adsorption and indicates the need to reduce the hygroscopicity of the adsorbent.

  2. Effects of alkaline catalysts on acetone-based organosolv pretreatment of rice straw.

    PubMed

    Raita, Marisa; Denchokepraguy, Naphatsaya; Champreda, Verawat; Laosiripojana, Navadol

    2017-10-01

    Organosolv is an effective pretreatment strategy for increasing digestibility of lignocellulosic materials owing to selectivity of solvents on separating biopolymeric constituents of plant biomass. In the present work, a novel low-temperature alkali-catalyzed organosolv pretreatment of rice straw was studied. The effects of alkaline catalysts (i.e., NaOH, ammonia, and tri-ethylamine) and solvent types (i.e., acetone, ethanol, and water) were carried out. Addition of alkalis led to increasing sugar from enzymatic hydrolysis while acetone was found to be superior to ethanol and water on selectivity towards cellulose preservation. The optimal alkaline-catalyzed pretreatment reaction contained 5% (w/v) NaOH in an aqueous-acetone mixture (1:4) at 80 °C for 5 min. A glucose yield of 913 mg/g of pretreated biomass was achieved, equivalent to a maximal glucose recovery of 93.0% from glucan in the native biomass. Scanning electron microscope revealed efficient removal of non-cellulosic components, resulting in exposed cellulose microfibers with a reduced crystallite size as determined by X-ray diffraction. With potential on obtaining high-quality lignin, the work demonstrated potential of the novel low-temperature alkaline-catalyzed acetone-based organosolv process for pretreatment of lignocellulosic materials in biorefineries.

  3. Polytherm of the CO(NH2)2-KNO3-H2O phase diagram

    NASA Astrophysics Data System (ADS)

    Yulina, I. V.; Trunin, A. S.

    2017-05-01

    The crystallization polytherm of the ternary CO(NH2)2-KNO3-H2O system is plotted for the first time via visual polythermal analysis and calculating ternary eutonics characteristics from data on the boundary elements of two-component systems. The ternary eutonics modeling error does not exceed 3.5%. In addition to the crystallization fields of individual components, the field of the redox reaction that occurs in the system between potassium nitrate and carbamide is shown in the CO(NH2)2-KNO3-H2O diagram by a dashed outline.

  4. Excess sludge reduction using pilot-scale lysis-cryptic growth system integrated ultrasonic/alkaline disintegration and hydrolysis/acidogenesis pretreatment.

    PubMed

    Ma, Huaji; Zhang, Shuting; Lu, Xuebin; Xi, Bo; Guo, Xingli; Wang, Han; Duan, Jingxiao

    2012-07-01

    A pilot-scale lysis-cryptic growth system was built and operated continuously for excess sludge reduction. Combined ultrasonic/alkaline disintegration and hydrolysis/acidogenesis were integrated into its sludge pretreatment system. Continuous operation showed that the observed biomass yield and the sludge reduction efficiency of the lysis-cryptic growth system were 0.27 kg VSS/kg COD consumed and 56.5%, respectively. The water quality of its effluent was satisfactory. The sludge pretreatment system performed well and its TCOD removal efficiency was 7.9% which contributed a sludge reduction efficiency of 2.1%. The SCOD, VFA, TN, NH(4)(+)-N, TP and pH in the supernatant of pretreated sludge were 1790 mg/L, 1530 mg COD/L, 261.1mg/L, 114.0mg/L, 93.1mg/L and 8.69, respectively. The total operation cost of the lysis-cryptic growth system was $ 0.186/m(3) wastewater, which was 11.4% less than that of conventional activated sludge (CAS) system without excess sludge pretreatment. Copyright © 2012 Elsevier Ltd. All rights reserved.

  5. Comparison of genes required for H2O2 resistance in Streptococcus gordonii and Streptococcus sanguinis

    PubMed Central

    Xu, Yifan; Itzek, Andreas

    2014-01-01

    Hydrogen peroxide (H2O2) is produced by several members of the genus Streptococcus mainly through the pyruvate oxidase SpxB under aerobic growth conditions. The acute toxic nature of H2O2 raises the interesting question of how streptococci cope with intrinsically produced H2O2, which subsequently accumulates in the microenvironment and threatens the closely surrounding population. Here, we investigate the H2O2 susceptibility of oral Streptococcus gordonii and Streptococcus sanguinis and elucidate potential mechanisms of how they protect themselves from the deleterious effect of H2O2. Both organisms are considered primary colonizers and occupy the same intraoral niche making them potential targets for H2O2 produced by other species. We demonstrate that S. gordonii produces relatively more H2O2 and has a greater ability for resistance to H2O2 stress. Functional studies show that, unlike in Streptococcus pneumoniae, H2O2 resistance is not dependent on a functional SpxB and confirms the important role of the ferritin-like DNA-binding protein Dps. However, the observed increased H2O2 resistance of S. gordonii over S. sanguinis is likely to be caused by an oxidative stress protection machinery present even under anaerobic conditions, while S. sanguinis requires a longer period of time for adaptation. The ability to produce more H2O2 and be more resistant to H2O2 might aid S. gordonii in the competitive oral biofilm environment, since it is lower in abundance yet manages to survive quite efficiently in the oral biofilm. PMID:25280752

  6. Cyclic AMP and alkaline pH downregulate carbonic anhydrase 2 in mouse fibroblasts.

    PubMed

    Mardones, Pablo; Chang, Jung Chin; Oude Elferink, Ronald P J

    2014-06-01

    The hydration of CO2 catalyzed by the ubiquitous carbonic anhydrase 2 (Ca2) is central for bicarbonate transport, bone metabolism and acid-base homeostasis in metazoans. There is evidence that in some tissues Ca2 expression can be acutely induced by cAMP, whereas in other cell types it is unresponsive to cAMP-mediated transcriptional activation. We isolated fibroblasts from wild type and mice lacking the ubiquitous chloride/bicarbonate exchanger (Ae2a,b(-/-) mice). In these cells the regulation of carbonic anhydrase 2 by cAMP was studied. We show that Ca2 expression is strongly inhibited by chronic incubation with dibutyryl-cAMP, forskolin or alkaline pH in cultured mouse fibroblasts. Furthermore, fibroblasts obtained from anion exchanger 2 deficient (Ae2a,b(-/-)) mice, which display intracellular alkalosis and increased cAMP production, express less than 10% of control Ca2 mRNA and protein. Surprisingly, inhibition of the bicarbonate-sensitive soluble adenylyl cyclase (sAC) was found to reduce CA2 expression instead of increasing it. CA2 expression is strongly regulated by intracellular pH and by cAMP, suggesting a role for soluble adenylyl cyclase. Regulation occurs in opposite directions which may be explained by an incoherent feedforward loop consisting of activation by pCREB and repression by ICER. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Dynamics, magnetic properties, and electron binding energies of H2O2 in water.

    PubMed

    C Cabral, Benedito J

    2017-06-21

    Results for the magnetic properties and electron binding energies of H 2 O 2 in liquid water are presented. The adopted methodology relies on the combination of Born-Oppenheimer molecular dynamics and electronic structure calculations. The Keal-Tozer functional was applied for predicting magnetic shieldings and H 2 O 2 intramolecular spin-spin coupling constants. Electron binding energies were calculated with electron propagator theory. In water, H 2 O 2 is a better proton donor than proton acceptor, and the present results indicate that this feature is important for understanding magnetic properties in solution. In comparison with the gas-phase, H 2 O 2 atoms are deshielded in water. For oxygen atoms, the deshielding is mainly determined by structural/conformational changes. Hydrogen-bond interactions explain the deshielding of protons in water. The predicted chemical shift for the H 2 O 2 protons in water (δ∼11.8 ppm) is in good agreement with experimental information (δ=11.2 ppm). The two lowest electron binding energies of H 2 O 2 in water (10.7±0.5 and 11.2±0.5 eV) are in reasonable agreement with experiment. In keeping with data from photoelectron spectroscopy, an ∼1.6 eV red-shift of the two first ionisation energies relative to the gas-phase is observed in water. The strong dependence of magnetic properties on changes of the electronic density in the nuclei environment is illustrated by a correlation between the σ( 17 O) magnetic shielding constant and the energy gap between the [2a] lowest valence and [1a] core orbitals of H 2 O 2 .

  8. Comparison of O2 and H2O as oxygen source for homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Konishi, Keita; Goto, Ken; Togashi, Rie; Murakami, Hisashi; Higashiwaki, Masataka; Kuramata, Akito; Yamakoshi, Shigenobu; Monemar, Bo; Kumagai, Yoshinao

    2018-06-01

    Homoepitaxial growth of β-Ga2O3 layers by halide vapor phase epitaxy (HVPE) using O2 or H2O as an oxygen source was investigated by thermodynamic analysis, and compared with measured properties after growth. The thermodynamic analysis revealed that Ga2O3 growth is expected even at 1000 °C using both oxygen sources due to positive driving forces for Ga2O3 deposition. The experimental results for homoepitaxial growth on (0 0 1) β-Ga2O3 substrates showed that the surfaces of the layers grown with H2O were smoother than those grown with O2, although the growth rate with H2O was approximately half that with O2. However, in the homoepitaxial layer grown using H2O, incorporation of Si impurities with a concentration almost equal to the effective donor concentration (2 × 1016 cm-3) was confirmed, which was caused by decomposition of the quartz glass reactor due to the presence of hydrogen in the system.

  9. Alkali-based pretreatments distinctively extract lignin and pectin for enhancing biomass saccharification by altering cellulose features in sugar-rich Jerusalem artichoke stem.

    PubMed

    Li, Meng; Wang, Jun; Yang, Yuezhou; Xie, Guanghui

    2016-05-01

    Jerusalem artichoke (JA) has been known as a potential nonfood feedstock for biofuels. Based on systems analysis of total 59 accessions, both soluble sugar and ash could positively affect biomass digestibility after dilute sodium hydroxide pretreatment (A). In this study, one representative accession (HEN-3) was used to illustrate its enzymatic digestibility with pretreatments of ultrasonic-assisted dilute sodium hydroxide (B), alkaline peroxide (C), and ultrasonic-assisted alkaline peroxide (D). Pretreatment D exhibited the highest hexose release rate (79.4%) and total sugar yield (10.4 g/L), which were 2.4 and 2.6 times higher, respectively, than those of the control. The analysis of cellulose crystalline index (CrI), cellulose degree of polymerization (DP), thermal behavior and SEM suggested that alkali-based pretreatments could distinctively extract lignin and pectin polymers, leading to significant alterations of cellulose CrI and DP for high biomass saccharification. Additionally, hydrogen peroxide (H2O2) could significant reduce the generation of fermentation inhibitors during alkali-based pretreatments. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Ordered bimetallic ferromagnets of chromium(III): [Cr(NH 3) 6][Cr(CN) 6], [Cr(H 2O)(NH 3) 5][Cr(CN) 6], and trans-[Cr(en) 2(H 2O) 2]trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O

    NASA Astrophysics Data System (ADS)

    Burriel, Ramón; Casabó, Jaime; Pons, Josefina; Carnegie, David W.; Carlin, Richard L.

    1985-07-01

    The magnetic bahavior of the isomorphous compounds [Cr(NH 3) 6][Cr(CN) 6] and [Cr(H 2O)(NH 3) 5][Cr(CN) 6] has been studied by means of zero-field susceptibility measurements. The materials order ferromagnetically at 0.60 and 0.38K, respectively. The compounds behave as examples of the ferromagnetic ( S=3/2) Heisenberg body-center-cubic lattice. The susceptibilities have been analyzed and compared to the Padé approximants of the high-temperature series expansion for this model, a remarkably good fit being obtained with exchange constants 0.042 and 0.022 K, respectively. Another bimetallic substance, trans-[Cr(en) 2(H 2O) 2] trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O, with a dominant Heisenberg ferromagnetic interaction J/ kB=0.122 K in one dimension, orders antiferromagnetically at 0.14 K due to a weaker interchain interaction with exchange constant z‧ J‧/ kB=-0.019 K. The three sets of measurements have been carried out on powdered samples for which demagnetization effects are important. The exchange interactions are remarkably weak for such concentrated magnetic materials, yet they are stronger than those found in a number of other such Cr/Cr compounds.

  11. 2,4-Dinitrophenylhydrazine, redetermined at 120 K: a three-dimensional framework built from N-H...O, N-H...(O)2, N-H...pi(arene) and C-H...O hydrogen bonds.

    PubMed

    Wardell, James L; Low, John N; Glidewell, Christopher

    2006-06-01

    In the title compound, C6H6N4O4, the bond distances indicate significant bond fixation, consistent with charge-separated polar forms. The molecules are almost planar and there is an intramolecular N-H...O hydrogen bond. The molecules are linked into a complex three-dimensional framework structure by a combination of N-H...O, N-H...(O)2, N-H...pi(arene) and C-H...O hydrogen bonds.

  12. New Insight into SO2 Poisoning and Regeneration of CeO2-WO3/TiO2 and V2O5-WO3/TiO2 Catalysts for Low-Temperature NH3-SCR.

    PubMed

    Xu, Liwen; Wang, Chizhong; Chang, Huazhen; Wu, Qingru; Zhang, Tao; Li, Junhua

    2018-06-19

    In this study, the poisoning effects of SO 2 on the V 2 O 5 -WO 3 /TiO 2 (1%VWTi) and CeO 2 -WO 3 /TiO 2 (5%CeWTi) selective catalytic reduction (SCR) catalysts were investigated in the presence of steam, and also the regeneration of deactivated catalysts was studied. After pretreating the catalysts in a flow of NH 3 + SO 2 + H 2 O + O 2 at 200 °C for 24 h, it was observed that the low-temperature SCR (LT-SCR) activity decreased significantly over the 1%VWTi and 5%CeWTi catalysts. For 1%VWTi, NH 4 HSO 4 (ABS) was the main product detected after the poisoning process. Both of NH 4 HSO 4 and cerium sulfate species were formed on the poisoned 5%CeWTi catalyst, indicating that SO 2 reacted with Ce 3+ /Ce 4+ , even in the presence of high concentration of NH 3 . The decrease of BET specific surface area, NO x adsorption capacity, the ratio of chemisorbed oxygen, and reducibility were responsible for the irreversible deactivation of the poisoned 5%CeWTi catalyst. Meanwhile, the LT-SCR activity could be recovered over the poisoned 1%VWTi after regeneration at 400 °C, but not for the 5%CeWTi catalyst. For industrial application, it is suggested that the regeneration process can be utilized for 1%VWTi catalysts after a period of time after NH 4 HSO 4 accumulated on the catalysts.

  13. Infrared Spectroscopy of the H2/HD/D2-O2 Van Der Waals Complexes

    NASA Astrophysics Data System (ADS)

    Raston, Paul; Bunn, Hayley

    2016-06-01

    Hydrogen is the most abundant element in the universe and oxygen is the third, so understanding the interaction between the two in their different forms is important to understanding astrochemical processes. The interaction between H2 and O2 has been explored in low energy scattering experiments and by far infrared synchrotron spectroscopy of the van der Waals complex. The far infrared spectra suggest a parallel stacked average structure with seven bound rotationally excited states. Here, we present the far infrared spectrum of HD/D2-O2 and the mid infrared spectrum of H2-O2 at 80 K, recorded at the infrared beamline facility of the Australian Synchrotron. We observed 'sharp' peaks in the mid infrared region, corresponding to the end over end rotation of H2-O2, that are comparatively noisier than analogous peaks in the far infrared where the synchrotron light is brightest. The larger reduced mass of HD and D2 compared to H2 is expected to result in more rotational bound states and narrower bands. The latest results in our ongoing efforts to explore this system will be presented. Y. Kalugina, et al., Phys. Chem. Chem. Phys. 14, 16458 (2012) S. Chefdeville et al. Science 341, 1094 (2013) H. Bunn et al. ApJ 799, 65 (2015)

  14. Antiapoptotic effects of anthocyanin from the seed coat of black soybean against oxidative damage of human lens epithelial cell induced by H2O2.

    PubMed

    Mok, Jee Won; Chang, Dong-Jin; Joo, Choun-Ki

    2014-11-01

    To describe the protective effect of anthocyanin from black soybean in human lens epithelial cell line (HLE-B3) under H2O2-induced oxidative stress. Cytotoxicity of anthocyanin and H2O2 were determined by Cell Counting Kit-8 test. Viability of HLE-B3 cells under various H2O2 concentration (0, 50 and 100 μM) with or without pretreatment of anthocyanin (0, 50, 100 and 200 μg/ml) was measured. After quantifying the percentage of the apoptosis by Annexin V assay and APO-BrdU TUNEL assay, we conducted western blot and immunostaining of apoptosis-related molecules; Bcl2, BAD, BAX, p53 and caspase-3. To confirm the effect of anthocyanin on an ex vivo model, its effect on cultures of the lenses of porcine were examined. Anthocyanin reduced cell death of HLE-B3 under H2O2-induced oxidative stress in a dose-dependent manner. In Annexin V analysis, anthocyanin protected HLE-B3 cells from apoptosis. H2O2 increased the expression of BAX, BAD, p53 and caspase-3 in a time-dependent manner, those of which anthocyanin significantly decreased. On the other hand, Bcl2 was increased from anthocyanin-treated lens cells. And in anthocyanin-treated lens organ culture, transparency was maintained. This study showed that anthocyanin protects HLE-B3 cells under oxidative stress from apoptosis, and the mechanism of the effect is related to the intrinsic pathway of apoptosis. Anthocyanin has a potential in prevention of cataract.

  15. Study on tribological and electrochemistry properties of metal materials in H2O2 solutions

    NASA Astrophysics Data System (ADS)

    Yuan, Chengqing; Yu, Li; Li, Jian; Yan, Xinping

    2012-03-01

    Hydrogen peroxide (H2O2) is a kind of ideal green propellant. It is crucial to study the wear behavior and failure modes of the metal materials under the strong oxidizing environment of H2O2. This study aims to investigate the wear of rubbing pairs of 2Cr13 stainless steel against 1045 metal in H2O2 solutions, which has a great effect on wear, the decomposition and damage mechanism of materials. The comparison analysis of the friction coefficients, wear mass loss, worn surface topographies and current densities was conducted under different concentrations of H2O2 solutions. There were significant differences in the tribological and electrochemistry properties of the rubbing pairs in different H2O2 solutions.

  16. Ordering of calcium and vacancies in calcium catapleiite CaZr[Si{sub 3}O{sub 9}] • 2H{sub 2}O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aksenov, S. M., E-mail: aks.crys@gmail.com; Portnov, A. M.; Chukanov, N. V.

    A sample of holotypic calcium catapleiite from the Burpala alkaline massif (Northern Baikal, Russia) is studied by single crystal X-ray analysis at 120 K and IR spectroscopy. The empirical formula of calcium catapleiite is Ca{sub 0.97}Na{sub 0.02}Zr{sub 1.01}Si{sub 3}O{sub 9} • 2H{sub 2}O (Z = 4). The X-ray diffraction study confirms the orthorhombic unit cell with the following parameters: a = 7.406(1), b = 12.687(1), and c = 10.112(1) Å; V = 950.1(2) Å{sup 3}; space group Pbnn. The crystal structure is refined in the anisotropic approximation of atomic displacement parameters using 1177 reflections with I > 2σ(I) to themore » final R = 2.91%. The structure of calcium catapleiite under study is based on the microporous heteropolyhedral framework formed by ZrO{sub 6} octahedra and threemembered silicon–oxygen rings [Si{sub 3}O{sub 9}]. It is on the whole analogous to the structures of the samples studied earlier, but differs from them by a high degree of ordering of calcium and vacancies at extraframework positions. The distribution of calcium over Ca1 and Ca2 positions in the calcium catapleiite structure leads to the formation of zigzag chains of the …Ca1–Zr–Ca1–Zr… and …Ca2–h–Ca2–□… types. Low occupancy of the Ca2 position and its alternation with the vacancy are prerequisites for potential Ca{sup 2+} cationic conduction.« less

  17. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    NASA Astrophysics Data System (ADS)

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-03-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

  18. Influence of γ-radiation on the reactivity of montmorillonite towards H 2O 2

    NASA Astrophysics Data System (ADS)

    Holmboe, Michael; Jonsson, Mats; Wold, Susanna

    2012-02-01

    Compacted and water saturated bentonite will be used as an engineered barrier in deep geological repositories for radioactive waste in many countries. Due to the high dose rate of ionizing radiation outside the canisters holding the nuclear waste, radiolysis of the interlayer and pore water in the compacted bentonite is unavoidable. Upon reaction with the oxidizing and reducing species formed by water radiolysis (OH •, e -(aq), H •, H 2O 2, H 2, HO 2•, H 3O +), the overall redox properties in the bentonite barrier may change. In this study the influence of γ-radiation on the structural Fe(II)/Fe Tot ratio in montmorillonite and its reactivity towards hydrogen peroxide (H 2O 2) was investigated in parallel experiments. The results show that under anoxic conditions the structural Fe(II)/Fe Tot ratio of dispersed Montmorillonite increased from ≤3 to 25-30% after γ-doses comparable to repository conditions. Furthermore, a strong correlation between the structural Fe(II)/Fe Tot ratio and the H 2O 2 decomposition rate in montmorillonite dispersions was found. This correlation was further verified in experiments with consecutive H 2O 2 additions, since the structural Fe(II)/Fe Tot ratio was seen to decrease concordantly. This work shows that the structural iron in montmorillonite could be a sink for one of the major oxidants formed upon water radiolysis in the bentonite barrier, H 2O 2.

  19. Symmetry and topology code of the cluster self-assembly of framework MT structures of alumophosphates AlPO4(H2O)2 (metavariscite and variscite) and Al2(PO4)2(H2O)3 (APC)

    NASA Astrophysics Data System (ADS)

    Ilyushin, G. D.; Blatov, V. A.

    2017-03-01

    The supramolecular chemistry of alumophosphates, which form framework 3D MT structures from polyhedral AlO4(H2O)2 clusters with octahedral O coordination (of M polyhedra) and PO4 and AlO4 with tetrahedral O coordination (of T polyhedra), is considered. A combinatorial-topological modeling of the formation of possible types of linear (six types) and ring (two types) tetrapolyhedral cluster precursors M2T2 from MT monomers is carried out. Different versions of chain formation from linked (MT)2 rings (six types) are considered. The model, which has a universal character, has been used to simulate the cluster selfassembly of the crystal structure of AlPO4(H2O)2 minerals (metavariscite, m-VAR, and variscite, VAR) and zeolite [Al2(PO4)2(H2O)2] · H2O (APC). A tetrapolyhedral linear precursor is established for m-VAR and a ring precursor (MT)2 is established for VAR and APC. The symmetry and topology code of the processes of crystal structure self-assembly from cluster precursors is completely reconstructed. The functional role of the O-H···O hydrogen bonds is considered for the first time. The cluster self-assembly model explains the specific features of the morphogenesis of single crystals: m-VAR prisms, flattened VAR octahedra, and needleshaped APC square-base prisms.

  20. Descent without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds.

    PubMed

    Loeffler, Mark J; Hudson, Reggie L

    2015-06-01

    The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NH4+ and SO2 making SO(4)2- by H+ and e- transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.