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Sample records for 3-5 compound oxides

  1. Thermal oxidation of 3-5 compound semiconductors

    NASA Astrophysics Data System (ADS)

    Monteironeto, Othon Derego

    1988-11-01

    Thermal oxidation of 3-5 compound semiconductors has been studied in the temperature range of 300 to 600 C. Two members of this class of materials, namely InP and GaAs, were the object of the experimental work carried out here. The main analytical tools used were transmission electron microscopy (TEM) and secondary ion mass spectroscopy (SIMS). TEM was employed to access microstructural changes and SIMS to access the composition redistribution that takes place as a consequence of the oxidation reaction. Below 400 C oxidation of both materials led to the formation of amorphous scales, which consisted of a mixture of gallium and arsenic oxides in the case of GaAs, and indium phosphate and oxide in the case of InP. The oxidation kinetics of InP was found to be slower than that of GaAs. In the high temperature regime, i.e., above 400 C, the oxidation of both materials resulted in crystalline products. Precipitation of the group 5 element at the scale/semiconductor interface took place during oxidation. At the GaAs/Ga2O3interface, As precipitates were formed with a truncated square pyramid shape bound by (111) sub GaAs planes. The precipitates found at the InPO4/InP interface were either a phosphorus rich phase or red phosphorus. Strong vaporization under the electron beam prohibited a more accurate determination. The morphology of those precipitates were very similar to the As ones in GaAs.

  2. Growth mechanism and properties of the thermal and anodic oxides of the 3-5 compound semiconductors

    NASA Astrophysics Data System (ADS)

    Wilmsen, C. W.

    1985-03-01

    The mechanisms of oxide growth on InP, GaP, GaAs, and InGaAs were investigated and their electrical properties measured. Islands were observed as the initial stage of anodization of InP and GaAs, but the details of the growth on the two materials are different. The thermal oxides of InP and GaP also differ in composition and surface topography. InP forms bubbles and GaP has pits under the oxide. Traps at the deposited insulator/InP interface were also investigated.

  3. Free surface properties of 3-5 compound semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Kahn, A.

    1980-06-01

    Studies of free compound semiconductor surfaces as well as gas-solid and metal-solid interaction are summarized. An experimental and theoretical analysis of the GaAs(110) surface reconstruction was conducted and applied to three additional compounds: InSb, InP and ZnTe. Attempts were made to relate the type and the magnitude of the surface reconstruction of these materials to the covalent-ionic character of the bonding. Knowledge of the atomic reconstructions of these surfaces was used to investigate the reactivity of semiconductor surfaces (GaAs(110)) with gas (oxygen) and metal (aluminum) atoms. These multicomponent systems are at the center of the author's essays to understand the chemistry of these surfaces and its relationship with their atomic reconstruction. Using Low Energy Electron Diffraction (LEED) as the principal tool to investigation, structural information has been obtained which correlates chemical and electronic information obtained by other surface analysis techniques.

  4. Rat liver microsomal cytochrome P450-dependent oxidation of 3,5-disubstituted analogues of paracetamol.

    PubMed

    Bessems, J G; Te Koppele, J M; Van Dijk, P A; Van Stee, L L; Commandeur, J N; Vermeulen, N P

    1996-06-01

    1. The cytochrome P450-dependent binding of paracetamol and a series of 3,5-disubstituted paracetamol analogues (R = -F, -Cl, -Br, -I, -CH3, -C2H5, -iC3H7) have been determined with beta-naphthoflavone (beta NF)-induced rat liver microsomes and produced reverse type I spectral changes. Ks,app varied from 0.14 mM for 3,5-diiC3H7-paracetamol to 2.8 mM for paracetamol. 2. All seven analogues underwent rat liver microsomal cytochrome P450-dependent oxidation, as reflected by the formation of GSSG in the presence of GSH. The GSSG-formation was increased in all cases upon pretreatment of rats by beta-naphthoflavone (beta NF) and was generally decreased upon pretreatment by phenobarbital (PB). 3. Rat liver microsomal cytochrome P450 as well as horseradish peroxidase catalysed the formation of 3,5-disubstituted NAPQI analogues from the corresponding parent compounds, as identified by UV-spectrophotometry of the NAPQI analogues and by GC/MS detection of the following GSH-conjugates: 2-glutathione-S-yl-3,5-dimethyl-1,4-dihydroxybenzene, 2-glutathione-S-yl-3,5-dichloro-paracetamol, and 2-glutathione-S-yl-3,5-dibromo-paracetamol. 4. In liver microsomal (beta NF-induced) incubations, apparent K(m) values, as determined for the cytochrome P450 catalysis-dependent oxidation of GSH, for seven 3,5-disubstituted paracetamol analogues (R = -F, -Cl, -Br, -I, -CH3, -C2H5, iC3H7) varied from 0.07 to 0.64 mM. Paracetamol exhibited an apparent K(m) of 0.73 mM. Apparent Vmax values for the cytochrome P450 catalysis dependent oxidation of GSH varied from 0.66 nmol min-1 mg-1 protein for paracetamol to 3.0 nmol min-1 mg-1 protein for 3,5-dimethyl-paracetamol. PMID:8810035

  5. Persulfate Oxidation of Gasoline Compounds

    NASA Astrophysics Data System (ADS)

    Sra, K.; Thomson, N.; Barker, J.

    2009-05-01

    %). The decrease in concentration of all the compounds was higher for a molar ratio of 1.0 (<27%) as compared with a molar ratio of 0.1 (<11%). The activation by ferrous concentration resulted in higher oxidation of compounds (except naphthalene) as compared with unactivated or peroxide activated persulfate. 1,3,5-TMB was completed oxidized after 4 days using higher chelated ferrous concentration and after 12 days using lower chelated ferrous concentration for persulfate activation. In general, increase in chelated ferrous concentration resulted in higher oxidation of the gasoline compounds. While oxidation of F1 fraction was similar for two ferrous activation conditions, the oxidation of F2 fraction was lower when ferrous activation at 600 mg/L was employed. Use of persulfate at high dosages by itself or in combination with higher doses of chelated ferrous or optimum doses of peroxide as an activator seems to be a viable option for remediation of gasoline compounds examined in this study. Persulfate appears to be particularly effective in the oxidation of BTEX compounds, but may require ferrous activation for a complete oxidation of TMBs and peroxide activation for oxidation of naphthalene.

  6. Microbially Mediated Biodegradation of Hexahydro-1,3,5-Trinitro-1,3,5- Triazine by Extracellular Electron Shuttling Compounds

    PubMed Central

    Kwon, Man Jae; Finneran, Kevin T.

    2006-01-01

    The potential for humic substances to stimulate the reduction of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) was investigated. This study describes a novel approach for the remediation of RDX-contaminated environments using microbially mediated electron shuttling. Incubations without cells demonstrated that reduced AQDS transfers electrons directly to RDX, which was reduced without significant accumulation of the nitroso intermediates. Three times as much reduced AQDS (molar basis) was needed to completely reduce RDX. The rate and extent of RDX reduction differed greatly among electron shuttle/acceptor amendments for resting cell suspensions of Geobacter metallireducens and G. sulfurreducens with acetate as the sole electron donor. AQDS and purified humic substances stimulated the fastest rate of RDX reduction. The nitroso metabolites did not significantly accumulate in the presence of AQDS or humic substances. RDX reduction in the presence of poorly crystalline Fe(III) was relatively slow and metabolites transiently accumulated. However, adding humic substances or AQDS to Fe(III)-containing incubations increased the reduction rates. Cells of G. metallireducens alone reduced RDX; however, the rate of RDX reduction was slow relative to AQDS-amended incubations. These data suggest that extracellular electron shuttle-mediated RDX transformation is not organism specific but rather is catalyzed by multiple Fe(III)- and humic-reducing species. Electron shuttle-mediated RDX reduction may eventually become a rapid and effective cleanup strategy in both Fe(III)-rich and Fe(III)-poor environments. PMID:16957213

  7. Down-Regulation of Porcine Heart Diaphorase Reactivity by Trimanganese Hexakis(3,5-Diisopropylsalicylate), Mn(3)(3,5-DIPS)6, and Down-Regulation of Nitric Oxide Synthase Reactivity by Mn(3)(3,5-DIPS)(6) and Cu(II)(2)(3,5-DIPS)(4).

    PubMed

    Booth, B L; Pitters, E; Mayer, B; Sorenson, J R

    1999-01-01

    Purposes of this work were to examine the plausible down-regulation of porcine heart diaphorase (PHD) enzyme reactivity and nitric oxide synthase (NOS) enzyme reactivity by trimanganese hexakis(3,5-diisopropylsalicylate), [Mn(3)(3,5-DIPS)(6)] as well as dicopper tetrakis(3,5- diisopropylsalicylate, [Cu(II)(2)(3,5-DIPS)(4)] as a mechanistic accounting for their pharmacological activities.Porcine heart disease was found to oxidize 114 muM reduced nicotinamide-adenine- dinucleotide-'(3)-phosphate (NADPH) with a corresponding reduction of an equivalent concentration of 2,6-dichlorophenolindophenol (DCPIP). As reported for Cu(II)(2) (3,5-DIPS)(4), addition of Mn(3)(3,5-DIPS)(6) to this reaction mixture decreased the reduction of DCPIP without significantly affecting the oxidation of NADPH. The concentration of Mn(3)(3,5-DIPS)(6) that produced a 50% decrease in DCPIP reduction (IC(50)) was found to be 5muM. Mechanistically, this inhibition of DCPIP reduction with ongoing NADPH oxidation by PHD was found to be due to the ability of Mn(3)(3,5-DIPS)(6) to serve as a catalytic electron acceptor for reduced PHD as had been reported for Cu(II)(2)(3,5-DIPS)(4). This catalytic decrease in reduction of DCPIP by Mn(3)(3,5-DIPS)(6) was enhanced by the presence of a large concentration of DCPIP and decreased by the presence of a large concentration of NADPH, consistent with what had been observed for the activity of Cu(II)(2)(3,5-DIPS)(4)Oxidation of NADPH by PHD in the presence of Mn(3)(3,5-DIPS)(6) and the absence of DCPIP was linearly related to the concentration of added Mn(3)(3,5-DIPS)(6) through the concentration range of 2.4 muM to 38muM with a 50% recovery of NADPH oxidation by PHD at a concentration of 6 muM Mn(3)(3,5-DIPS)(6)Conversion of [(3)H] L-Arginine to [(3)H] L-Citrulline by purified rat brain nitric oxide synthase (NOS) was decreased in a concentrated related fashion with the addition of Mn(3)(3,5-DIPS)(6) as well as Cu(II)(2)(3,5-DIPS)(4) which is an extention of

  8. Synthesis and Thermal Decomposition Mechanism of the Energetic Compound 3,5-Dinitro-4-nitroxypyrazole

    NASA Astrophysics Data System (ADS)

    Feng, Xiao-Qin; Cao, Duan-Lin; Cui, Jian-Lan

    2016-07-01

    A novel energetic material, 3,5-dinitro-4-nitroxypyrazole (DNNP), was synthesized via nitration and nucleophilic substitution reaction using 4-chloropyrazole as raw material. The structure of DNNP was characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and elemental analysis. Its detonation properties were calculated and compared with those of other commonly used energetic compounds. The thermal decomposition mechanism of DNNP was studied by means of thermogravimetry and differential scanning calorimetry coupled with a mass spectrometry (DSC-MS). The results show that the detonation properties of DNNP were better than those of TNT and comparable to those of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). In addition, the thermal decomposition mechanism of DNNP was supposed. Initially, the O-NO2 bond was broken, thereby producing a nitropyrazole oxygen radical. Subsequently, the nitropyrazole oxygen radical was decomposed by free radical cleavage of nitro or isomerized to nitritepyrazole and subsequently decomposed by free radical cleavage of the nitroso group. Finally, pyrazole ring fission occurred and produced N2, NO, N2O, and CO2.

  9. Hypocrellin B graft on activated carbon and photocatalytic oxidation of 2,3,5-trimethylphenol

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Li, Ying; Zhang, Pei; Zhang, Jucheng; Min, Yong; Yi, Zhongzhou; Zhang, Canbang; Wu, Mingzhu; Chen, Rui

    2008-12-01

    Hypocrellin B, a photosensitizer isolated from Hypocrella Bambuase sacc in Yunnan province, has significant anti-tumor and anti-virus character. In this article, hypocrellin B, which was grafted on activated carbon, was used as photocatalysts to catalytic oxidize 2,3,5-trimethylphenol to 2,3,5-trimethylhydrobenzoquinone because of its high photons efficiency. This study realized nearly 100% selectivity for 2,3,5-trimethylhydrobenzoquinone under visible light irradiation (>400nm) at aerobic atmosphere. The photocatalytic oxidation process has been studied by different parameters like the pretreatment of activated carbon, synthetic mehtod of grafted hypocrellin, and photo-assisted oxidation catalysis of 2,3,5-trimethylphenol to 2,3,5-trimethylhdrobenzoquinone. Compared to the conventional methods, this process could be more eco-friendly.

  10. The role of biotransformation and oxidative stress in 3,5-dichloroaniline (3,5-DCA) induced nephrotoxicity in isolated renal cortical cells from male Fischer 344 rats.

    PubMed

    Racine, Christopher R; Ferguson, Travis; Preston, Debbie; Ward, Dakota; Ball, John; Anestis, Dianne; Valentovic, Monica; Rankin, Gary O

    2016-02-01

    Among the mono- and dichloroanilines, 3,5-dichloroaniline (3,5-DCA) is the most potent nephrotoxicant in vivo and in vitro. However, the role of renal biotransformation in 3,5-DCA induced nephrotoxicity is unknown. The current study was designed to determine the in vitro nephrotoxic potential of 3,5-DCA in isolated renal cortical cells (IRCC) obtained from male Fischer 344 rats, and the role of renal bioactivation and oxidative stress in 3,5-DCA nephrotoxicity. IRCC (∼ 4 million cells/ml) from male rats were exposed to 3,5-DCA (0-1.0mM) for up to 120 min. In IRCC, 3,5-DCA was cytotoxic at 1.0mM by 60 min as evidenced by the increased release of lactate dehydrogenase (LDH), but 120 min was required for 3,5-DCA 0.5mM to increase LDH release. In subsequent studies, IRCC were exposed to a pretreatment (antioxidant or enzyme inhibitor) prior to exposure to 3,5-DCA (1.0mM) for 90 min. Cytotoxicity induced by 3,5-DCA was attenuated by pretreatment with inhibitors of flavin-containing monooxygenase (FMO; methimazole, N-octylamine), cytochrome P450 (CYP; piperonyl butoxide, metyrapone), or peroxidase (indomethacin, mercaptosuccinate) enzymes. Use of more selective CYP inhibitors suggested that the CYP 2C family contributed to 3,5-DCA bioactivation. Antioxidants (glutathione, N-acetyl-l-cysteine, α-tocopherol, ascorbate, pyruvate) also attenuated 3,5-DCA nephrotoxicity, but oxidized glutathione levels and the oxidized/reduced glutathione ratios were not increased. These results indicate that 3,5-DCA may be activated via several renal enzyme systems to toxic metabolites, and that free radicals, but not oxidative stress, contribute to 3,5-DCA induced nephrotoxicity in vitro. PMID:26808022

  11. Aromatic fluorine compounds. I. The synthesis of 2,5- and 3,5-difluorobenzotrifluorides

    USGS Publications Warehouse

    Finger, G.C.; Reed, F.H.

    1944-01-01

    The preparation of 2,5- and 3,5-difluorobenzotrifluoride and some of their intermediates is described. 3,5-Dinitrobenzotrifluoride was prepared from 3-nitrobenzotrifluoride with a fuming nitric-sulfuric acid mixture.

  12. Sensitivity of 2,6-Diamino-3, 5-Dinitropyrazine-1-Oxide

    SciTech Connect

    Tarver, C M; Urtiew, P A; Tran, T D

    2005-01-20

    The thermal and shock sensitivities of plastic bonded explosive formations based on 2,6-diamino-3,5-dinitropyrazine-1-oxide (commonly called LLM-105 for Lawrence Livermore Molecule No.105) are reported. The One Dimensional Time to Explosion (ODTX) apparatus was used to generate times to thermal explosion at various initial temperatures. A four-reaction chemical decomposition model was developed to calculate the time to thermal explosion versus inverse temperature curve. Three embedded manganin pressure gauge experiments were fired at different initial pressures to measure the pressure buildup and the distance required for transition to detonation. An Ignition and Growth reactive model was calibrated to this shock initiation data. LLM-105 exhibited thermal and shock sensitivities intermediate between those of triaminotrinitrobenzene (TATB) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine (HMX).

  13. Compound semiconductor oxide antireflection coatings

    NASA Astrophysics Data System (ADS)

    Knopp, K. J.; Mirin, R. P.; Bertness, K. A.; Silverman, K. L.; Christensen, D. H.

    2000-05-01

    We report the development of high quality, broad-bandwidth, antireflection (AR) coatings using the low index provided by wet thermally oxidized Al0.98Ga0.02As. We address the design criteria, fabrication, and characterizations of AR coatings composed of surface and buried oxide layers on GaAs. We show, using native-oxide dispersion data, that surface oxide coatings can be designed to offer a nearly zero minimum of reflectance and a reflectance of <1% over bandwidths as large as 500 nm. Surface coatings having a reflectance minimum of 0.4% and a reflectance of <1% over >250 nm have been experimentally demonstrated at a design wavelength of 1 micrometer. Additionally, buried oxide coatings can be designed with an AlxGa1-xAs matching layer of any composition to exactly match the admittance of any substrate with effective index between 2.5 and 3.5. We have demonstrated buried oxide coatings, also designed for 1 micrometer, having a reflectance minimum of 0.4% and a reflectance of <1% over 21 nm. The calculated optical scattering loss from measured roughness data indicates that reflectance minima as low as 10-4 % are ultimately achievable with native-oxide antireflection coatings.

  14. Cerium Oxide and Cerium Compounds

    Integrated Risk Information System (IRIS)

    Cerium oxide and cerium compounds ; CASRN 1306 - 38 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  15. SYNTHESIS AND IN VITRO ANTIMICROBIAL ACTIVITY OF NOVEL SERIES OF 3,5-DIACETYLPYRIDINE COMPOUNDS.

    PubMed

    Morsy, Eman M H; Kotb, Eman R; Soliman, Hanan A; Sayyed, Hayam H; Abdelwahed, Nayira A M

    2015-01-01

    Bis diacetylpyridine derivative (1) was prepared and reacted with different halo-compounds, namely: epichlorohydrine and dichloroethyl ethyl ether to give 2a,b, respectively, and reacted with morpholine and piperidine to afford Mannich products 3a,b, successively. Compound 4 was synthesized by reaction of 1 with potassium thiocyanate. Reaction of 4 with 4-chlorobenzaldehyde, glucose and phthalic or maleic anhydrides produced 5, 6 and 7a,b. Compound 1 reacted with 4-chlorobenzaldehyde to give bisanylmethylene derivative 8. Also some new compounds 9-11 were prepared from the reaction of compound 8 with nucleophiles, namely: hydrazine hydrate, thiosemicarbazide and hydroxylamine via Michael condensation reaction. On the other hand, compound 8 was reacted with cyclohexanone and cyclopentanone to give 12a,b. The structures of newly synthesized products have been deduced on the basis of elemental analysis and spectral data. Some synthesized compounds were screened for their antimicrobial evaluation. Among the assayed compounds, derivatives 3b and 12a showed the highest antimicrobial activities. PMID:26642655

  16. 3,3',5,5'-Tetramethylbenzidine Oxidation on Paper Devices for Horseradish Peroxidase-based Assays.

    PubMed

    Busa, Lori Shayne Alamo; Komatsu, Takeshi; Mohammadi, Saeed; Maeki, Masatoshi; Ishida, Akihiko; Tani, Hirofumi; Tokeshi, Manabu

    2016-01-01

    We report on the colorimetric oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by hydrogen peroxide using horseradish peroxidase on photolithography-fabricated (P-PAD) and wax-printed (W-PAD) paper-based analytical devices. Fabricating PADs via photolithography exposes the hydrophilic areas to polymers (photoresists) and solvents, not only reducing the hydrophilicity, but also affecting the TMB-H2O2 assay system with an unavoidable incomplete elimination of photoresist during fabrication. Detection signals are then observed in the presence of photoresist residues on the P-PAD, even at a blank HRP concentration. PMID:27506705

  17. Heteroepitaxial growth of 3-5 semiconductor compounds by metal-organic chemical vapor deposition for device applications

    NASA Technical Reports Server (NTRS)

    Collis, Ward J.; Abul-Fadl, Ali

    1988-01-01

    The purpose of this research is to design, install and operate a metal-organic chemical vapor deposition system which is to be used for the epitaxial growth of 3-5 semiconductor binary compounds, and ternary and quaternary alloys. The long-term goal is to utilize this vapor phase deposition in conjunction with existing current controlled liquid phase epitaxy facilities to perform hybrid growth sequences for fabricating integrated optoelectronic devices.

  18. Feasibility studies of the growth of 3-5 compounds of boron by MOCVD

    NASA Technical Reports Server (NTRS)

    Manasevit, H. M.

    1988-01-01

    Boron-arsenic and boron-phosphorus films have been grown on Si sapphire and silicon-on-sapphire (SOS) by pyrolyzing Group 3 alkyls of boron, i.e., trimethylborane (TMB) and triethylborane (TEB), in the presence of AsH3 and PH3, respectively, in an H2 atmosphere. No evidence for reaction between the alkyls and the hydrides on mixing at room temperature was found. However, the films were predominantly amorphous. The film growth rate was found to depend on the concentration of alkyl boron compound and was essentially constant when TEB and AsH3 were pyrolyzed over the temperature range 550 C to 900 C. The films were found to contain mainly carbon impurities (the amount varying with growth temperature), some oxygen, and were highly stressed and bowed on Si substrates, with some crazing evident in thin (2 micron) B-P and thick (5 micron) B-As films. The carbon level was generally higher in films grown using TEB as the boron source. Films grown from PH3 and TMB showed a higher carbon content than those grown from AsH3 and TMB. Based on their B/As and B/P ratios, films with nominal compositions B sub12-16 As2 and B sub1.1-1.3 P were grown using TMB as the boron source.

  19. Feasibility studies of the growth of 3-5 compounds of boron by MOCVD. Final report

    SciTech Connect

    Manasevit, H.M.

    1988-03-01

    Boron-arsenic and boron-phosphorus films have been grown on Si sapphire and silicon-on-sapphire (SOS) by pyrolyzing Group 3 alkyls of boron, i.e., trimethylborane (TMB) and triethylborane (TEB), in the presence of AsH/sub 3/ and PH/sub 3/, respectively, in an H/sub 2/ atmosphere. No evidence for reaction between the alkyls and the hydrides on mixing at room temperature was found. However, the films were predominantly amorphous. The film growth rate was found to depend on the concentration of alkyl boron compound and was essentially constant when TEB and AsH/sub 3/ were pyrolyzed over the temperature range 550 C to 900 C. The films were found to contain mainly carbon impurities (the amount varying with growth temperature), some oxygen, and were highly stressed and bowed on Si substrates, with some crazing evident in thin (2 micron) B-P and thick (5 micron) B-As films. The carbon level was generally higher in films grown using TEB as the boron source. Films grown from PH/sub 3/ and TMB showed a higher carbon content than those grown from AsH/sub 3/ and TMB. Based on their B/As and B/P ratios, films with nominal compositions B/sub12-16 As2/ and B/sub1.1-1.3/ P were grown using TMB as the boron source.

  20. Equations of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide

    NASA Astrophysics Data System (ADS)

    Gump, Jared C.; Stoltz, Chad A.; Mason, Brian P.; Freedman, Benjamin G.; Ball, Jason R.; Peiris, Suhithi M.

    2011-10-01

    2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) is an energetic ingredient that has an impact sensitivity close to that of TATB, yet a calculated energy content close to HMX. Reported tests of formulated LLM-105 reveal that it is a good candidate for a new insensitive high-performance explosive. As use of LLM-105 increases, thermodynamic parameters and phase stability will need to be determined for accurate modeling. In order to accomplish this goal, isothermal equations of state of LLM-105 at static high-pressure and temperature were investigated using synchrotron angle-dispersive x-ray diffraction and diamond anvil cells. Data at ambient temperature, 100 °C (373 K), and 180 °C (453 K) were used to obtain isothermal equations of state, and data at ambient pressure were used to obtain the volume thermal expansion coefficient. At ambient temperature, 100 °C (373 K), and 180 °C (453 K) no phase change was evident up to the highest measured pressure; and at ambient pressure, LLM-105 was stable up to 240 °C (513 K) and thermally decomposed by 260 °C (533 K).

  1. Catalyst for Oxidation of Volatile Organic Compounds

    NASA Technical Reports Server (NTRS)

    Wood, George M. (Inventor); Upchurch, Billy T. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); Schyryer, Jacqueline L. (Inventor); DAmbrosia, Christine M. (Inventor)

    2000-01-01

    Disclosed is a process for oxidizing volatile organic compounds to carbon dioxide and water with the minimal addition of energy. A mixture of the volatile organic compound and an oxidizing agent (e.g. ambient air containing the volatile organic compound) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  2. Calcium(II)(3) (3,5-Diisopropylsalicylate)(6)(H(2)O)(6) Activates Nitric Oxide Synthase: An Accounting for its Action in Decreasing Platelet Aggregation.

    PubMed

    Donham, D C; Sorenson, J R

    2000-01-01

    Purposes of these studies were first; to determine whether or not Calcium(II)(3) (3,5- diisopropylsalicylate)(6)(H(2)O)(6) [Ca(II)(3)(3,5-DIPS)(6)], a lipophilic calcium complex, could decrease activated-platelet aggregation, and second; to determine whether or not it is plausible that Ca(II)(3)(3,5-DIPS)(6) decreases activated-platelet aggregation by facilitating the synthesis of Nitric Oxide (NO) by Nitric Oxide Synthase (NOS). The influence of Ca(II)(3)(3,5-DIPS)(6) on the initial rate of activated-platelet aggregation was determined by measuring the decrease in rate of increase in transmission at 550 nm for a suspension of Thrombin-CaCl(2) activated platelets following the addition of 0, 50, 100, 250, or 500 muM Ca(II)(3)(3,5-DIPS)(6). To establish that the Ca(lI)(3)(3,5- DIPS)(6)-mediated decrease in aggregation was due to activation of NOS, the effect of L-NMMA, an inhibitor of NOS, on the inhibition of platelet aggregation by Ca(II)(3)(3,5-DIPS)(6) was determined using a suspension of activated platelets contaimng 0 or 250 muM Ca(II)(3)(3,5-DIPS)(6) without or with 1 mM L-NMMA. An in vitro Bovine Brain NOS reaction mixture, containing CaCl(2) for the activation of Phosphodiesterase-3' ,5'-Cyclic Nucleotide Activator required for the activation of NOS, was used to determine whether or not Ca(II)(3)(3,5-DIPS)(6) could be used as a substitute for the addition of Ca. The decrease in absorbance at 340 nm, lambda maximum for NADPH, was measured to determine NOS activity following the addition of NOS to the complete reaction mixture containing either CaCl(2), Ca(II)(3)(3,5-DIPS)(6), or neither Ca compound. Increasing the concentration of Ca(II)(3)(3,5-DIPS)(6) caused a concentration related decrease in activated platelet aggregation. The addition of L-NMMA to activated platelets, in the absence of Ca(II)(3)(3,5-DIPS)(6), caused a 129% increase in initial rate of platelet aggregation. The initial rate of platelet aggregation decreased 74% with the addition of 250 mu

  3. Oxidative electrochemical switching of photochromic diarylethene compounds

    NASA Astrophysics Data System (ADS)

    Fan, Congbin; Pu, Shouzhi; Liu, Weijun; Yang, Tianshe; Liu, Gang

    2008-12-01

    A series of photochromic diarylethenes compounds were synthesized and the electrochemistry and electrochemistry reaction mechanism properties were investigated. The cyclic voltammetry tests demonstrated that the colorless open-ring isomers were assigned to the unique oxidation process, but the color closed-ring isomers of these compounds were assigned to two oxidation processes. In addition, the electrochromism of diarylethene compound is observed in solution: The closed-ring reaction can be triggered by electrochemical oxidation, while the open-ring reaction must be photochemically driven. These oxidation processes properties can be useful as the oxidation processes electrochemical switching and the oxidation electrochemical switching properties of these different diarylethene isomers can be potential for electrochemistry data storages.

  4. Straightforward synthesis of 2,4,6-trisubstituted 1,3,5-triazine compounds targeting cysteine cathepsins K and S.

    PubMed

    Plebanek, Elżbieta; Chevrier, Florian; Roy, Vincent; Garenne, Thibault; Lecaille, Fabien; Warszycki, Dawid; Bojarski, Andrzej J; Lalmanach, Gilles; Agrofoglio, Luigi A

    2016-10-01

    The synthesis and evaluation against various cysteine cathepsins with endopeptidase activity, of two new families of hitherto unknown 1,3,5-triazines, substituted by a nitrile function and either a cyclohexylamine moiety (5-like) or a piperazine moiety (9-like) are described. The structure-activity relationship was discussed; from 16 synthesized novel compounds, 9h was the most active and selectively inhibitor of Cat K (IC50 = 28 nM) and Cat S (IC50 = 23 nM). Molecular docking of 9h to X-ray crystal structure of cathepsins K and S confirmed a common binding mode with a crucial covalent bond with Cys25. We observed for 9h that p-trifluorophenyl group is located in S2 pocket and possess hydrophobic interactions with Tyr67 and Met68. Triazine and piperazine moieties are located in S'1 pocket and interact with Gly23, Cys63, Gly64 and Gly65. Altogether, these results indicate that the new analogs can make them effective agents against some viruses for which the glycoprotein cleavage is mediated by an array of proteases. PMID:27214508

  5. Direct oxidative coupling of amidine hydrochlorides and methylarenes: TBHP-mediated synthesis of substituted 1,3,5-triazines under metal-free conditions.

    PubMed

    Guo, Wei

    2015-11-01

    Various 2,4,6-trisubstituted 1,3,5-triazines were smoothly formed via TBHP-mediated direct oxidative coupling of amidine and methylarenes. This tandem oxidation-imination-cyclization transformation exhibits a straightforward protocol to prepare 1,3,5-triazines from easily available starting materials and green oxidants under metal-free conditions. PMID:26411699

  6. Galangin (3,5,7-Trihydroxyflavone) Shields Human Keratinocytes from Ultraviolet B-Induced Oxidative Stress

    PubMed Central

    Madduma Hewage, Susara Ruwan Kumara; Piao, Mei Jing; Kim, Ki Cheon; Cha, Ji Won; Han, Xia; Choi, Yung Hyun; Chae, Sungwook; Hyun, Jin Won

    2015-01-01

    Most skin damage caused by ultraviolet B (UVB) radiation is owing to the generation of reactive oxygen species. Phytochemicals can act as antioxidants against UVB-induced oxidative stress. This study investigated the protective effects of the flavone galangin against UVB-induced oxidative damage in human keratinocytes. Galangin efficiently scavenged free radicals and reduced UVB-induced damage to cellular macromolecules, such as DNA, lipids, and proteins. Furthermore, galangin rescued cells undergoing apoptosis induced by UVB radiation via recovering mitochondrial polarization and down-regulating apoptotic proteins. These results showed that galangin protects human keratinocytes against UVB radiation-induced cellular damage and apoptosis via its antioxidant effects. PMID:25767685

  7. Synthesis, scale-up, and characterization of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105)

    SciTech Connect

    Pagoria, P. F.

    1998-04-27

    We have synthesized 4OOg of the new, insensitive, energetic heterocycle, 2,6-diamino-3,5-dinitropyrazine-l-oxide (LLM-105) with 81% the energy of HMX and excellent thermal stability. The synthesis is a three step reaction sequence from the commercially available starting material, 2,6-dichloropyrazine, with an overall yield of 36%. In this paper we will describe the scale-up of the synthesis of LLM- 105 and report on performance and shock sensitivity experiments performed on this material.

  8. Photocatalytic oxidation of organic compounds on Mars

    NASA Technical Reports Server (NTRS)

    Chun, S. F. S.; Pang, K. D.; Cutts, J. A.; Ajello, J. M.

    1978-01-01

    Ultraviolet-stimulated catalytic oxidation is proposed as a mechanism for the destruction of organic compounds on Mars. The process involves the presence of gaseous oxygen, UV radiation, and a catalyst (titanium dioxide), and all three of these have been found to be present in the Martian environment. Therefore it seems plausible that UV-stimulated oxidation of organics is responsible for degrading organic molecules into inorganic end products.

  9. Application of photocatalytic cadmium sulfide nanoparticles to detection of enzymatic activities of glucose oxidase and glutathione reductase using oxidation of 3,3',5,5'-tetramethylbenzidine.

    PubMed

    Grinyte, Ruta; Garai-Ibabe, Gaizka; Saa, Laura; Pavlov, Valeri

    2015-06-30

    It was found out that semiconductor CdS nanoparticles (NPs) are able to catalyze photooxidation of the well known chromogenic enzymatic substrate 3,3',5,5'-tetramethylbenzidine (TMB) by oxygen. The photocatalytical oxidation of TMB does not require hydrogen peroxide and its rate is directly proportional to the quantity of CdS NPs produced in situ through the interaction of Cd(2+) and S(2-) ions in an aqueous medium. This phenomenon was applied to development of colorimetric sensitive assays for glucose oxidase and glutathione reductase based on enzymatic generation of CdS NPs acting as light-powered catalysts. Sensitivity of the developed chromogenic assays was of the same order of magnitude or even better than that of relevant fluorogenic assays. The present approach opens the possibility for the design of simple and sensitive colorimetric assays for a number of enzymes using inexpensive and available TMB as a universal chromogenic compound. PMID:26041529

  10. Nitric oxide binding and photodelivery based on ruthenium(II) complexes of 4-arylazo-3,5-dimethylpyrazole.

    PubMed

    Ortiz, Mayreli; Torréns, Mabel; Mola, José L; Ortiz, Pedro J; Fragoso, Alex; Díaz, Alicia; Cao, Roberto; Prados, Pilar; de Mendoza, Javier; Otero, Antonio; Antiñolo, Antonio; Lara, Agustin

    2008-07-21

    Two fluorescent ligands, 3,5-dimethyl-4-(6'-sulfonylammonium-1'-azonaphthyl)pyrazole (dmpzn, 1) and 3,5-dimethyl-4-(4'-N,N'-dimethylaminoazophenyl)pyrazole (dmpza, 2) were obtained by condensation of ketoenolic derivatives with hydrazine. 1 and 2 formed the novel dinuclear complexes [(H(2)O)(3)ClRu(micro-L)(2)RuCl(H(2)O)(3)] (3 or 4) and [(H(2)O)(NO)Cl(2)Ru(micro-L)(2)RuCl(2)(NO)(H(2)O)] (6 or 7) (where L 1 = 2 or , respectively) which were characterized by IR, NMR and elemental analysis. The nitrosyl complexes were prepared by bubbling purified nitric oxide through methanol solutions of the corresponding ruthenium(II) chloroderivative or by reaction of the appropriate ligands with Ru(NO)Cl(3). Complexes 3 and 4 were found to bind NO, resulting in an increase in fluorescence. Ligand 1 also formed the mononuclear nitrosyl complex [Ru(NO)(bpy)(2)(dmpzn)]Cl(2) (8) which released NO in water at physiological pH and in the solid state as revealed by fluorescence and IR measurements, respectively. PMID:18594704

  11. Effect of ring coordination of pyridine-3,5-dicarboxylate and metatungstate to Ln ions on metatungstate structure: Synthesis, structure and optical property of four new compounds

    SciTech Connect

    Liu Dandan; Chen Yaguang; Zhang Chunjing; Meng Huaxin; Zhang Zhichao; Zhang Chunxia

    2011-06-15

    Four novel compounds based on {alpha}-metatungstate [H{sub 2}W{sub 12}O{sub 40}]{sup 6-} (W{sub 12}) and Ln-organic complexes, (NH{sub 4}){sub 4}[Ln{sub 2}(L){sub 2}(H{sub 2}O){sub 9}(H{sub 2}W{sub 12}O{sub 40})].nH{sub 2}O (Ln=Eu{sup III} (1), Gd{sup III} (2), Dy{sup III} (4), n=11; Tb{sup III} (3), n=12; L=pyridine-3,5-dicarboxylate dianion) have been synthesized in aqueous solution and characterized by element analysis, IR spectrometry and thermogravimetric analysis. Single-crystal X-ray diffraction analyses reveal these compounds are isostructural with a P21/n space group. The W{sub 12} cluster acting as a tridentate ligand connects three Ln{sup 3+} ions, in turn, each Ln2 ion links two W{sub 12} clusters, as a result, a W{sub 12}-Ln polymeric chain is formed. Coordination of pyridine-3,5-dicarboxylate ligands to the Ln{sup 3+} ions leads to a Ln-L polymeric chain. The two chains, W{sub 12}-Ln and Ln-L, share Ln2 ions, resulting in a 2-D layer. Ring coordination of pyridine-3,5-dicarboxylate and W{sub 12} to the Ln ions changes some bond angles of W{sub 12} that leads to a slight distortion of W{sub 12} and splitting of vibration band of W-Oc-W. Solid-state photoluminescence properties of compounds 1-4 have been investigated. - Graphical abstract: Four two-dimensional {alpha}-metatungstate and Ln-pyridine-3,5-dicarboxylate compounds have been synthesized. During the research, we elucidated the effect of ring coordination of pyridine-3,5-dicarboxylate on the structures of the POM-based hybrids. Highlights: > Four new 2-D compounds based on [H{sub 2}W{sub 12}O{sub 40}]{sup 6-} and Ln-organic complexes have been synthesized. > We study the ring coordination of pyridine-3, 5-dicarboxylate and W{sub 12} to Ln ions. > The luminescent properties of these compounds have been investigated.

  12. NIS-catalyzed oxidative cyclization of alcohols with amidines: a simple and efficient transition-metal free method for the synthesis of 1,3,5-triazines.

    PubMed

    Tiwari, Abhishek R; T, Akash; Bhanage, Bhalchandra M

    2015-12-01

    An efficient method for the synthesis of 1,3,5-triazines by NIS-catalyzed oxidative cyclization of alcohols with amidines has been developed. The reaction works smoothly under transition-metal free and phosphine-free conditions to afford a wide range of 1,3,5-triazine derivatives in moderate to good yields. The synthetic methodology was achieved via in situ oxidation of alcohols to aldehydes. PMID:26477749

  13. Butene oxidation by molybdenum crystallographic shear compounds

    SciTech Connect

    McCormick, R.L.

    1984-06-01

    The reduced molybdenum oxides Mo/sub 4/O/sub 11/-orh, Mo/sub 4/O/sub 11/-mon, Mo/sub 8/O/sub 23/, and Mo/sub 18/O/sub 52/ were synthesized. These compounds, as well as MoO/sub 3/, were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, Raman and FT-IR spectroscopies, and BET surface area measurements. The oxides were then studied in a pulsed reactor at 500/sup 0/C in the selective oxidation of butene and butadiene. The data suggested a process in which the surface site must become more oxidized in parallel with the oxidation of the adsorbed hydrocarbon. Evidence supporting this idea included the high selectivity to maleic anhydride observed over a completely oxidized surface and differences in the reactivity of butene and butadiende. In particular, oxygen insertion into butadiene to form furan occurred in the absence of gas phase O/sub 2/ over the reduced phases, while oxygen insertion into butene required the presence of molecular oxygen. Maleic anhydride formation required the presence of molecular oxygen except in the case of butadiene oxidation over MoO/sub 3/. The long range ordering of defects, known as crystallographic shear, was not shown to have any influence on the initial interaction of reactant and solid. However, the unusual coordination geometries and surface structures that are thought to be caused by the presence of shear planes may be related to the differences in catalytic selectivity observed for these oxides.

  14. GaAs and 3-5 compound solar cells status and prospects for use in space

    NASA Technical Reports Server (NTRS)

    Flood, D. J.; Brinker, D. J.

    1984-01-01

    Gallium arsenide solar cells equal or supass the best silicon solar cells in efficiency, radiation resistance, annealability, and in the capability to produce usable power output at elevated temperatures. NASA has been involved in a long range research and development program to capitalize on these manifold advantages, and to explore alternative III-V compounds for additional potential improvements. The current status and future prospects for research and development in this area are reviewed and the progress being made toward development of GaAs cells suitable for variety of space missions is discussed. Cell types under various stages of development include n(+)/p shallow homojunction thin film GaAs cells, x100 concentration ratio p/n and n/p GaAs small area concentrator cells, mechanically-stacked, two-junction tandem cells, and three-junction monolithic cascade cells, among various other cell types.

  15. X-ray photoelectron spectroscopic study of the oxide film on an aluminum-tin alloy in 3.5% sodium chloride solution

    SciTech Connect

    Venugopal, A.; Selvam, P.; Raja, V.S.; Veluchamy, P.; Minoura, H.

    1997-10-01

    Oxide films on Al and an Al-Sn alloy were analyzed by x-ray photoelectron spectroscopy (XPS) after immersion in 3.5% sodium chloride (NaCl) solution. Results showed Sn exhibited both Sn{sup 2+} and Sn{sup 4+} oxidation stats in the oxide film. It was proposed that incorporation of these cations in the film would result in generation of more anionic and cationic vacancies in aluminum oxide (Al{sub 2}O{sub 3}), leading to active dissolution of Al.

  16. Electrochemical oxidation of perfluorinated compounds in water.

    PubMed

    Niu, Junfeng; Li, Yang; Shang, Enxiang; Xu, Zesheng; Liu, Jinzi

    2016-03-01

    Perfluorinated compounds (PFCs) are persistent and refractory organic pollutants that have been detected in various environmental matrices and municipal wastewater. Electrochemical oxidation (EO) is a promising remediation technique for wastewater contaminated with PFCs. A number of recent studies have demonstrated that the "non-active" anodes, including boron-doped diamond, tin oxide, and lead dioxide, are effective in PFCs elimination in wastewater due to their high oxygen evolution potential. Many researchers have conducted experiments to investigate the optimal conditions (i.e., potential, current density, pH value, plate distance, initial PFCs concentration, electrolyte, and other factors) for PFCs elimination to obtain the maximal elimination efficiency and current efficiency. The EO mechanism and pathways of PFCs have been clearly elucidated, which undergo electron transfer, Kolbe decarboxylation or desulfonation, hydrolysis, and radical reaction. In addition, the safety evaluation and energy consumption evaluation of the EO technology have also been summarized to decrease toxic ion release from electrode and reduce the cost of this technique. Although the ultrasonication and hydrothermal techniques combined with the EO process can improve the removal efficiency and current efficiency significantly, these coupled techniques have not been commercialized and applied in industrial wastewater treatment. Finally, key challenges facing EO technology are listed and the directions for further research are pointed out (such as combination with other techniques, treatment for natural waters contaminated by low levels of PFCs, and reactor design). PMID:26745381

  17. Method and reaction pathway for selectively oxidizing organic compounds

    DOEpatents

    Camaioni, Donald M.; Lilga, Michael A.

    1998-01-01

    A method of selectively oxidizing an organic compound in a single vessel comprises: a) combining an organic compound, an acid solution in which the organic compound is soluble, a compound containing two oxygen atoms bonded to one another, and a metal ion reducing agent capable of reducing one of such oxygen atoms, and thereby forming a mixture; b) reducing the compound containing the two oxygen atoms by reducing one of such oxygen atoms with the metal ion reducing agent to, 1) oxidize the metal ion reducing agent to a higher valence state, and 2) produce an oxygen containing intermediate capable of oxidizing the organic compound; c) reacting the oxygen containing intermediate with the organic compound to oxidize the organic compound into an oxidized organic intermediate, the oxidized organic intermediate having an oxidized carbon atom; d) reacting the oxidized organic intermediate with the acid counter ion and higher valence state metal ion to bond the acid counter ion to the oxidized carbon atom and thereby produce a quantity of an ester incorporating the organic intermediate and acid counter ion; and e) reacting the oxidized organic intermediate with the higher valence state metal ion and water to produce a quantity of alcohol which is less than the quantity of ester, the acid counter ion incorporated in the ester rendering the carbon atom bonded to the counter ion less reactive with the oxygen containing intermediate in the mixture than is the alcohol with the oxygen containing intermediate.

  18. Novel self-assembled bimetallic structure of Bi/Fe(0): the oxidative and reductive degradation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX).

    PubMed

    Gong, Jianyu; Lee, Chung-Seop; Chang, Yoon-Young; Chang, Yoon-Seok

    2015-04-01

    A novel self-assembled bimetallic zero-valent bismuth/iron (Bi/Fe(0)) composite was synthesized, characterized, and used successfully to remove hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from wastewater. To assess the oxidative and reductive reactivities of Bi/Fe(0) nanoparticles (NPs), RDX degradation experiments were conducted in either ambient or anaerobic conditions, respectively. The best RDX degradation was achieved using 4%-Bi/Fe(0) (atomic ratio) NPs. In ambient conditions, concentrations of Fe(2+) ions and H2O2 were lower in the Bi/Fe(0) solution than in the Fe(0) solution; this difference indicates that most Fe(2+) ions and H2O2 reacted to produce hydroxyl radicals (*OH) and superoxide radical anions (O2(*-)), thereby resulting in the remarkable degradation of RDX. In anaerobic conditions, the presence of Bi increased the electron generation rate from the surfaces of the Bi/Fe(0) NPs. This increase was responsible for the excellent reductive degradation of RDX. Based on Density Functional Theory (DFT) calculations, the adsorption of water was endothermic on Fe(0) NPs and exothermic on Bi/Fe(0) NPs. Therefore, only the dissociation reactions of H2O in the Bi/Fe(0) system were spontaneous, and these reactions resulted in the prominent reactivity of the Bi/Fe(0) NPs. PMID:25559864

  19. The effect of intermetallic compound evolution on the fracture behavior of Au stud bumps joined with Sn-3.5Ag solder

    NASA Astrophysics Data System (ADS)

    Lee, Young-Kyu; Ko, Yong-Ho; Kim, Jun-Ki; Lee, Chang-Woo; Yoo, Sehoon

    2013-01-01

    The microstructure and joint properties of Au stud bumps joined with Sn-3.5Ag solder were investigated as functions of flip chip bonding temperature and aging time. Au stud bumps were bonded on solder-onpad (SOP) at bonding temperature of 260°C and 300°C for 10 s, respectively. Aging treatment was carried out at 150°C for 100 h, 300 h, and 500 h, respectively. After flip chip bonding, intermetallic compounds (IMCs) of AuSn, AuSn2, and AuSn4 were formed at the interface between the Au stud bump and Sn-3.5Ag solder. At a bonding temperature of 300°C, AuSn2 IMC clusters, which were surrounded by AuSn4 IMCs, were observed in the Sn-3.5Ag solder bump. After flip chip bonding, bonding strength was approximately 220.5mN/bump. As aging time increased, the bonding strength decreased. After 100 h of aging treatment, the bonding strength of the joint bonded at 300°C was lower than that bonded at 260°C due to the fast growth rate of the AuSn2 IMCs. The main failure modes were interface fractures between the AuSn2 IMCs and AuSn4 IMCs, fractures through the AuSn2 IMCs and pad lift. Initial joint microstructures after flip chip bonding strongly affected the bonding strengths of aged samples.

  20. Probing the Electronic Structure and Chemical Bonding of Mono-Uranium Oxides with Different Oxidation States: UOx(-) and UOx (x = 3-5).

    PubMed

    Su, Jing; Li, Wei-Li; Lopez, Gary V; Jian, Tian; Cao, Guo-Jin; Li, Wan-Lu; Schwarz, W H Eugen; Wang, Lai-Sheng; Li, Jun

    2016-02-25

    Uranium oxide clusters UOx(-) (x = 3-5) were produced by laser vaporization and characterized by photoelectron spectroscopy and quantum theory. Photoelectron spectra were obtained for UOx(-) at various photon energies with well-resolved detachment transitions and vibrational resolution for x = 3 and 4. The electron affinities of UOx were measured as 1.12, 3.60, and 4.02 eV for x = 3, 4, and 5, respectively. The geometric and electronic structures of both the anions and the corresponding neutrals were investigated by quasi-relativistic electron-correlation quantum theory to interpret the photoelectron spectra and to provide insight into their chemical bonding. For UOx clusters with x ≤ 3, the O atoms appear as divalent closed-shell anions around the U atom, which is in various oxidation states from U(II)(fds)(4) in UO to U(VI)(fds)(0) in UO3. For x > 3, there are no longer sufficient valence electrons from the U atom to fill the O(2p) shell, resulting in fractionally charged and multicenter delocalized valence states for the O ligands as well as η(1)- or η(2)-bonded O2 units, with unusual spin couplings and complicated electron correlations in the unfilled poly oxo shell. The present work expands our understanding of both the bonding capacities of actinide elements with extended spdf valence shells as well as the multitude of oxygen's charge and bonding states. PMID:26825216

  1. Studies on green and efficient catalytic oxidation of a triazole compound

    NASA Astrophysics Data System (ADS)

    Luo, J.; Liu, Y. C.; Huang, K. H.; Chai, T.; Wang, J. H.; Yu, Y. W.; Yuan, J. M.; Chang, S. J.; Guo, J. H.; Zhang, J.

    2016-07-01

    1-Methyl-3,5-dinitro-1,2,4-triazole is an insensitive energetic compound that can be prepared by oxidizing the nitrate salt of 1-methylguanazole. The influence of the reaction time, reaction temperature, reactant ratio, feeding method and catalytic oxidation method on the yield were discussed. The results show that the optimum reaction conditions are as follows: mass ratio of sodium tungstate to nitrate salt to 1-methylguanazole, 4:4.4; time, 5.5h; and temperature, 65-75°C. The yield of this oxidation reaction reached 51.36%.

  2. Optically enhanced oxidation of III-V compound semiconductors

    NASA Astrophysics Data System (ADS)

    Fukuda, Mitsuo; Takahei, Kenichiro

    1985-01-01

    Oxidation of III-V compound semiconductor (110) cleaved surfaces under light irradiation is studied. The light irradiation enhanced the reaction rate of oxidation but the relationship between oxide growth and oxidation time under logarithmic law scarcely changed within this experimental range. The oxidation trend observed under light irradiation is similar to that of thermal oxidation for GaP, GaAs, InP, InAs, InGaAs, and InGaAsP. Semiconductors having As as the V element tend to be easily oxidized, while those of the above mentioned six kinds of materials having Ga as the III element are quickly oxidized in their initial stage. Ternary and quaternary compound semiconductors have less tendency to be oxidized compared to their constituent binary materials. off

  3. On the stoichiometry between uncouplers of oxidative phosphorylation and respiratory chains. The catalytic action of SF 6847 (3,5-di-tert-butyl-4-hydroxy-benzylidenemalononitrile).

    PubMed

    Terada, H; VAN Dam, K

    1975-06-17

    Titration of State 4 rat-liver mitochondria at pH 7.2 with the uncoupler 3,5-di-tert-butyl-4-hydroxybenzylidenemalononitrile (SF 6847) at various concentrations of mitochondria and using various substrates indicates that under optimal conditions less than 0.2 molecule of 3,5-di-tert-butyl-4-hydroxybenzylidenemalononitrile per respiratory chain is sufficient to induce complete uncoupling. This result suggests that there is not a stoichiometric relationship between uncoupler molecules and cytochrome c oxidase, involved in oxidative phosphorylation, or between the former and phosphorylation assemblies. Experiments on the release by 3,5-di-tert-butyl-4-hydroxybenzylidenemalononitrile of azide-inhibited respiration of State 3 mitochondria and titrations with 5-chloro-3-tert-butyl-2'-chloro-4'-nitrosalicylanilide (S13) of State 4 mitochondria at various mitochondrial concentrations confirm this conclusion. PMID:1138887

  4. Copper-Mediated [3 + 2] Oxidative Cyclization Reaction of N-Tosylhydrazones and β-Ketoesters: Synthesis of 2,3,5-Trisubstituted Furans.

    PubMed

    Huang, Yubing; Li, Xianwei; Yu, Yue; Zhu, Chuanle; Wu, Wanqing; Jiang, Huanfeng

    2016-06-17

    The first attempt at utilizing N-tosylhydrazones as two-carbon synthons has been successfully achieved, which underwent a copper-mediated [3 + 2] oxidative cyclization reaction to afford 2,3,5-trisubstituted furans in moderate to good yields. The features of this method include inexpensive metal catalyst, readily available substrates, high regioselectivity, and convenient operation. The studies provide important approaches for further exploration of the powerful and diverse reaction abilities of N-tosylhydrazones. PMID:27227374

  5. Formation of iodinated organic compounds by oxidation of iodide-containing waters with manganese dioxide.

    PubMed

    Gallard, Hervé; Allard, Sébastien; Nicolau, Rudy; von Gunten, Urs; Croué, Jean Philippe

    2009-09-15

    This study shows that iodinated organic compounds can be produced when iodide-containing waters are in contact with manganese oxide birnessite (delta-MnO2) in the pH range of 5-7. In the absence of natural organic matter (NOM), iodide is oxidized to iodate that is also adsorbed onto delta-MnO2. In the presence of iodide and NOM, adsordable organic iodine compounds (AOI) are formed at pH < 7 because of the oxidation of iodide to iodine by delta-MnO2 and the reactions of iodine with NOM. In addition, iodoacetic acid and iodoform have been identified as specific iodinated byproducts. Formation of iodoform is not observed for high NOM/delta-MnO2 ratios due to inhibition of the catalytic effect of delta-MnO2 by NOM poisoning. Experiments with model compounds such as resorcinol and 3,5-heptanedione confirmed that the delta-MnO2/l(-) system is very effective for the formation of iodinated organic compounds. These results suggest that birnessite acts as a catalyst through the oxidation of iodide to iodine and the polarization of the iodine molecule, which then reacts with NOM moieties. Furthermore, our results indicate that during water treatment in the presence of manganese oxide, iodinated organic compounds may be formed, which may lead to taste and odor or toxicological problems. PMID:19806734

  6. The Temperature-Dependent Thermal Expansion of 2,6-Diamino-3,5-dinitropyrazine-1-oxide Effected by Hydrogen Bond Network Relaxation

    NASA Astrophysics Data System (ADS)

    Li, Jingyou; Zhang, Haobin; Wen, Maoping; Xu, Jinjiang; Liu, Xiaofeng; Sun, Jie

    2016-04-01

    The temperature-dependent thermal expansion of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) was investigated by using powder X-ray diffraction (PXRD) together with Rietveld refinement to estimate the dimension at a crystal lattice level. In the temperature range of 30-200°C, the coefficient of thermal expansion (CTE) of LLM-105 is temperature dependent, which is different from other explosives, such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,2‧,4,4‧,6,6‧-hexanitrostilbene (HNS) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), with constant CTEs. The results of temperature-dependent infrared (IR) spectra indicated that the intermolecular hydrogen bond network relaxes with increasing temperature, which results in temperature-dependent thermal expansion. In this work, more accurate CTEs for LLM-105 crystals are obtained and the effects of the hydrogen bond network on the thermal expansion are further clarified. These results are beneficial to the design of materials with structural peculiarities and as-expected thermal expansion to satisfy different application requirements.

  7. The oxidation degradation of aromatic compounds

    NASA Technical Reports Server (NTRS)

    Brezinsky, Kenneth; Glassman, Irvin

    1987-01-01

    A series of experiments were conducted which focused on understanding the role that the O atom addition to aromatic rings plays in the oxidation of benzene and toluene. Flow reactor studies of the oxidation of toluene gave an indication of the amount of O atoms available during an oxidation and the degree to which the O atom adds to the ring. Flow reactor studies of the oxidation of toluene and benzene to which NO2 was added, have shown that NO2 appears to suppress the formation of O atoms and consequently reduce the amount of phenols and cresols formed by O atom addition. A high temperature pyrolysis study of phenol has confirmed that the major decomposition products are carbon monoxide and cyclopentadiene. A preliminary value for the overall decomposition rate constant was also obtained.

  8. Compound oxidized styrylphosphine. [flame resistant vinyl polymers

    NASA Technical Reports Server (NTRS)

    Paciorek, K. J. L. (Inventor)

    1979-01-01

    A process is described for preparing flame resistant, nontoxic vinyl polymers which contain phosphazene groups and which do not emit any toxic or corrosive products when they are oxidatively degraded. Homopolymers, copolymers, and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer from a group of organic azides, or by polymerizing p-diphenylphosphinestyrene and then oxidizing that monomer with an organoazide from the group of (C6H5)2P(O)N3, (C6H5O)2P(O)N3, (C6H5)2C3N3(N3), and C6H5C3N3(N3)2. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer.

  9. Effect of Ni layer thickness and soldering time on intermetallic compound formation at the interface between molten Sn-3.5Ag and Ni/Cu substrate

    SciTech Connect

    Choi, W.K.; Lee, H.M.

    1999-11-01

    The binary eutectic Sn-3.5wt.%Ag alloy was soldered on the Ni/Cu plate at 250 C, the thickness of the Ni layer changing from 0 through 2 and 4 {micro}m to infinity, and soldering time changing from 30 to 120 s at intervals of 30 s. The infinite thickness was equivalent to the bare Ni plate. The morphology, composition and phase identification of the intermetallic compound (IMC, hereafter) formed at the interface were examined. Depending on the initial Ni thickness, different IMC phases were observed at 30 s: Cu{sub 6}Sn{sub 5} on bare Cu, detestable NiSn{sub 3} + Ni{sub 3}Sn{sub 4} on Ni(2 {micro}m)/Cu, Ni{sub 3}Sn{sub 4} on Ni(4 {micro}m)/Cu, and Ni{sub 3}Sn + Ni{sub 3}Sn{sub 4} on bare Ni. With increased soldering time, a Cu-Sn-based {eta}-(Cu{sub 6}Sn{sub 5}){sub 1{minus}x}Ni{sub x} phase formed under the pre-formed Ni-Sn IMC layer both at 60s in the Ni(2 {micro}m)/Cu plate and at 90s in the Ni(4 {micro}m)/Cu plate. The two-layer IMC pattern remained thereafter. The wetting behavior of each joint was different and it may have resulted from the type of IMC formed on each plate. The thickness of the protective Ni layer over the Cu plate was found to be an important factor in determining the interfacial reaction and the wetting behavior.

  10. The crystal structure and physicochemical characteristics of 2-hydroxy-N-[3(5)-pyrazolyl]-1,4-naphthoquinone-4-imine, a new antitrypanosomal compound.

    PubMed

    Sperandeo, Norma R; Karlsson, Alicia; Cuffini, Silvia; Pagola, Silvina; Stephens, Peter W

    2005-01-01

    This study was designed to investigate the physical characteristics and crystalline structure of 2-hydroxy-N-[3(5)-pyrazolyl]-1,4-naphthoquinone-4-imine (PNQ), a new active compound against Trypanosoma cruzi, the causative agent of American trypanosomiasis. Methods used included differential scanning calorimetry, thermogravimetry, hot stage microscopy, polarized light microscopy (PLM), Fourier-transform infrared (FTIR) spectroscopy, and high-resolution X-ray powder diffraction (HR-XRPD). According to PLM and HR-XRPD data, PNQ crystallized as red oolitic crystals (absolute methanol) or prisms (dimethyl sulfoxide [DMSO]-water) with the same internal structure. The findings obtained with HR-XRPD data (applying molecular location methods) showed a monoclinic unit cell [a = 18.4437(1) A, b = 3.9968(2) A, c = 14.5304(1) A, alpha = 90 degrees , beta = 102.71(6) degrees , gamma = 90 degrees , V = 1044.9(1) A(3), Z = 4, space group P2(1)/c], and a crystal structure (excluding H-positions) described by parallel layers in the direction of the b-axis, with molecules held by homochemical (phenyl-phenyl and pyrazole-pyrazole) van der Waals interactions. In addition, FTIR spectra displayed the NH-pyrazole stretch overlapped with the OH absorption at 3222 cm(-1), typical of -NH and -OH groups associated through H-bondings; and a carbonyl stretching absorption at 1694 cm(-1), indicating a nonextensively H-bonded quinonic C=O, which was in accordance with the solved crystal structure of PNQ. The existence of such cohesive forces shed light on the thermoanalytical data, which revealed that PNQ is a stable solid, unaffected by oxygen that decomposed without melting above 260 degrees C. PMID:16408868

  11. Molecular design of new nitramine explosives: 1,3,5,7-tetranitro-8-(nitromethyl)-4-imidazolino[4,5-b]4-imidazolino-[4,5-e] pyridine and its N-oxide.

    PubMed

    Liu, Hui; Du, Hongchen; Wang, Guixiang; Liu, Yan; Gong, Xuedong

    2012-04-01

    Two new nitramine compounds containing pyridine, 1,3,5,7-tetranitro-8-(nitromethyl) -4-imidazolino[4,5-b]4-imidazolino-[4,5-e]pyridine and its N-oxide 1,3,5,7-tetranitro-8- (nitromethyl)-4-imidazolino[4,5-b]4-imidazolino-[4,5-e]pyridine-4-ol were proposed. Density functional theory (DFT) has been employed to study the molecular geometries, electronic structures, infrared spectra, and thermodynamic properties at the B3LYP/6-31G* level. Their detonation performances evaluated using the Kamlet-Jacobs equations with the calculated densities and heats of formation are superior to those of HMX. The predicted densities of them were ca. 2 g cm(-3), detonation velocities were over 9 km s(-1), and detonation pressures were about 40 GPa, showing that they may be potential candidates of high energy density materials (HEDMs). The natural bond orbital analysis indicated that N-NO(2) bond is the trigger bond during thermolysis process. The stability of the title compounds is slightly lower than that of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12- hexaazaisowurtzitane (CL-20). The results of this study may provide basic information for the molecular design of new HEDMs. PMID:21748326

  12. One-electron oxidation of alcohols by the 1,3,5-trimethoxybenzene radical cation in the excited state during two-color two-laser flash photolysis.

    PubMed

    Cai, Xichen; Sakamoto, Masanori; Fujitsuka, Mamoru; Majima, Tetsuro

    2007-03-15

    One-electron oxidation of alcohols such as methanol, ethanol, and 2-propanol by 1,3,5-trimethoxybenzene radical cation (TMB*+) in the excited state (TMB*+*) was observed during the two-color two-laser flash photolysis. TMB*+ was formed by the photoinduced bimolecular electron-transfer reaction from TMB to 2,3,5,6-tetrachlorobenzoquinone (TCQ) in the triplet excited-state during the first 355-nm laser flash photolysis. Then, TMB*+* was generated from the selective excitation of TMB*+ during the second 532 nm laser flash photolysis. Hole transfer rate constants from TMB*+* to methanol, ethanol, and 2-propanol were calculated to be (5.2 +/- 0.5) x 10(10), (1.4 +/- 0.3) x 10(11), and (3.2 +/- 0.6) x 10(11) M-1 s-1, respectively. The order of the hole transfer rate constants is consistent with oxidation potentials of alcohol. Formation of TCQH radical (TCQH*) with a characteristic absorption peak at 435 nm was observed in the microsecond time scale, suggesting that deprotonation of the alcohol radical cation occurs after the hole transfer and that TCQ radical anion (TCQ*-), generated together with TMB*+ by the photoinduced electron-transfer reaction, reacts with H+ to give TCQH*. PMID:17295459

  13. Anti-Oxidative Polyphenolic Compounds of Cocoa.

    PubMed

    Nabavi, Seyed F; Sureda, Antoni; Daglia, Maria; Rezaei, Parizad; Nabavi, Seyed M

    2015-01-01

    Oxidative stress plays a key role in the pathogenesis of different serious chronic diseases such as cancer, diabetes, cardiovascular and neurodegenerative disorders, etc. Recent research has been focused on the beneficial role of dietary antioxidants against oxidative stress both under in vitro and in vivo conditions. Theobroma cacao L. (cacao tree) is an evergreen tree which is native to South America. It is a plant of great economic importance and its seeds are commonly used to produce cocoa powder and chocolate. In addition to its uses in food industry, cocoa is a rich source of polyphenolic antioxidants. There is a plethora of in vitro and in vivo studies that report cocoa antioxidant capacity. The protective activity of cocoa seems to be due to its phytochemical constituents, especially catechins. However, bioavailability of cocoa polyphenolic constituents following oral administration is very low (nanomolar concentrations). In the present paper, we critically reviewed the available literature on the antioxidant and free radical scavenging activities of cocoa and its polyphenolic constituents. In addition to these, we provide brief information about cultivation, phytochemistry, bioavailability and clinical impacts of cocoa. PMID:26059107

  14. Enzymatic oxidation of phenolic compounds in coffee processing wastewater.

    PubMed

    Torres, Juliana Arriel; Batista Chagas, Pricila Maria; Silva, Maria Cristina; dos Santos, Custódio Donizete; Duarte Corrêa, Angelita

    2016-01-01

    Peroxidases can be used in the treatment of wastewater containing phenolic compounds. The effluent from the wet processing of coffee fruits contains high content of these pollutants and although some studies propose treatments for this wastewater, none targets specifically the removal of these recalcitrant compounds. This study evaluates the potential use of different peroxidase sources in the oxidation of caffeic acid and of total phenolic compounds in coffee processing wastewater (CPW). The identification and quantification of phenolic compounds in CPW was performed and caffeic acid was found to be the major phenolic compound. Some factors, such as reaction time, pH, amount of H2O2 and enzyme were evaluated, in order to determine the optimum conditions for the enzyme performance for maximum oxidation of caffeic acid. The turnip peroxidase (TPE) proved efficient in the removal of caffeic acid, reaching an oxidation of 51.05% in just 15 minutes of reaction. However, in the bioremediation of the CPW, the horseradish peroxidase (HRP) was more efficient with 32.70%±0.16 of oxidation, followed by TPE with 18.25%±0.11. The treatment proposed in this work has potential as a complementary technology, since the efficiency of the existing process is intimately conditioned to the presence of these pollutants. PMID:26744933

  15. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G. ); Sims, R.C. . Dept. of Civil and Environmental Engineering)

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ''humic-like'' material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  16. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G.; Sims, R.C.

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment? Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ``humic-like`` material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  17. Some observations on the periodate oxidation of amino compounds

    PubMed Central

    Clamp, J. R.; Hough, L.

    1966-01-01

    Various aliphatic and aromatic amines are oxidized by sodium metaperiodate and these reactions have been studied quantitatively in acidic, unbuffered and basic media. Significant differences have been observed between the behaviour of aliphatic and aromatic amines. Certain compounds also behaved differently under acidic and basic conditions. These reactions are related to the periodate oxidation of amino acids and, from observations on a number of glycine derivatives, a reaction mechanism is proposed for this process. PMID:4291354

  18. Electron microscopy of compound oxide laser materials

    NASA Astrophysics Data System (ADS)

    Eakins, Daniel E.; LeBret, Joel B.; Norton, M. G.; Bahr, David F.; Dumm, John Q.

    2003-06-01

    Oxide single crystals, such as yttrium aluminum garnet (YAG) and yttrium orthovanadate (YVO4), are important host crystals for solid-state laser applications. These crystals are often grown by the Czochralski process and are doped with neodymium during growth. The microstructure of the resultant crystal affects the overall laser performance and it is necessary to be able to characterize grown-in defects in the material. Scanning electron microscopy has been used to examine the fracture surfaces of YAG and has shown the presence of microscopic voids, which act as stress concentrators and in some cases appear to be the cause of fracture. Transmission electron microscopy (TEM) has been used to characterize various defects in both YAG and YVO4 crystals. The defects found depend on the growth conditions, specifically the Nd concentration in the crystal and the position within the boule. One of the most common defects identified in both materials were microscopic spherical particles. In YAG these particles appeared to be located primarily in the core regions and analysis of high resolution images indicate that they are due to regions that are both compositionally and orientationally different from the matrix phase. Direct observation of dislocations in YVO4 was made using TEM. In YAG only indirect evidence for dislocations could be found from the observation of river marks on fracture surfaces.

  19. Electrolytic photodissociation of chemical compounds by iron oxide electrodes

    DOEpatents

    Somorjai, Gabor A.; Leygraf, Christofer H.

    1984-01-01

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor diode having visible light as its sole source of energy. The diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  20. Electrolytic photodissociation of chemical compounds by iron oxide photochemical diodes

    DOEpatents

    Somorjai, Gabor A.; Leygraf, Christofer H.

    1985-01-01

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor photochemical diode having visible light as its sole source of energy. The photochemical diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  1. Synthesis, structure and magnetic properties of mono-, dinuclear and polymeric compounds of transition metals with 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole

    NASA Astrophysics Data System (ADS)

    Martín-Ramos, Pablo; Silva, Manuela Ramos; de A. e Silva, Joana; Martins, Nuno D.; Yuste-Vivas, Consuelo; Pereira da Silva, Pedro S.; Sobral, Abílio J. F. N.; Pereira, Laura C. J.

    2016-03-01

    Five new complexes were obtained from solution of transition metal salts (M=Co(II), Cu(II)) with 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (abpt) in different molar ratios. X-ray structural elucidation revealed low-dimensional compounds with the metal ions assembled in monomers, dimers or chains. Two similar polymorphs were obtained for the monomer synthesized from Cu(II) chloride. Temperature-dependent magnetic susceptibility measurements were conducted for the non-monomeric compounds, and efficient super-exchange interaction was found for the mostly planar dinuclear Co(II) complex.

  2. Oxidations of alkenes and lignin model compounds in aqueous dispersions

    SciTech Connect

    Zhu, Weiming.

    1991-01-01

    The objective was to develop methods to oxidize water-immiscible alkenes and lignin model compounds with polymer colloid supported transition metal catalysts. The oxidations of organic compounds were carried out in aqueous phase with several water-soluble oxidants and dioxygen. Cationic polymer latexes were prepared by the emulsion copolymerization of vinylbenzyl chloride, divinylbenzene, and vinyl octadecyl ether, or styrene, or n-decyl methacrylate, and the subsequent quaternization of copolymers with trimethylamine. The latex particles were 44 nm to 71 nm in diameter. The latex bound Mn porphyrin catalysts were formed with MnTSPP [TSPP = meso-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphyrin], which catalyzed the oxidation of cyclohexene, cycloocetene, allylbenzene, and 1-octene by sodium hypochlorite (NaOCl) and potassium peroxymonosulfate (KHSO[sub 5]). The latex bound porphyrin catalysts showed higher activity than MnTSPP in solution. Oxidations of 3,4-dimethoxybenzyl alcohol (DMBA), 4-hydroxy-3-methoxytoluene (HMT), and 3,4-dimethoxytoluene (DMT) were performed with either dioxygen or hydrogen peroxide and CoPcTS (PcTS = tetrasulfonatophthalocyanine), FePcTS, CuPcTS, NiPcTS, FeTCPP [TCPP = meso-tetrakis(4-carboxyphenyl)porphyrin], and MnTSPP. CoPcTS catalyzed the autoxidation of DMBA and HMT at 70-85[degrees]C and pH [ge] 8. All catalysts were active for the oxidation of DMBA, HMT, and DMT with H[sub 2]O[sub 2]. Aqueous solutions of KHSO[sub 5] oxidized water-immiscible alkenes at room temperature in the absence of organic solvent. The acidic pH [le] 1.7 solutions of commercial 2KHSO[sub 5][center dot]K[sub 2]SO[sub 4] in water produced diols from all reactive alkenes except cyclooctene. Adjustment of initial pH to [ge]6.7 with NaHCO[sub 3] enabled selective epoxidations.

  3. Rapid deposition of oxidized biogenic compounds to a temperate forest

    NASA Astrophysics Data System (ADS)

    Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.; St. Clair, Jason M.; Paulot, Fabien; Wolfe, Glenn M.; Wennberg, Paul O.

    2015-02-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m-2ṡs-1). GEOS-Chem, a widely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS-Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.

  4. Rapid deposition of oxidized biogenic compounds to a temperate forest.

    PubMed

    Nguyen, Tran B; Crounse, John D; Teng, Alex P; St Clair, Jason M; Paulot, Fabien; Wolfe, Glenn M; Wennberg, Paul O

    2015-02-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m(-2)⋅s(-1)). GEOS-Chem, a widely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS-Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases. PMID:25605913

  5. Rapid deposition of oxidized biogenic compounds to a temperate forest

    PubMed Central

    Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.; St. Clair, Jason M.; Paulot, Fabien; Wolfe, Glenn M.; Wennberg, Paul O.

    2015-01-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m−2⋅s−1). GEOS−Chem, a widely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS−Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases. PMID:25605913

  6. Rapid Deposition of Oxidized Biogenic Compounds to a Temperate Forest

    NASA Technical Reports Server (NTRS)

    Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.; St. Clair, Jason M.; Paulot, Fabien; Wolfe, Glenn M.; Wennberg, Paul O.

    2015-01-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (approx. 1 nmol m(exp.-2)·s(exp.-1)). GEOS-Chem, awidely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS-Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.

  7. Modeling toxic compounds from nitric oxide emission measurements

    NASA Astrophysics Data System (ADS)

    Vallero, Daniel A.; Peirce, Jeffrey; Cho, Ki Don

    Determining the amount and rate of degradation of toxic pollutants in soil and groundwater is difficult and often requires invasive techniques, such as deploying extensive monitoring well networks. Even with these networks, degradation rates across entire systems cannot readily be extrapolated from the samples. When organic compounds are degraded by microbes, especially nitrifying bacteria, oxides or nitrogen (NO x) are released to the atmosphere. Thus, the flux of nitric oxide (NO) from the soil to the lower troposphere can be used to predict the rate at which organic compounds are degraded. By characterizing and applying biogenic and anthropogenic processes in soils the rates of degradation of organic compounds. Toluene was selected as a representative of toxic aromatic compounds, since it is inherently toxic, it is a substituted benzene compound and is listed as a hazardous air pollutant under Section 12 of the Clean Air Act Amendments of 1990. Measured toluene concentrations in soil, microbial population growth and NO fluxes in chamber studies were used to develop and parameterize a numerical model based on carbon and nitrogen cycling. These measurements, in turn, were used as indicators of bioremediation of air toxic (i.e. toluene) concentrations. The model found that chemical concentration, soil microbial abundance, and NO production can be directly related to the experimental results (significant at P < 0.01) for all toluene concentrations tested. This indicates that the model may prove useful in monitoring and predicting the fate of toxic aromatic contaminants in a complex soil system. It may also be useful in predicting the release of ozone precursors, such as changes in reservoirs of hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.

  8. Selective extraction and release using (EDTA-Ni)-layered double hydroxide coupled with catalytic oxidation of 3,3',5,5'-tetramethylbenzidine for sensitive detection of copper ion.

    PubMed

    Tang, Sheng; Chang, Yuepeng; Chia, Guo Hui; Lee, Hian Kee

    2015-07-23

    Copper is an important heavy metal in various biological processes. Many methods have been developed for detecting of copper ions (Cu(2+)) in aqueous samples. However, an easy, cheap, selective and sensitive method is still desired. In this study, a selective extraction-release-catalysis approach has been developed for sensitive detection of copper ion. Ethylenediaminetetraacetic acid (EDTA) chelated with nickel ion (Ni(2+)) were intercalated in a layered double hydroxide via a co-precipitation reaction. The product was subsequently applied as sorbent in dispersive solid-phase extraction for the enrichment of Cu(2+) at pH 6. Since Cu(2+) has a stronger complex formation constant with EDTA, Ni(2+) exchanged with Cu(2+) selectively. The resulting sorbent containing Cu(2+) was transferred to catalyze the 3,3',5,5'-tetramethylbenzidine oxidation reaction, since Cu(2+) could be released by the sorbent effectively and has high catalytic ability for the reaction. Blue light emitted from the oxidation product was measured by ultraviolet-visible spectrophotometry for the determination of Cu(2+). The extraction temperature, extraction time, and catalysis time were optimized. The results showed that this method provided a low limit of detection of 10nM, a wide linear range (0.05-100μM) and good linearity (r(2)=0.9977). The optimized conditions were applied to environmental water samples. Using Cu(2+) as an example, this work provided a new and interesting approach for the convenient and efficient detection of metal cations in aqueous samples. PMID:26231895

  9. First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105)

    SciTech Connect

    Manaa, M. Riad Kuo, I-Feng W.; Fried, Laurence E.

    2014-08-14

    We report dispersion-corrected density functional theoretical calculations of the unreacted equation of state (EOS) of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) under hydrostatic compression of up to 45 GPa. Convergence tests for k-points sampling in the Brillouin zone show that a 3 × 1 × 2 mesh is required to reproduce the X-ray crystal structure at ambient conditions, and we confirm our finding with a separate supercell calculation. Our high-pressure EOS yields a bulk modulus of 19.2 GPa, and indicates a tendency towards anisotropic compression along the b lattice vector due to molecular orientations within the lattice. We find that the electronic energy band gap decreases from a semiconductor type of 1.3 eV at 0 GPa to quasi-metallic type of 0.6 eV at 45 GPa. The extensive intermolecular hydrogen bonds involving the oxide (–NO) and dioxide (–NO{sub 2}) interactions with the amine (–NH{sub 2}) group showed enhanced interactions with increasing pressure that should be discernible in the mid IR spectral region. We do not find evidence for structural phase transitions or chemically induced transformations within the pressure range of our study. The gas phase heat of formation is calculated at the G4 level of theory to be 22.48 kcal/mol, while we obtain 25.92 kcal/mol using the ccCA-PS3 method. Density functional theory calculations of the crystal and the gas phases provided an estimate for the heat of sublimation of 32.4 kcal/mol. We thus determine the room-temperature solid heat of formation of LLM-105 to be −9.9 or −6.5 kcal/mol based on the G4 or ccCA-PS3 methods, respectively.

  10. First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105)

    NASA Astrophysics Data System (ADS)

    Manaa, M. Riad; Kuo, I.-Feng W.; Fried, Laurence E.

    2014-08-01

    We report dispersion-corrected density functional theoretical calculations of the unreacted equation of state (EOS) of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) under hydrostatic compression of up to 45 GPa. Convergence tests for k-points sampling in the Brillouin zone show that a 3 × 1 × 2 mesh is required to reproduce the X-ray crystal structure at ambient conditions, and we confirm our finding with a separate supercell calculation. Our high-pressure EOS yields a bulk modulus of 19.2 GPa, and indicates a tendency towards anisotropic compression along the b lattice vector due to molecular orientations within the lattice. We find that the electronic energy band gap decreases from a semiconductor type of 1.3 eV at 0 GPa to quasi-metallic type of 0.6 eV at 45 GPa. The extensive intermolecular hydrogen bonds involving the oxide (-NO) and dioxide (-NO2) interactions with the amine (-NH2) group showed enhanced interactions with increasing pressure that should be discernible in the mid IR spectral region. We do not find evidence for structural phase transitions or chemically induced transformations within the pressure range of our study. The gas phase heat of formation is calculated at the G4 level of theory to be 22.48 kcal/mol, while we obtain 25.92 kcal/mol using the ccCA-PS3 method. Density functional theory calculations of the crystal and the gas phases provided an estimate for the heat of sublimation of 32.4 kcal/mol. We thus determine the room-temperature solid heat of formation of LLM-105 to be -9.9 or -6.5 kcal/mol based on the G4 or ccCA-PS3 methods, respectively.

  11. Method for predicting photocatalytic oxidation rates of organic compounds.

    PubMed

    Sattler, Melanie L; Liljestrand, Howard M

    2003-01-01

    In designing a photocatalytic oxidation (PCO) system for a given air pollution source, destruction rates for volatile organic compounds (VOCs) are required. The objective of this research was to develop a systematic method of predicting PCO rate constants by correlating rate constants with physical-chemical characteristics of compounds. Accordingly, reaction rate constants were determined for destruction of volatile organics over a titanium dioxide (TiO2) catalyst in a continuous mixed-batch reactor. It was found that PCO rate constants for alkanes and alkenes vary linearly with gas-phase ionization potential (IP) and with gas-phase hydroxyl radical reaction rate constant. The correlations allow rates of destruction of compounds not tested in this research to be predicted based on physical-chemical characteristics. PMID:12568248

  12. Polyelectrolyte-surfactant complexes formed by poly[3,5-bis(trimethylammoniummethyl)4-hydroxystyrene iodide]-block-poly(ethylene oxide) and sodium dodecyl sulfate in aqueous solutions.

    PubMed

    Štěpánek, Miroslav; Matějíček, Pavel; Procházka, Karel; Filippov, Sergey K; Angelov, Borislav; Šlouf, Miroslav; Mountrichas, Grigoris; Pispas, Stergios

    2011-05-01

    Formation of polyelectrolyte-surfactant (PE-S) complexes of poly[3,5-bis(trimethylammoniummethyl)-4-hydroxystyrene iodide]-block-poly(ethylene oxide) (QNPHOS-PEO) and sodium dodecyl sulfate (SDS) in aqueous solution was studied by dynamic and electrophoretic light scattering, small-angle X-ray scattering (SAXS), atomic force microscopy, and fluorometry, using pyrene as a fluorescent probe. SAXS data from the QNPHOS-PEO/SDS solutions were fitted assuming contributions from free copolymer, PE-S aggregates described by a mass fractal model, and densely packed surfactant micelles inside the aggregates. It was found that, unlike other systems of a double hydrophilic block polyelectrolyte and an oppositely charged surfactant, PE-S aggregates of the QNPHOS-PEO/SDS system do not form core-shell particles and the PE-S complex precipitates before reaching the charge equivalence between dodecyl sulfate anions and QNPHOS polycationic blocks, most likely because of conformational rigidity of the QNPHOS blocks, which prevents the system from the corresponding rearrangement. PMID:21446735

  13. Immobilization of Metal-Organic Framework Copper(II) Benzene-1,3,5-tricarboxylate (CuBTC) onto Cotton Fabric as a Nitric Oxide Release Catalyst.

    PubMed

    Neufeld, Megan J; Harding, Jacqueline L; Reynolds, Melissa M

    2015-12-01

    Immobilization of metal-organic frameworks (MOFs) onto flexible polymeric substrates as secondary supports expands the versatility of MOFs for surface coatings for the development of functional materials. In this work, we demonstrate the deposition of copper(II) benzene-1,3,5-tricarboxylate (CuBTC) crystals directly onto the surface of carboxyl-functionalized cotton capable of generating the therapeutic bioagent nitric oxide (NO) from endogenous sources. Characterization of the CuBTC-cotton material by XRD, ATR-IR, and UV-vis indicate that CuBTC is successfully immobilized on the cotton fabric. In addition, SEM imaging reveals excellent surface coverage with well-defined CuBTC crystals. Subsequently, the CuBTC-cotton material was evaluated as a supported heterogeneous catalyst for the generation of NO using S-nitrosocysteamine as the substrate. The resulting reactivity is consistent with the activity observed for unsupported CuBTC particles. Overall, this work demonstrates deposition of MOFs onto a flexible polymeric material with excellent coverage as well as catalytic NO release from S-nitrosocysteamine at therapeutic levels. PMID:26595600

  14. Formation of highly oxidized multifunctional organic compounds from anthropogenic volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Molteni, Ugo; Baltensperger, Urs; Bianchi, Federico; Dommen, Josef; El Haddad, Imad; Frege, Carla; Klein, Felix; Rossi, Michel

    2016-04-01

    Recent studies have shown that highly oxidized multifunctional organic compounds (HOMs) from biogenic volatile organic compounds are important for new particle formation and early particle growth (e.g., Ehn et al., 2014). The formation mechanism has extensively been studied for biogenic precursors like alpha-pinene and was shown to proceed through an initial reaction with either OH radicals or ozone followed by radical propagation in a mechanism that involves O2 attack and hydrogen abstraction (Crounse et al., 2013). While the same processes can be expected for anthropogenic volatile organic compounds (AVOC), few studies have investigated these so far. Here we present the formation of HOMs from a variety of aromatic compounds after reaction with OH. All the compounds analyzed show HOM formation. AVOC could therefore play an important role in new particle formation events that have been detected in urban areas. References Crounse, J.D. et al., Autoxidation of organic compounds in the atmosphere. J. Phys.Chem. Lett. 4, 3513-3520 (2013). Ehn, M., et al. A large source of low-volatility secondary organic aerosol, Nature 506, 476-479 (2014).

  15. Molecular structure, quantum mechanical calculation and radical scavenging activities of (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds

    NASA Astrophysics Data System (ADS)

    Alaşalvar, Can; Soylu, Mustafa Serkan; Güder, Aytaç; Albayrak, Çiğdem; Apaydın, Gökhan; Dilek, Nefise

    2014-09-01

    In this study, (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds have been synthesized and characterized by using X-ray crystallographic method, FT-IR and Density functional method. The molecular geometry, vibrational frequencies of the title compounds in the ground state have been calculated by using B3LYP with the 6-31G(d,p) basis set. The tautomeric form of the compounds has been demonstrated by using single crystal X-ray method, FT-IR spectrometer and DFT method. In addition, HOMO-LUMO energy gap, molecular electrostatic potential map and NBO analysis of the compounds are performed at B3LYP/6-31G(d,p) level. It may be remarked that the free radical scavenging activities of the title compounds were assessed using DPPHrad , DMPDrad +, and ABTSrad + assays. The obtained results show that especially compound 2 has effective DPPHrad (SC50 1.52 ± 0.14 μg/mL), DMPDrad + (SC50 1.22 ± 0.21 μg/mL), and ABTSrad + (SC50 3.32 ± 0.17 μg/mL) scavenging activities compared with standards (BHA, rutin, and trolox).

  16. Determination of an Effective Perfluorinated Compounds (PFCs) Oxidation Method

    NASA Astrophysics Data System (ADS)

    Siriwardena, D. P.; Crimi, M.; Holsen, T.; Bellona, C.

    2014-12-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a stable synthetic class of chemicals ubiquitously spread in environmental media (i.e. air, soil, biota, surface water and groundwater). The substances' strong polar carbon-fluorine bonds and their high thermal and chemical stability make them resistant to biological, chemical, and physical degradation. The purpose of this research is to identify the most effective oxidation method to treat perfluorinated compounds (PFCs) and their by-products that is suitable for in situ application. The laboratory oxidation study focuses on the more commonly detected and studied long-chain (C-8) PFAS; perfluorooctanoic acids (PFOA) and perfluorooctane sulfonic acid (PFOS). Existing research evaluating oxidizing treatment effectiveness on perfluoroalkyl sulfoinoic acids (PFSAs) is limited. A review of the literature and results from preliminary studies indicate that activated persulfate and catalyzed hydrogen peroxide propagation (CHP) reactions appear to be promising oxidants for PFOA. It has been demonstrated that the reactivity of superoxide in water increases in the presence of hydrogen peroxide (H2O2) and solids. Superoxide generated in CHP reactions degrades PFOA seemingly similar to superoxide-mediated destruction of the perhalogenated compounds.The goal of this study is to look at conditions that promote generation of superoxide and look at PFASs treatment effectiveness and byproduct generation. CHP reactions are conducted with varying amount of H2O2 and Fe(III) to determine the optimum conditions for PFC degradation. Results will be compared to those of another experiment using manganese dioxide as a CHP catalyst with varied H2O2 concentration to generate superoxide to degrade PFASs. Activated persulfate conditions to be compared include alkaline pH activation, heat activation, and dual oxidation (combined H2O2 and persulfate ). This presentation will focus on a comparison of oxidation effectiveness under the

  17. Effects of 3,5-Diiodotyrosine and Potassium Iodide on Thyroid Function and Oxidative Stress in Iodine-Excess Wistar Rats.

    PubMed

    Liu, Dan; Lin, Xinying; Yu, Fugui; Zhang, Man; Chen, Hongxia; Bao, Wei; Wang, Xia

    2015-12-01

    The objective of this study was to investigate the effects of organic iodine (3,5-diiodotyrosine, DIT) and inorganic iodine (potassium iodine, KI) on thyroid function and oxidative stress in iodine-excess Wistar rats. Seventy-two Wistar rats were randomly divided into eight groups: normal control (NC), thyroid tablet-induced hyperthyroidism model (HM), low DIT (L-DIT), medium DIT (M-DIT), high DIT (H-DIT), low KI (L-KI), medium KI (M-KI), and high KI (H-KI). All rats were fed ad libitum for 30 days. Morphological changes in the thyroid, absolute and relative weights of the thyroid, thyroid function markers free triiodothyronine (FT3) and free thyroxine (FT4), urinary iodine level, and oxidative stress indicators were measured. Compared to the HM groups, the FT3 and FT4 levels decreased in the L-DIT groups; the thyroid weight and thyroid weight/body weight values decreased markedly in the L-DIT and M-DIT groups; serum superoxide dismutase/malondialdehyde increased markedly; glutathione peroxidase activity increased markedly in the L-DIT groups; and malondialdehyde levels decreased significantly in the M-DIT groups. However, the FT3 and FT4 levels decreased and glutathione peroxidase levels increased significantly in the DIT groups compared to their corresponding KI groups. Additionally, urinary iodine levels increased significantly in both DIT and KI groups, while the highest urinary iodine excretion was showed in the DIT groups among groups. When the addition of iodine with the same doses in iodine-excess rats, although neither DIT nor KI normalized iodine levels in the iodine-excess rats, the DIT did less damage than did KI to thyroid follicular cells. Therefore, DIT rather than KI had a protective effect by balancing the antioxidant system when exposed to supraphysiological iodine. These suggest that DIT may be used as a new alternative iodized salt in the universal salt iodization to avoid the potential damage of surplus KI. PMID:26002813

  18. Catalytic oxidation of volatile organic compounds (VOCs) - A review

    NASA Astrophysics Data System (ADS)

    Kamal, Muhammad Shahzad; Razzak, Shaikh A.; Hossain, Mohammad M.

    2016-09-01

    Emission of volatile organic compounds (VOCs) is one of the major contributors to air pollution. The main sources of VOCs are petroleum refineries, fuel combustions, chemical industries, decomposition in the biosphere and biomass, pharmaceutical plants, automobile industries, textile manufacturers, solvents processes, cleaning products, printing presses, insulating materials, office supplies, printers etc. The most common VOCs are halogenated compounds, aldehydes, alcohols, ketones, aromatic compounds, and ethers. High concentrations of these VOCs can cause irritations, nausea, dizziness, and headaches. Some VOCs are also carcinogenic for both humans and animals. Therefore, it is crucial to minimize the emission of VOCs. Among the available technologies, the catalytic oxidation of VOCs is the most popular because of its versatility of handling a range of organic emissions under mild operating conditions. Due to that fact, there are numerous research initiatives focused on developing advanced technologies for the catalytic destruction of VOCs. This review discusses recent developments in catalytic systems for the destruction of VOCs. Review also describes various VOCs and their sources of emission, mechanisms of catalytic destruction, the causes of catalyst deactivation, and catalyst regeneration methods.

  19. Release of substituents from phenolic compounds during oxidative coupling reactions.

    PubMed

    Dec, Jerzy; Haider, Konrad; Bollag, Jean-Marc

    2003-07-01

    Phenolic compounds originating from plant residue decomposition or microbial metabolism form humic-like polymers during oxidative coupling reactions mediated by various phenoloxidases or metal oxides. Xenobiotic phenols participating in these reactions undergo either polymerization or binding to soil organic matter. Another effect of oxidative coupling is dehalogenation, decarboxylation or demethoxylation of the substrates. To investigate these phenomena, several naturally occurring and xenobiotic phenols were incubated with various phenoloxidases (peroxidase, laccase, tyrosinase) or with birnessite (delta-MnO(2)), and monitored for chloride release, CO(2) evolution, and methanol or methane production. The release of chloride ions during polymerization and binding ranged between 0.2% and 41.4%. Using the test compounds labeled with 14C in three different locations (carboxyl group, aromatic ring, or aliphatic chain), it was demonstrated that 14CO(2) evolution was mainly associated with the release of carboxyl groups (17.8-54.8% of the initial radioactivity). Little mineralization of 14C-labeled aromatic rings or aliphatic carbons occurred in catechol, ferulic or p-coumaric acids (0.1-0.7%). Demethoxylation ranged from 0.5% to 13.9% for 2,6-dimethoxyphenol and syringic acid, respectively. Methylphenols showed no demethylation. In conclusion, dehalogenation, decarboxylation and demethoxylation of phenolic substrates appear to be controlled by a common mechanism, in which various substituents are released if they are attached to carbon atoms involved in coupling. Electron-withdrawing substituents, such as -COOH and -Cl, are more susceptible to release than electron-donating ones, such as -OCH(3) and -CH(3). The release of organic substituents during polymerization and binding of phenols may add to CO(2) production in soil. PMID:12738292

  20. Treated Nanolayered Mn Oxide by Oxidizable Compounds: A Strategy To Improve the Catalytic Activity toward Water Oxidation.

    PubMed

    Mahdi Najafpour, Mohammad; Jafarian Sedigh, Davood; Maedeh Hosseini, Seyedeh; Zaharieva, Ivelina

    2016-09-01

    Herein, we investigate the effect of post-treatment of nanolayered manganese oxide by different inorganic and organic compounds. We use the fact that nanolayered manganese oxides are among the strongest naturally occurring oxidants, capable of oxidizing a wide range of organic molecules. Post-treatment of the synthetic Mn oxides with oxidizable compounds increases the cerium(IV)-driven water oxidation catalyzed by treated layered manganese oxides more than 25 times. On the basis of X-ray absorption investigations, we attribute this effect to the increased amount of manganese(III) ions. This finding can explain some puzzles in water oxidation by manganese oxides and may help to advance toward an efficient design strategy of water-oxidizing catalyst in artificial photosynthetic systems. PMID:27537432

  1. Chemical process for the catalytic oxidation of formaldehyde and other organic compounds

    SciTech Connect

    Murphy, A.P.

    1991-01-01

    The invention discusses a chemical process for the catalytic oxidation of formaldehyde and other organic compounds contained in a dilute aqueous solution, particularly waste water. The inventive feature resides in the use of a cobalt catalyst to increase the rate of oxidation of the organic compounds when hypochlorous acid is the oxidant. The latter may be provided by a chlorine compound, such as sodium hypochlorite, calcium hypochlorite or chlorine gas dissolved in water.

  2. Effects of Post-Pyrolysis Air Oxidation of Biomass Chars on Adsorption of Neutral and Ionizable Compounds.

    PubMed

    Xiao, Feng; Pignatello, Joseph J

    2016-06-21

    This study was conducted to understand the effects of thermal air oxidation of biomass chars experienced during formation or production on their adsorptive properties toward various compounds, including five neutral nonpolar and polar compounds and seven weak acids and bases (pKa = 3-5.2) selected from among industrial chemicals and the triazine and phenoxyacetic acid herbicide classes. Post-pyrolysis air oxidation (PPAO) at 400 °C of anoxically prepared wood and pecan shell chars for up to 40 min enhanced the mass-normalized adsorption at pH ∼ 7.4 of all test compounds, especially the weak acids and bases, by up to 100-fold. Both general and specific effects were identified. The general effect results from "reaming" of pores by the oxidative removal of pore wall matter and/or tarry deposits generated during the pyrolysis step. Reaming creates new surface area and enlarges nanopores, which helps relieve steric hindrance to adsorption. The specific effect results from creation of new acidic functionality that provides sites for the formation of very strong, charge-assisted hydrogen bonds (CAHB) with solutes having comparable pKa. The CAHB hypothesis was supported by competition experiments and the finding that weak acid anion adsorption increased with surface carboxyl content, despite electrostatic repulsion from the growing negative charge. The results provide insight into the effects of air oxidation on pollutant retention. PMID:27152745

  3. [Health effect of volatile aldehyde compounds in photocatalytic oxidation of aromatics compounds].

    PubMed

    Zhao, Wei-rong; Liao, Qiu-wen; Yang, Ya-nan; Dai, Jiu-song

    2013-05-01

    Photocatalytic oxidation (PCO) of toluene and benzaldehyde in indoor air by N doped TiO2 (N-TiO2) was conducted under UV irradiation of 254 nm. The intermediates were identified and monitored on real-time by proton transfer reaction-mass spectrometry. The health risks of PCO of toluene and benzaldehyde were assessed based on health risk influence index (eta). Results indicated that both the conversion rate and mineralization rate of toluene and benzaldehyde were relatively high, however, the volatile aldehyde compounds (VAs), including acetaldehyde and formaldehyde generated from ring-opening, significantly influenced the health risks of PCO of toluene and benzaldehyde. Acetaldehyde played a crucial role on health risks, which was inclined to desorb from the surface of catalysts, accumulate in gas-phase, and increase the health risks of PCO of the aromatic compounds. The concentration of formaldehyde kept stable at a relatively low level, however its impact cannot be neglected. In the PCO process of toluene and benzaldehyde, eta reached the maximum values of 8 499.68 and 21.43, with the eta(VAs), contribution of VAs to the health risk influence index of outlet, reaching 99.3% and 98.3%, respectively. The average values of eta in the PCO process of 30 min were 932.86 and 8.52, and for which eta(VAs), reached 98.5% and 98.0%, respectively. When PCO of toluene and benzaldehyde reached steady state, eta were 236.09 and 2.30, and eta(VAs) reached 97.9% and 97.8%, respectively. Hence, eta(VAs), can be taken as a characteristic parameter in assessment of health risks of PCO of aromatic compounds. PMID:23914541

  4. Inhibitory effects of sulfur compounds on methane oxidation by a methane-oxidizing consortium.

    PubMed

    Lee, Eun-Hee; Moon, Kyung-Eun; Kim, Tae Gwan; Lee, Sang-Don; Cho, Kyung-Suk

    2015-12-01

    Kinetic and enzymatic inhibition experiments were performed to investigate the effects of methanethiol (MT) and hydrogen sulfide (H2S) on methane oxidation by a methane-oxidizing consortium. In the coexistence of MT and H2S, the oxidation of methane was delayed until MT and H2S were completely degraded. MT and H2S could be degraded, both with and without methane. The kinetic analysis revealed that the methane-oxidizing consortium showed a maximum methane oxidation rate (Vmax) of 3.7 mmol g-dry cell weight (DCW)(-1) h(-1) and a saturation constant (Km) of 184.1 μM. MT and H2S show competitive inhibition on methane oxidation, with inhibition values (Ki) of 1504.8 and 359.8 μM, respectively. MT was primary removed by particulate methane monooxygenases (pMMO) of the consortium, while H2S was degraded by the other microorganisms or enzymes in the consortium. DNA and mRNA transcript levels of the pmoA gene expressions were decreased to ∼10(6) and 10(3)pmoA gene copy number g-DCW(-1) after MT and H2S degradation, respectively; however, both the amount of the DNA and mRNA transcript recovered their initial levels of ∼10(7) and 10(5)pmoA gene copy number g-DCW(-1) after methane oxidation, respectively. The gene expression results indicate that the pmoA gene could be rapidly reproducible after methane oxidation. This study provides comprehensive information of kinetic interactions between methane and sulfur compounds. PMID:26143035

  5. IRIS Toxicological Review of Cerium Oxide and Cerium Compounds (Interagency Science Discussion Draft)

    EPA Science Inventory

    On September 29, 2009, the IRIS Summary and Toxicological Review of Cerium Oxide and Cerium Compounds was finalized and loaded onto the IRIS database. The Toxicological Review of Cerium Oxide and Cerium Compounds was reviewed internally by EPA, by other federal agencies and Whit...

  6. Theoretical studies on vicinal-tetrazine compounds: furoxano-1,2,3,4-tetrazine-1,3,5-trioxide (FTTO-α) and furoxano-1,2,3,4-tetrazine-1,3,7-trioxide (FTTO-β).

    PubMed

    Wang, Tianyi; Zhang, Tao; Xu, Liwen; Wu, Xionghui; Gong, Xuedong; Xia, Mingzhu

    2014-12-01

    The derivatives of 1,2,3,4-tetrazine may be promising candidates of high-energy density compounds and are receiving more and more attention. In this study, two 1,2,3,4-tetrazines, furoxano-1,2,3,4-tetrazine-1,3,5-trioxide (FTTO-α) and furoxano-1,2,3,4-tetrazine-1,3,7-trioxide (FTTO-β), were theoretically studied. The geometrical structures in gas phase were studied at the B3LYP/6-311++G(d,p) level of density functional theory (DFT). The gas phase enthalpies of formation were calculated by the homodesmotic reaction method. The enthalpies of sublimation and solid phase enthalpies of formation were predicted with corrections of electrostatic potential method at the B3PW91/6-31G(d,p) level. The detonation properties were estimated with the Kamlet-Jacobs equations based on the predicted densities and enthalpies of formation in solid state. The available free space in the lattice was calculated to evaluate their stability. Calculations of potential energy surface and structure interconversion thermodynamics under different temperatures were carried out to further confirm their stability. FTTOs have better performance than HMX and FTDO but are easy to decompose to 5,6-dinitroso-v-tetrazine 1,3-dioxide. A synthesis route for FTTO-β was proposed to provide a consideration for the further study. We believe FTTOs could be the key compounds to synthesize other v-tetrazines such as TTTO. PMID:25413679

  7. Unexpectedly Stable (Chlorocarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, and Related Compounds That Model the Zumach-Weiss-Kühle (ZWK) Reaction for Synthesis of 1,2,4-Dithiazolidine-3,5-diones.

    PubMed

    Barany, George; Britton, Doyle; Chen, Lin; Hammer, Robert P; Henley, Matthew J; Schrader, Alex M; Young, Victor G

    2015-11-20

    The Zumach-Weiss-Kühle (ZWK) reaction provides 1,2,4-dithiazolidine-3,5-diones [dithiasuccinoyl (Dts)-amines] by the rapid reaction of O-ethyl thiocarbamates plus (chlorocarbonyl)sulfenyl chloride, with ethyl chloride and hydrogen chloride being formed as coproducts, and carbamoyl chlorides or isocyanates generated as yield-diminishing byproducts. However, when the ZWK reaction is applied with (N-ethoxythiocarbonyl)urethane as the starting material, heterocyclization to the putative "Dts-urethane" does not occur. Instead, the reaction directly provides (chlorocarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, a reasonably stable crystalline compound; modified conditions stop at the (chlorocarbonyl)[1-ethoxy-(N-ethoxycarbonyl)formimidoyl]disulfane intermediate. The title (chlorocarbonyl)(carbamoyl)disulfane cannot be converted to the elusive Dts derivative, but rather gives (N-ethoxycarbonyl)carbamoyl chloride upon thermolysis, or (N-ethoxycarbonyl)isocyanate upon treatment with tertiary amines. Additional transformations of these compounds have been discovered, providing entries to both known and novel species. X-ray crystallographic structures are reported for the title (chlorocarbonyl)(carbamoyl)disulfane; for (methoxycarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, which is the corresponding adduct after quenching in methanol; for [1-ethoxy-(N-ethoxycarbonyl)formimidoyl](N'-methyl-N'-phenylcarbamoyl)disulfane, which is obtained by trapping the title intermediate with N-methylaniline; and for (N-ethoxycarbonylcarbamoyl)(N'-methyl-N'-phenylcarbamoyl)disulfane, which is a short-lived intermediate in the reaction of the title (chlorocarbonyl)(carbamoyl)disulfane with excess N-methylaniline. The new chemistry and structural information reported herein is expected to contribute to accurate modeling of the ZWK reaction trajectory. PMID:26418818

  8. Theoretical studies on a new high energy density compound 6-amino-7-nitropyrazino[2,3-e][1,2,3,4]tetrazine 1,3,5-trioxide (ANPTTO).

    PubMed

    Wang, Tianyi; Zheng, Chunmei; Yang, Junqing; Zhang, Xueli; Gong, Xuedong; Xia, Mingzhu

    2014-06-01

    The derivatives of 1,2,3,4-tetrazine may be promising candidates for high-energy density compounds and are receiving more and more attentions. In this study, a new derivative 6-amino-7-nitropyrazino[2,3-e][1,2,3,4]tetrazine 1,3,5-trioxide (ANPTTO) has been designed. The geometrical structure and IR spectrum in the gas phase were studied at the B3LYP/6-31G* level of density functional theory (DFT). The crystal structure was predicted by molecular mechanics method and refined by the GGA/BOP function of periodic DFT with the basis set of TNP. The gas phase enthalpy of formation was calculated by the homodesmotic reaction method. The enthalpy of sublimation and solid phase enthalpy of formation were also predicted. The detonation properties were estimated with the Kamlet-Jacobs equations based on the predicted density and enthalpy of formation in solid state. The available free space in the lattice and resonance energy were calculated to evaluate its stability. ANPTTO has a high stability and is a promising high energetic component with the density >2 g · cm(-3), detonation velocity >9000 m · s(-1), and detonation pressure >40 GPa. A synthetic route was proposed to provide a consideration for further study. PMID:24859447

  9. The water soluble ruthenium(II) organometallic compound [Ru(p-cymene)(bis(3,5 dimethylpyrazol-1-yl)methane)Cl]Cl suppresses triple negative breast cancer growth by inhibiting tumor infiltration of regulatory T cells.

    PubMed

    Montani, Maura; Pazmay, Gretta V Badillo; Hysi, Albana; Lupidi, Giulio; Pettinari, Riccardo; Gambini, Valentina; Tilio, Martina; Marchetti, Fabio; Pettinari, Claudio; Ferraro, Stefano; Iezzi, Manuela; Marchini, Cristina; Amici, Augusto

    2016-05-01

    Ruthenium compounds have become promising alternatives to platinum drugs by displaying specific activities against different cancers and favorable toxicity and clearance properties. Here, we show that the ruthenium(II) complex [Ru(p-cymene)(bis(3,5-dimethylpyrazol-1-yl)methane)Cl]Cl (UNICAM-1) exhibits potent in vivo antitumor effects. When administered as four-dose course, by repeating a single dose (52.4mgkg-1) every three days, UNICAM-1 significantly reduces the growth of A17 triple negative breast cancer cells transplanted into FVB syngeneic mice. Pharmacokinetic studies indicate that UNICAM-1 is rapidly eliminated from kidney, liver and bloodstream thanks to its high hydrosolubility, exerting excellent therapeutic activity with minimal side effects. Immunohistological analysis revealed that the efficacy of UNICAM-1, mainly relies on its capacity to reverse tumor-associated immune suppression by significantly reducing the number of tumor-infiltrating regulatory T cells. Therefore, UNICAM-1 appears very promising for the treatment of TNBC. PMID:27038531

  10. Preparation and properties of a compound containing nickel in highest oxidation states

    SciTech Connect

    Nikol'skii, V.A.; Bekreneva, L.A.; Garmash, L.A.; Makashev, Yu.A.; Mikhailova, K.A.; Raikhel'son, L.B.; Shchelkunova, L.I.

    1986-04-10

    The purpose of this paper is to obtain nickel hydroxide oxide of the optimal composition both by chemical and by electrochemical oxidation for use as the cathode material in alkaline batteries. The authors selected the oxidation conditions (oxidant, component ratio) for production of gamma-NiOOH; hydrogen peroxide, potassium permanganate, and potassium persulfate were used as oxidants. Gamma-NiOOH was also obtained by electrochemical oxidation of nickel (II) oxide hydrate in alkaline solutions. In samples obtained by electrochemical oxidation virtually 100% of the nickel is in the highly oxidized state. It is shown that gamma-NiOOH obtained by both chemical and electrochemical oxidation is a complex individual compound containing nickel and in the highest oxidation states, Ni/sup 3 +/ and Ni/sup 4 +/, together with salt-forming potassium ions and water molecules. The gamma-NiOOH obtained may be used with success in galvanic cells.

  11. pH-dependent one- and two-electron oxidation of 3,5-dicarbethoxy-2,6-dimethyl-4-ethyl-1,4-dihydropyridine catalyzed by horseradish peroxidase.

    PubMed

    Sugiyama, K; Correia, M A; Thummel, K E; Nagata, K; Darbyshire, J F; Osawa, Y; Gillette, J R

    1994-01-01

    The porphyrinogenic agent 3,5-dicarbethoxy-2,6-dimethyl-4-ethyl-1,4-dihydropyridine (DDEP) is known to inactivate hepatic cytochrome P450 (P450) enzymes 2C11, 2C6, and 3A1 [Correia et al. (1987) Arch. Biochem. Biophys. 258, 436-451] by different mechanisms. The inactivation of P450 2C11 and 2C6 appears to be due to the ethylation of the heme in the active sites of the enzymes [Augusto et al. (1982) J. Biol. Chem. 257, 11288-11295], whereas the inactivation of P450 3A1 appears to involve the covalent binding of the heme to the apoprotein [Correia et al. (1987)]. Moreover, we have found that DDEP inactivates horseradish peroxidase (HRP) pretreated with hydrogen peroxide. In this system, DDEP was oxidized predominately to 3,5-dicarbethoxy-2,6-dimethyl-4-ethylpyridine (EDP) under weakly acidic conditions and predominately to 3,5-dicarbethoxy-2,6-dimethylpyridine (DP) under basic conditions. The loss of heme and the formation of altered heme products were also pH-dependent and were correlated with the formation of DP and the inactivation of HRP. Thus the inactivation of HRP appears to depend on the formation of an ethyl radical, which presumably reacts with the heme in the active site of the enzyme. Similar product ratios were obtained for the oxidation of DDEP by K3Fe(CN)6, indicating that product ratios of DP over EDP are mainly determined by the pH of buffer. These results, in addition to semiemperical calculations (AM1) for the oxidation of DDEP in the gas phase, are consistent with the idea that the inhibitor undergoes a single-electron oxidation to form the DDEP radical cation, the fate of which depends on the environment of the active site of the enzyme. The proposed formation of a radical cation by the abstraction of an electron from nitrogen is consistent with the finding of low intramolecular isotope effects of the metabolism of 3,5-dicarbethoxy-2,6-dimethyl-[4-2H,4-1H]-1,4-dihydropyridine by P450 2C11 and 3A4. Under basic or aprotic conditions, the radical

  12. Dynamics of oxidation of inorganic sulphur compounds in upper soil horizons of spruce forests.

    PubMed

    Lettl, A; Langkramer, O; Lochman, V

    1981-01-01

    Dynamics of oxidation of inorganic sulphur compounds to sulphate by the soil of spruce forests was investigated. Sulphide, sulphite and thiosulphate are oxidized to sulphate at a maximal rate at the beginning of the reaction, oxidation of elemental sulphur exhibits a lag phase. Linear relationships between the amounts of the produced sulphate and concentrations of substrates in the soil could be detected. On the basis of ;this finding a method for comparison of the oxidative activity of various soils was proposed. PMID:7203284

  13. A 3.5-4.5 GHz Complementary Metal-Oxide-Semiconductor Ultrawideband Receiver Frontend Low-Noise Amplifier with On-Chip Integrated Antenna for Interchip Communication

    NASA Astrophysics Data System (ADS)

    Azhari, Afreen; Kimoto, Kentaro; Sasaki, Nobuo; Kikkawa, Takamaro

    2010-04-01

    Chip-to-chip ultrawideband (UWB) wireless interconnections are essential for reducing resistance capacitance (RC) delay in wired interconnections and three-dimensional (3D) highly integrated packaging. In this study, we demonstrated a wireless interchip signal transmission between two on-chip meander antennas on printed circuit board (PCB) for 1 to 20 mm transmission distances where the low power gain of each antenna due to a lossy Si substrate has been amplified by a low-noise amplifier (LNA). The measured result shows that the LNA produces 26 dB of improvement in antenna power gain at 4.5 GHz on a lossy Si substrate. Moreover, a Gaussian monocycle pulse with a center frequency of 2.75 GHz was also received by an on-chip antenna and amplified by the LNA. The LNA was integrated with an on-chip antenna on a Si substrate with a resistivity of 10 Ω·cm using 180 nm complementary metal-oxide-semiconductor (CMOS) technology. The investigated system is required for future single chip transceiver front ends, integrated with an on-chip antenna for 3D mounting on a printed circuit (PC) board.

  14. Process for Producing Metal Compounds From Graphite Oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be fiber processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  15. Process for Producing Metal Compounds from Graphite Oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  16. Process for producing metal compounds from graphite oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  17. Phenolic compounds as enhancers in enzymatic and electrochemical oxidation of veratryl alcohol and lignins.

    PubMed

    Díaz-González, María; Vidal, Teresa; Tzanov, Tzanko

    2011-03-01

    Sixteen phenolic compounds, 14 of which naturally occurring, were compared to the synthetic 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and violuric acid (VA) in terms of their ability to act as mediators/enhancers in: (1) laccase oxidation of veratryl alcohol as a lignin model compound, and (2) electrochemical oxidation of kraft and flax lignins. HPLC analysis revealed that the syringyl-type phenols methyl syringate and acetosyringone were the most efficient natural enhancers in the laccase oxidation of veratryl alcohol. Both compounds, though far from the performance of ABTS were able to generate veratraldehyde in amount similar to that obtained with VA. By contrast, the best performing phenolic enhancers for the electrochemical oxidation of lignins were sinapinaldehyde, vanillin, acetovanillone, and syringic acid. Catalytic efficiencies close to those achieved with ABTS and VA were calculated for these phenolic compounds. PMID:21110019

  18. IRIS Toxicological Review of Cerium Oxide and Cerium Compounds (External Review Draft)

    EPA Science Inventory

    EPA conducted a peer review of the scientific basis supporting the human health hazard and dose-response assessment of cerium oxide and cerium compounds that will appear on the Integrated Risk Information System (IRIS) database.

  19. Mononuclear and dinuclear osmium(II) compounds containing 2,2 prime -bipyridine and 3,5-bis(pyridin-2-yl)-1,2,4-triazole: Synthesis, electrochemistry, absorption spectra, and luminescence properties

    SciTech Connect

    Barigelletti, F.; De Cola, L. ); Balzani, V. )); Hage, R.; Haasnoot, J.G.; Reedijk, J. ); Vos, J.G. )

    1991-02-20

    The synthesis, structure, electrochemical behavior, absorption spectra, luminescence spectra (from 90 to 298 K), luminescence lifetimes (from 90 to 298 K), and photoreactivity of the complexes Os(bpy){sub 2}(bpt){sup +} (1) and (Os(bpy){sub 2}){sub 2}(bpt){sup 3+} (2), where by = 2,2{prime}-bipyridine and Hbpt = 3,5-bis(pyridin-2-yl)-1,2,4-triazole, are reported. The properties exhibited by 1 and 2 are compared with those of Os(bpy){sub 3}{sup 2+} and of the analogous Ru(II) complexes. For both 1 and 2, the lowest energy absorption band and the luminescence band are attributed to Os {yields} bpy metal-to-ligand charge-transfer (MLCT) singlet and triplet excited states, respectively. Electrochemical oxidation is centered on the metal(s), and electrochemical reduction is centered on the ligands, with bpy being reduced at less negative potentials than bpt{sup {minus}}. Because of the stronger {sigma}-donor ability of bpt{sup {minus}} compared with bpy, the Os {yields} bpy CT absorption and emission bands of 1 are red-shifted compared with those of the parent Os(bpy){sub 3}{sup 2+} complex. In nitrile rigid matrix at 90 K, the emission lifetimes are 250 and 340 ns for 1 and 2, respectively. For both complexes, increasing temperature causes a decrease of the emission lifetime but the ln (1/{tau}) vs 1/T plots between 90 and 298 K do not exhibit the highly activated decay processes characteristic of the {sup 3}MLCT {yields} {sup 3}MC crossover. In agreement with this result, no photodecomposition was observed in CH{sub 2}Cl{sub 2} solutions containing Cl{sup {minus}} ions.

  20. Fluorine compounds for doping conductive oxide thin films

    SciTech Connect

    Gessert, Tim; Li, Xiaonan; Barnes, Teresa M; Torres, Jr., Robert; Wyse, Carrie L

    2013-04-23

    Methods of forming a conductive fluorine-doped metal oxide layer on a substrate by chemical vapor deposition are described. The methods may include heating the substrate in a processing chamber, and introducing a metal-containing precursor and a fluorine-containing precursor to the processing chamber. The methods may also include adding an oxygen-containing precursor to the processing chamber. The precursors are reacted to deposit the fluorine-doped metal oxide layer on the substrate. Methods may also include forming the conductive fluorine-doped metal oxide layer by plasma-assisted chemical vapor deposition. These methods may include providing the substrate in a processing chamber, and introducing a metal-containing precursor, and a fluorine-containing precursor to the processing chamber. A plasma may be formed that includes species from the metal-containing precursor and the fluorine-containing precursor. The species may react to deposit the fluorine-doped metal oxide layer on the substrate.

  1. VOLATILE ORGANIC COMPOUNDS AND ISOPRENE OXIDATION PRODUCTS AT A TEMPERATE DECIDUOUS FOREST SITE

    EPA Science Inventory

    Biogenic volatile compounds (BVOCs) and their role in atmospheric oxidant formation were investigated at a forest site near Oak Ridge, Tennessee, as part of the Nashville Southern Oxidants Study (SOS) in July 1995. Of 98 VOCs detected, a major fraction were anthropogenic VOCs suc...

  2. IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR CERIUM OXIDE (STABLE) AND COMPOUNDS

    EPA Science Inventory

    Cerium is a member of the lanthanoid series of rare earth metals. It is also the most abundant and most reactive of the rare earth metals. Cerium oxidizes at room temperature and forms a variety of salt compounds including oxides, hydroxides, sulfates and chlorides. Cerium is ...

  3. Magnetic and structural properties of yellow europium oxide compound and Eu(OH){sub 3}

    SciTech Connect

    Lee, Dongwook; Seo, Jiwon; Valladares, Luis de los Santos; Avalos Quispe, O.; Barnes, Crispin H.W.

    2015-08-15

    A new material based on a yellow europium oxide compound was prepared from europium oxide in a high vacuum environment. The structural and magnetic properties of the material were investigated. Owing to the absence of a crystal structure, the material exhibited a disordered magnetic behavior. In a reaction with deionized (DI) water without applied heat, the compound assumed a white color as soon as the DI water reached the powder, and the structure became polycrystalline Eu(OH){sub 3}. The magnetic properties, such as the thermal hysteresis, disappeared after the reaction with DI water, and the magnetic susceptibility of the yellow oxide compound weakened. The magnetic properties of Eu(OH){sub 3} were also examined. Although Eu{sup 3+} is present in Eu(OH){sub 3}, a high magnetic moment due to the crystal field effect was observed. - Graphical abstract: (top left) Optical image of the yellow europium oxide compound. (top right) Optical image of the product of DI water and yellow europium oxide. (bottom) Magnetization curves as a function of temperature measured in various magnetic field. - Highlights: • We prepared a new material based on a yellow europium oxide compound from europium oxide. • We characterized the magnetic properties of the material which exhibits a disordered magnetic behavior such as thermal hysteresis. • The compound turned white (Eu(OH){sub 3}) as soon as the DI water reached the powder. • The thermal hysteresis disappeared after the reaction with DI water and the magnetic susceptibility of the yellow oxide compound weakened.

  4. Phenolic mediators enhance the manganese peroxidase catalyzed oxidation of recalcitrant lignin model compounds and synthetic lignin.

    PubMed

    Nousiainen, Paula; Kontro, Jussi; Manner, Helmiina; Hatakka, Annele; Sipilä, Jussi

    2014-11-01

    Fungal oxidative enzymes, such as peroxidases and laccases, are the key catalysts in lignin biodegradation in vivo, and consequently provide an important source for industrial ligninolytic biocatalysts. Recently, it has been shown that some syringyl-type phenolics have potential as industrial co-oxidants or mediators, in laccase-catalyzed modification of lignocellulosic material. We have now studied the effect of such mediators with ligninolytic peroxidases on oxidation of the most recalcitrant lignin model compounds. We found that they are able to enhance the manganese peroxidase (MnP) catalyzed oxidation reactions of small non-phenolic compounds, veratryl alcohol and veratrylglycerol β-guaiacyl ether (adlerol), which are not usually oxidized by manganese peroxidases alone. In these experiments we compared two peroxidases from white-rot fungi, MnP from Phlebia sp. Nf b19 and versatile peroxidase (VP) from Bjerkandera adusta under two oxidation conditions: (i) the Mn(III) initiated mediated oxidation by syringyl compounds and (ii) the system involving MnP-dependent lipid peroxidation, both with production of (hydrogen) peroxides in situ to maintain the peroxidase catalytic cycle. It was found that both peroxidases produced α-carbonyl oxidation product of veratryl alcohol in clearly higher yields in reactions mediated by phenoxy radicals than in lipid-peroxyl radical system. The oxidation of adlerol, on the other hand, was more efficient in lipid-peroxidation-system. VP was more efficient than MnP in the oxidation of veratryl alcohol and showed its lignin peroxidase type activity in the reaction conditions indicated by some cleavage of Cα-Cβ-bond of adlerol. Finally, the mediator assisted oxidation conditions were applied in the oxidation of synthetic lignin (DHP) and the structural analysis of the oxidized polymers showed clear modifications in the polymer outcome, e.g. the oxidation resulted in reduced amount of aliphatic hydroxyls indicated by (31)P NMR. PMID

  5. Formation of highly oxidized multifunctional compounds: Autoxidation of peroxy radicals formed in the oxidation of alkenes

    NASA Astrophysics Data System (ADS)

    Mentel, Thomas; Ehn, Mikael; Thornton, Joel; Kleist, Einhard; Pullinen, Iida; Springer, Monika; Wahner, Andreas; Wildt, Jürgen

    2015-04-01

    Recent studies show that peroxy radicals are key intermediates in particle formation. Permutation reactions involving highly oxidized peroxy radicals form stable products with extremely low volatility (ELVOC). We suggest that ELVOC are the postulated organic compounds that explain growth of small particles (Ehn et al., Nature, 2014). To elucidate the pathways of ELVOC formation, experiments were performed in the Juelich Plant Atmosphere Chamber. We applied High Resolution Nitrate-Chemical Ionization Mass Spectrometry for detection of ELVOC including highly oxidized peroxy radicals. ELVOC were produced by ozonolysis of a-pinene and other cyclic alkenes (Rissanen et al., JACS, 2014, Mentel et al., ACPD, 2015), as well as by reactions of the target compounds with OH. ELVOC with C10 skeletons carry a large number of oxygens, still containing 14 or 16 H-atoms. ELVOC-dimers with twice the number of C-atoms of the reactant were also observed. The formation of ELVOC can be explained by fast intramolecular H-shifts in combination with classical peroxy radical termination reactions, leading to ketones, alcohols, and hydroperoxides (including peroxy acids). The subsequent H-shifts enable the formation of an increasing number of hydroperoxide groups under reproduction of a peroxy radical (containing now two more oxygens). Addition of NOX to the system increases the concentrations of nitrates at the expense of the corresponding peroxy radicals, confirming their identification as peroxy radicals. Furthermore, the concentrations of ELVOC dimers decrease strongly with increasing NOX suggesting that they are indeed formed by peroxy-peroxy permutation reactions. ELVOC are involved in new particle formation, and can explain the major fraction of the early growth observed in field studies. ELVOC dimers are very likely key in new particle formation as their formation is strongly suppressed with increasing NOX in accordance with the observed NOX dependence of new particle formation (Ehn

  6. Porous desulfurization sorbent pellets containing a reactive metal oxide and an inert zirconium compound

    SciTech Connect

    Gardner, Todd H.; Gasper-Galvin, Lee D.

    1996-12-01

    Sorbent pellets for removing hydrogen sulfide from coal gas are prepared by combining a reactive oxide, in particular zinc oxide, with a zirconium compound such as an oxide, silicate, or aluminate of zirconium, and an inorganic binder and pelletizing and calcining the mixture. Alternately, the zinc oxide may be replaced by copper oxide or a combination of copper, molybdenum, and manganese oxides. The pellet components may be mixed in dry form, moistened to produce a paste, and converted to pellets by forming an aqueous slurry of the components and spray drying the slurry, or the reactive oxide may be formed on existing zirconium-containing catalyst-carrier pellets by infusing a solution of a salt of the active metal onto the existing pellets and firing at a high temperature to produce the oxide. Pellets made according to this invention show a high reactivity with hydrogen sulfide and durability such as to be useful over repeated cycles of sorption and regeneration.

  7. Effect of nitric oxide compounds on monkey ciliary muscle in vitro

    PubMed Central

    Gabelt, B’Ann T.; Kaufman, Paul L.; Rasmussen, Carol A.

    2012-01-01

    The effects of various nitric oxide compounds and their inhibitors on monkey ciliary muscle contraction in vitro were investigated in both the longitudinal and circular vectors. The responses to nitric oxide compounds in carbachol precontracted ciliary muscle consisted of an initial relaxation often followed by recovery to near carbachol precontracted levels while the compound was still present. Sodium nitroprusside produced the greatest relaxation responses (nearly 100% relaxation in both vectors at 10−3 M). The highest concentrations of isosorbide dinitrate (10−4 M) and L-arginine (10−3 M) produced relaxation responses of approximately 50% in both vectors. 8-Bromo cyclic GMP produced the smallest relaxation responses (25–35%). Nitric oxide synthase inhibition enhanced carbachol contraction up to 20% in the longitudinal but not the circular vector. Phosphodiesterase inhibition did not further enhance the relaxation response to L-arginine. Guanylate cyclase inhibition partially attenuated the relaxation response to sodium nitroprusside. Nitric oxide generating compounds were effective in relaxing precontracted monkey ciliary muscle in vitro. Endogenous production of nitric oxide is likely involved in the regulation of the contractile response in monkey ciliary muscle. Nitric oxide generating compounds may have potential value in therapeutic areas where modulation of ciliary muscle tension is desirable. PMID:21147103

  8. Zinc oxide and related compounds: order within the disorder

    NASA Astrophysics Data System (ADS)

    Martins, R.; Pereira, Luisa; Barquinha, P.; Ferreira, I.; Prabakaran, R.; Goncalves, G.; Goncalves, A.; Fortunato, E.

    2009-02-01

    This paper discusses the effect of order and disorder on the electrical and optical performance of ionic oxide semiconductors based on zinc oxide. These materials are used as active thin films in electronic devices such as pn heterojunction solar cells and thin-film transistors. Considering the expected conduction mechanism in ordered and disordered semiconductors the role of the spherical symmetry of the s electron conduction bands will be analyzed and compared to covalent semiconductors. The obtained results show p-type c-Si/a-IZO/poly-ZGO solar cells exhibiting efficiencies above 14%, in device areas of about 2.34 cm2. Amorphous oxide TFTs based on the Ga-Zn-Sn-O system demonstrate superior performance than the polycrystalline TFTs based on ZnO, translated by ION/IOFF ratio exceeding 107, turn-on voltage below 1-2 V and saturation mobility above 25 cm2/Vs. Apart from that, preliminary data on p-type oxide TFT based on the Zn-Cu-O system will also be presented.

  9. DESTRUCTION OF VOLATILE ORGANIC COMPOUNDS USING CATALYTIC OXIDATION

    EPA Science Inventory

    The paper discusses the application of catalytic oxidation to four types of air emission sources: (1) groundwater stripping operations, (2) graphic arts facilities, (3) f1exographic printing plants, and (4) latex monomer production. Characteristics of each of these emissions are ...

  10. Micromechanical properties of intercalated compounds of graphite oxide with dodecahydro- closо-dodecaboric acid

    NASA Astrophysics Data System (ADS)

    Karpenko, A. A.; Saldin, V. I.

    2016-08-01

    The micromechanical properties (Young's modulus, deformation, and adhesion) of the intercalated compound of graphite oxide with dodecahydro- closo-dodecaboric acid were studied by atomic force microscopy, transmission electron microscopy, and Raman spectroscopy and compared with the same characteristics of the starting graphite oxide. The significant difference in the micromechanical properties of the materials under study is dictated by differences in the topography and properties of their film surface, which, in turn, can be determined by their chemical composition. The introduction of dodecahydro- closo-dodecaboric acid in the interplanar space of graphite oxide affects the structuring of the latter. A considerable increase in the adhesion of the intercalated compound relative to that of oxide graphite is explained by high adhesive properties of the introduced acid, the Young's modulus of graphite oxide being higher than that of the intercalated compound. This was attributed to the high hydrophilicity of dodecahydro- closo-dodecaboric acid and the difficulty of water removal from the interplanar space; water plasticizes the material, which becomes softer than graphite oxide. The difference in the structure of the coating of the intercalated compounds and the starting graphite oxide was found to be also reflected by their Raman spectra, namely, by the increased intensity of the D line with the preserved position of the G line, which points to the impurity nature of the intercalate and the unchanged hexagonal lattice of graphite.

  11. Nitric oxide synthesis and biological functions of nitric oxide released from ruthenium compounds.

    PubMed

    Pereira, A C; Paulo, M; Araújo, A V; Rodrigues, G J; Bendhack, L M

    2011-09-01

    During three decades, an enormous number of studies have demonstrated the critical role of nitric oxide (NO) as a second messenger engaged in the activation of many systems including vascular smooth muscle relaxation. The underlying cellular mechanisms involved in vasodilatation are essentially due to soluble guanylyl-cyclase (sGC) modulation in the cytoplasm of vascular smooth cells. sGC activation culminates in cyclic GMP (cGMP) production, which in turn leads to protein kinase G (PKG) activation. NO binds to the sGC heme moiety, thereby activating this enzyme. Activation of the NO-sGC-cGMP-PKG pathway entails Ca(2+) signaling reduction and vasodilatation. Endothelium dysfunction leads to decreased production or bioavailability of endogenous NO that could contribute to vascular diseases. Nitrosyl ruthenium complexes have been studied as a new class of NO donors with potential therapeutic use in order to supply the NO deficiency. In this context, this article shall provide a brief review of the effects exerted by the NO that is enzymatically produced via endothelial NO-synthase (eNOS) activation and by the NO released from NO donor compounds in the vascular smooth muscle cells on both conduit and resistance arteries, as well as veins. In addition, the involvement of the nitrite molecule as an endogenous NO reservoir engaged in vasodilatation will be described. PMID:21755266

  12. Missing Iron-Oxidizing Acidophiles Highly Sensitive to Organic Compounds

    PubMed Central

    Ueoka, Nagayoshi; Kouzuma, Atsushi; Watanabe, Kazuya

    2016-01-01

    The genus Acidithiobacillus includes iron-oxidizing lithoautotrophs that thrive in acidic mine environments. Acidithiobacillus ferrooxidans is a representative species and has been extensively studied for its application to the bioleaching of precious metals. In our attempts to cultivate the type strain of A. ferrooxidans (ATCC 23270T), repeated transfers to fresh inorganic media resulted in the emergence of cultures with improved growth traits. Strains were isolated from the resultant culture by forming colonies on inorganic silica-gel plates. A representative isolate (strain NU-1) was unable to form colonies on agarose plates and was more sensitive to organics, such as glucose, than the type strain of A. ferrooxidans. Strain NU-1 exhibited superior growth traits in inorganic iron media to those of other iron-oxidizing acidithiobacilli, suggesting its potential for industrial applications. A draft genome of NU-1 uncovered unique features in catabolic enzymes, indicating that this strain is not a mutant of the A. ferrooxidans type strain. Our results indicate that the use of inorganic silica-gel plates facilitates the isolation of as-yet-unexamined iron-oxidizing acidithiobacilli from environmental samples and enrichment cultures. PMID:27356527

  13. Lipid oxidation in baked products: impact of formula and process on the generation of volatile compounds.

    PubMed

    Maire, Murielle; Rega, Barbara; Cuvelier, Marie-Elisabeth; Soto, Paola; Giampaoli, Pierre

    2013-12-15

    This paper investigates the effect of ingredients on the reactions occurring during the making of sponge cake and leading to the generation of volatile compounds related to flavour quality. To obtain systems sensitive to lipid oxidation (LO), a formulation design was applied varying the composition of fatty matter and eggs. Oxidation of polyunsaturated fatty acids (PUFA) and formation of related volatile compounds were followed at the different steps of cake-making. Optimised dynamic Solid Phase Micro Extraction was applied to selectively extract either volatile or semi-volatile compounds directly from the baking vapours. We show for the first time that in the case of alveolar baked products, lipid oxidation occurs very early during the step of dough preparation and to a minor extent during the baking process. The generation of lipid oxidation compounds depends on PUFA content and on the presence of endogenous antioxidants in the raw matter. Egg yolk seemed to play a double role on reactivity: protecting unsaturated lipids from oxidation and being necessary to generate a broad class of compounds of the Maillard reaction during baking and linked to the typical flavour of sponge cake. PMID:23993514

  14. Oxorhenium complexes bearing the water-soluble tris(pyrazol-1-yl)methanesulfonate, 1,3,5-triaza-7-phosphaadamantane, or related ligands, as catalysts for Baeyer-Villiger oxidation of ketones.

    PubMed

    Martins, Luísa M D R S; Alegria, Elisabete C B A; Smoleński, Piotr; Kuznetsov, Maxim L; Pombeiro, Armando J L

    2013-04-15

    New rhenium(VII or III) complexes [ReO3(PTA)2][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4]I (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)2][ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(η(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)3, pz = pyrazolyl], [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)3(-)] and [ReCl2{N2C(O)Ph}(PTA)3] (7) have been prepared from the Re(VII) oxide Re2O7 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2{N2C(O)Ph}(Hpz)(PPh3)2], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process. PMID:23534942

  15. Oxide-based method of making compound semiconductor films and making related electronic devices

    DOEpatents

    Kapur, Vijay K.; Basol, Bulent M.; Leidholm, Craig R.; Roe, Robert A.

    2000-01-01

    A method for forming a compound film includes the steps of preparing a source material, depositing the source material on a base and forming a preparatory film from the source material, heating the preparatory film in a suitable atmosphere to form a precursor film, and providing suitable material to said precursor film to form the compound film. The source material includes oxide-containing particles including Group IB and IIIA elements. The precursor film includes non-oxide Group IB and IIIA elements. The compound film includes a Group IB-IIIA-VIA compound. The oxides may constitute greater than about 95 molar percent of the Group IB elements and greater than about 95 molar percent of the Group IIIA elements in the source material. Similarly, non-oxides may constitute greater than about 95 molar percent of the Group IB elements and greater than about 95 molar percent of the Group IIIA elements in the precursor film. The molar ratio of Group IB to Group IIIA elements in the source material may be greater than about 0.6 and less than about 1.0, or substantially greater that 1.0, in which case this ratio in the compound film may be reduced to greater than about 0.6 and less than about 1.0. The source material may be prepared as an ink from particles in powder form. The oxide-containing particles may include a dopant, as may the compound film. Compound films including a Group IIB-IVA-VA compound may be substituted using appropriate substitutions in the method. The method, also, is applicable to fabrication of solar cells and other electronic devices.

  16. Quantum Mechanics/Molecular Mechanics Studies on the Sulfoxidation of Dimethyl Sulfide by Compound I and Compound 0 of Cytochrome P450: Which Is the Better Oxidant?

    NASA Astrophysics Data System (ADS)

    Porro, Cristina S.; Sutcliffe, Michael J.; de Visser, Sam P.

    2009-06-01

    The cytochromes P450 are ubiquitous enzymes that are involved in key metabolizing processes in the body through the monoxygenation of substrates; however, their active oxidant is elusive. There have been reports that implicate that two oxidants, namely, the iron(IV)-oxo porphyrin cation radical (compound I) and the iron(III)-hydroperoxo complex (compound 0), both act as oxidants of sulfoxidation reactions, which contrasts theoretical studies on alkene epoxidation by compounds I and 0 that implicated compound 0 as a sluggish oxidant. To resolve this controversy and to establish the potency of compound I and compound 0 in sulfoxidation reactions, we have studied dimethyl sulfide sulfoxidation by both oxidants using the quantum mechanics/molecular mechanics (QM/MM) technique on cytochrome P450 enzymes and have set up a model of two P450 isozymes: P450cam and P450BM3. The calculations support earlier gas-phase density functional theory modeling and show that compound 0 is a sluggish oxidant that is unable to compete with compound I. Furthermore, compound I is shown to react with dimethyl sulfide via single-state reactivity on a dominant quartet spin state surface.

  17. Physiological Studies of Methane and Methanol-Oxidizing Bacteria: Oxidation of C-1 Compounds by Methylococcus capsulatus

    PubMed Central

    Patel, Ramesh N.; Hoare, Derek S.

    1971-01-01

    Methylococcus capsulatus grows only on methane or methanol as its sole source of carbon and energy. Some amino acids serve as nitrogen sources and are converted to keto acids which accumulate in the culture medium. Cell suspensions oxidize methane, methanol, formaldehyde, and formate to carbon dioxide. Other primary alcohols are oxidized only to the corresponding aldehydes. Oxidation of formate by cell suspensions is more sensitive to inhibition by cyanide than is the oxidation of other one carbon compounds. This is due to the cyanide sensitivity of a soluble nicotinamide adenine dinucleotide-specific formate dehydrogenase. Oxidation of formaldehyde and methanol is catalyzed by a nonspecific primary alcohol dehydrogenase which is activated by ammonium ions and is independent of pyridine nucleotides. Some comparisons are made with a strain of Pseudomonas methanica. PMID:5563868

  18. Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene from 3,5-dichloroanisole

    DOEpatents

    Ott, D.G.; Benziger, T.M.

    1991-03-05

    Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) from 3,5-dichloroanisole is described. Nitration of 3,5-dichloroanisole under relatively mild conditions gave 3,5-dichloro-2,4,6-trinitroanisole in high yield and purity. Ammonolysis of this latter compound gave the desired TATB. Another route to TATB was through the treatment of the 3,5-dichloro-2,4,6-trinitroanisole with thionyl chloride and dimethylformamide to yield 1,3,5-trichloro-2,4,6-trinitrobenzene. Ammonolysis of this product produced TATB. 8 figures.

  19. Genetics of Bacteria That Oxidize On-Carbon Compounds

    SciTech Connect

    Hanson, Richard S.

    2001-01-01

    Facultative methanol oxidizing bacteria contain large amounts of methanol dehydrogenase which is expressed only in the presence of methanol. This technical report describes two-two component regulatory systems encoding histidine kinases and response regulators and another response regulator all of which are required for the expression of mxaF, the open reading frame encoding methanol dehydrogenase. The response regulators bind to sequences upstream of the mxaF when phosphoryled in a reaction catalyzed by the histidine kinases. The binding of the response regulators is required for the transcription of mxaF.

  20. Solid oxide fuel cell having compound cross flow gas patterns

    DOEpatents

    Fraioli, Anthony V.

    1985-01-01

    A core construction for a fuel cell is disclosed having both parallel and cross flow passageways for the fuel and the oxidant gases. Each core passageway is defined by electrolyte and interconnect walls. Each electrolyte wall consists of cathode and anode materials sandwiching an electrolyte material. Each interconnect wall is formed as a sheet of inert support material having therein spaced small plugs of interconnect material, where cathode and anode materials are formed as layers on opposite sides of each sheet and are electrically connected together by the interconnect material plugs. Each interconnect wall in a wavy shape is connected along spaced generally parallel line-like contact areas between corresponding spaced pairs of generally parallel electrolyte walls, operable to define one tier of generally parallel flow passageways for the fuel and oxidant gases. Alternate tiers are arranged to have the passageways disposed normal to one another. Solid mechanical connection of the interconnect walls of adjacent tiers to the opposite sides of the common electrolyte wall therebetween is only at spaced point-like contact areas, 90 where the previously mentioned line-like contact areas cross one another.

  1. Theoretical study of the effect of N-oxides on the performances of energetic compounds.

    PubMed

    Lai, Wei-peng; Lian, Peng; Ge, Zhong-xue; Liu, Ying-zhe; Yu, Tao; Lv, Jian

    2016-04-01

    In order to study the effects of N-oxide on structure and performance, six categories of energetic compounds were systemically investigated. The results indicated that the C-C bonds in the rings were shortened, and the C-N bonds close to the N → O bond were elongated when N atoms was oxidized to form N → O bonds. N → O bonds can increase the densities of most categories of compounds, and the increment will increase with the number of N → O bonds. As to their detonation performances, almost all categories of compounds had an increased trend, except for some NO2-, NHNO2- and ONO2-substituted compounds. The contribution of 1,2,3,4-tetrazine and 1,2,4,5-tetrazine to performances was better than that of pyrazine and [1,2,5] oxadiazolo [3,4-b] pyrazine on the whole, and the groups, especially energetic groups, made a huge contribution to performance. When R was a NH2 or ONO2 group, all compounds had lower impact sensitivities, and thus represent candidates for novel energetic compounds. However, other than the sixth category of compounds, all compounds had higher impact sensitivities when R was a NO2 or NHNO2 group, and have little significance in application. PMID:26983612

  2. Influence of Oxidants on the Pyrolysis of Organic Compounds in Martian Soil Analogs

    NASA Astrophysics Data System (ADS)

    Steininger, Harald; Goesmann, Fred

    The search for organic molecules and traces of past and present life is one of the main goals of the 2018 ExoMars mission of ESA. The Mars Organic Molecule Analyzer (MOMA) is for one part a pyrolysis gas chromatograph mass spectrometer (pyr-GC-MS), while the other is a laser desorption mass spectrometer. In the pyr-GC-MS a soil sample of app. 200 mg is heated to a temperature of 900C. The volatile compounds can enter the GC, are separated on the column of the GC and identified in the MS. The Phoenix mission discovered considerable amounts of magnesium perchlorate in the soil at the landing site. Perchlorates are oxidizing components and therefore might interact with the expected organics within the soil, especially if the soil is heated within the pyrolysis ovens. The end-product of this oxidation would be carbon dioxide which is in-designable from the atmospheric carbon dioxide. For the test several organic compounds have been used, for example phenylalanine and benzoic acid. Carboxylic acids are stable intermediates in the oxidation of aromatic compounds and therefore the simplest aromatic carboxylic acid, benzoic acid has been considered to be present on Mars. Along with oxidation of the used compounds also chlorination of the aromatic rings was observed after pyrolysis. Up to now not all observed experimental data from the Viking missions can be explained by the perchlorates and therefore other oxidizing compounds might be present. It is likely that they also influence the pyrolysis of organic samples. Further research on the pyrolysis of organic molecules in the presence of oxidizing compounds has to be done.

  3. Modeling the oxidation of phenolic compounds by hydrogen peroxide photolysis.

    PubMed

    Zhang, Tianqi; Cheng, Long; Ma, Lin; Meng, Fanchao; Arnold, Robert G; Sáez, A Eduardo

    2016-10-01

    Hydrogen peroxide UV photolysis is among the most widely used advanced oxidation processes (AOPs) for the destruction of trace organics in waters destined for reuse. Previous kinetic models of hydrogen peroxide photolysis focus on the dynamics of hydroxyl radical production and consumption, as well as the reaction of the target organic with hydroxyl radicals. However, the rate of target destruction may also be affected by radical scavenging by reaction products. In this work, we build a predictive kinetic model for the destruction of p-cresol by hydrogen peroxide photolysis based on a complete reaction mechanism that includes reactions of intermediates with hydroxyl radicals. The results show that development of a predictive kinetic model to evaluate process performance requires consideration of the complete reaction mechanism, including reactions of intermediates with hydroxyl radicals. PMID:27448315

  4. Protective effects of five allium derived organosulfur compounds against mutation and oxidation.

    PubMed

    Chiu, Chih-Kwang; Chen, Tai-Yuan; Lin, Jou-Hsing; Wang, Chen-Ya; Wang, Bor-Sen

    2016-04-15

    In this study, we examined the ability of five allium-derived organosulfur compounds to protect cells against mutation and oxidation. The compounds tested were 1-propylmercaptan (PM), dimethyl disulfide (DMDS), diallyl disulfide (DADS), propyl disulfide (PDS), and 2,5-dimethylthiophene (DMT). Our results showed that when used at concentrations of 100-400 μmol/l, the five compounds inhibited the mutagenicity of 4-nitroquinoline-N-oxide, a direct mutagen, and benzo[a]pyrene, an indirect mutagen, toward Salmonella typhimurium TA 98 and TA 100. Furthermore, at these concentrations, all five of the compounds protected HepG2 cells against tert-butyl hydroperoxide-induced oxidative cytotoxicity. The compounds likely enhanced cell viability by suppressing the formation of reactive oxygen species and the depletion of glutathione depletion in cells. DMT and PM inhibited mutation and oxidation to a greater extent than DMDS, DADS, and PDS. These results demonstrate for the first time that DMT and PM can contribute to the antimutagenic and the antioxidative property of Allium vegetables. PMID:26617023

  5. Oxidation and Reduction of Sulfite by Chloroplasts and Formation of Sulfite Addition Compounds 1

    PubMed Central

    Dittrich, Andreas P. M.; Pfanz, Hardy; Heber, Ulrich

    1992-01-01

    After exposing intact chloroplasts isolated from spinach (Spinacia oleracea L. cv Yates) and capable of photoreducing CO2 at high rates to different concentrations of radioactive sulfite in the light or in the dark, 35SO2 and H235S were removed from the acidified suspensions in a stream of nitrogen. Remaining activity could be fractionated into sulfate, organic sulfides, and sulfite addition compounds. When chloroplast suspensions contained catalase, superoxide dismutase and O-acetylserine, the oxidation of sulfite to sulfate was slower in the light than the reductive formation of sulfides that exhibited a maximum rate of about 2 micromoles per milligram chlorophyll per hour, equivalent to about 1% of maximum carbon assimilation. Botht the oxidative and the reductive detoxification of sulfite were very slow in the dark. Oxidation was somewhat, but not much, accelerated in the light in the absence of O-acetylserine, which caused a dramatic decrease in the formation of organic sulfides and an equally dramatic increase in the concentration of sulfite addition compounds whose formation was light-dependent. The sulfite addition compounds were not identified. Addition compounds did not accumulate in the dark. In the light, the electron transport inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea, diuron, decreased not only the reduction, but also the oxidation of sulfite and the formation of addition compounds. PMID:16668703

  6. NATURAL EMISSIONS OF NON-METHANE VOLATILE ORGANIC COMPOUNDS, CARBON MONOXIDE, AND OXIDES OF NITROGEN FROM NORTH AMERICA

    EPA Science Inventory

    The magnitudes, distributions, controlling processes and uncertainties associated with North American natural emissions of oxidant precursors are reviewed. Natural emissions are repsonsible for a major portion of the compounds, including non-methane volatile organic compounds (N...

  7. Solar-powered electrochemical oxidation of organic compounds coupled with the cathodic production of molecular hydrogen.

    PubMed

    Park, Hyunwoong; Vecitis, Chad D; Hoffmann, Michael R

    2008-08-21

    A Bi-doped TiO2 anode, which is prepared from a mixed metal oxide coating deposited on Ti metal, is shown to be efficient for conventional water splitting. In this hybrid photovoltaic-electrochemical system, a photovoltaic (PV) cell is used to convert solar light to electricity, which is then used to oxidize a series of phenolic compounds at the semiconductor anode to carbon dioxide with the simultaneous production of molecular hydrogen from water/proton reduction at the stainless steel cathode. Degradation of phenol in the presence of a background NaCl electrolyte produces chlorinated phenols as reaction intermediates, which are subsequently oxidized completely to carbon dioxide and low-molecular weight carboxylic acids. The anodic current efficiency for the complete oxidation of phenolic compounds ranges from 3% to 17%, while the cathodic current efficiency and the energy efficiency for hydrogen gas generation range from 68% to 95% and 30% to 70%, respectively. PMID:18656909

  8. Genomic Analysis Unravels Reduced Inorganic Sulfur Compound Oxidation of Heterotrophic Acidophilic Acidicaldus sp. Strain DX-1

    PubMed Central

    Liu, Yuanyuan; Yang, Hongying; Zhang, Xian; Xiao, Yunhua; Guo, Xue; Liu, Xueduan

    2016-01-01

    Although reduced inorganic sulfur compound (RISC) oxidation in many chemolithoautotrophic sulfur oxidizers has been investigated in recent years, there is little information about RISC oxidation in heterotrophic acidophiles. In this study, Acidicaldus sp. strain DX-1, a heterotrophic sulfur-oxidizing acidophile, was isolated. Its genome was sequenced and then used for comparative genomics. Furthermore, real-time quantitative PCR was performed to identify the expression of genes involved in the RISC oxidation. Gene encoding thiosulfate: quinone oxidoreductase was present in Acidicaldus sp. strain DX-1, while no candidate genes with significant similarity to tetrathionate hydrolase were found. Additionally, there were genes encoding heterodisulfide reductase complex, which was proposed to play a crucial role in oxidizing cytoplasmic sulfur. Like many heterotrophic sulfur oxidizers, Acidicaldus sp. strain DX-1 had no genes encoding enzymes essential for the direct oxidation of sulfite. An indirect oxidation of sulfite via adenosine-5′-phosphosulfate was proposed in Acidicaldus strain DX-1. However, compared to other closely related bacteria Acidiphilium cryptum and Acidiphilium multivorum, which harbored the genes encoding Sox system, almost all of these genes were not detected in Acidicaldus sp. strain DX-1. This study might provide some references for the future study of RISC oxidation in heterotrophic sulfur-oxidizing acidophiles. PMID:27239474

  9. Genomic Analysis Unravels Reduced Inorganic Sulfur Compound Oxidation of Heterotrophic Acidophilic Acidicaldus sp. Strain DX-1.

    PubMed

    Liu, Yuanyuan; Yang, Hongying; Zhang, Xian; Xiao, Yunhua; Guo, Xue; Liu, Xueduan

    2016-01-01

    Although reduced inorganic sulfur compound (RISC) oxidation in many chemolithoautotrophic sulfur oxidizers has been investigated in recent years, there is little information about RISC oxidation in heterotrophic acidophiles. In this study, Acidicaldus sp. strain DX-1, a heterotrophic sulfur-oxidizing acidophile, was isolated. Its genome was sequenced and then used for comparative genomics. Furthermore, real-time quantitative PCR was performed to identify the expression of genes involved in the RISC oxidation. Gene encoding thiosulfate: quinone oxidoreductase was present in Acidicaldus sp. strain DX-1, while no candidate genes with significant similarity to tetrathionate hydrolase were found. Additionally, there were genes encoding heterodisulfide reductase complex, which was proposed to play a crucial role in oxidizing cytoplasmic sulfur. Like many heterotrophic sulfur oxidizers, Acidicaldus sp. strain DX-1 had no genes encoding enzymes essential for the direct oxidation of sulfite. An indirect oxidation of sulfite via adenosine-5'-phosphosulfate was proposed in Acidicaldus strain DX-1. However, compared to other closely related bacteria Acidiphilium cryptum and Acidiphilium multivorum, which harbored the genes encoding Sox system, almost all of these genes were not detected in Acidicaldus sp. strain DX-1. This study might provide some references for the future study of RISC oxidation in heterotrophic sulfur-oxidizing acidophiles. PMID:27239474

  10. Ozone Promotes Chloropicrin Formation by Oxidizing Amines to Nitro Compounds.

    PubMed

    McCurry, Daniel L; Quay, Amanda N; Mitch, William A

    2016-02-01

    Chloropicrin formation has been associated with ozonation followed by chlorination, but the reaction pathway and precursors have been poorly characterized. Experiments with methylamine demonstrated that ozonation converts methylamine to nitromethane at ∼100% yield. Subsequent chlorination converts nitromethane to chloropicrin at ∼50% yield under the conditions evaluated. Similarly high yields from other primary amines were limited to those with functional groups on the β-carbon (e.g., the carboxylic acid in glycine) that facilitate carbon-carbon bond cleavage to release nitromethyl anion. Secondary amines featuring these reactive primary amines as functional groups (e.g., secondary N-methylamines) formed chloropicrin at high yields, likely by facile dealkylation to release the primary nitro compound. Chloropicrin yields from tertiary amines were low. Natural water experiments, including derivatization to transform primary and secondary amines to less reactive carbamate functional groups, indicated that primary and secondary amines were the dominant chloropicrin precursors during ozonation/chlorination. Ozonation followed by chlorination of the primary amine side chain of lysine demonstrated low yields (∼0.2%) of chloropicrin, but high yields (∼17%) of dichloronitrolysine, a halonitroalkane structural analogue to chloropicrin. However, chloropicrin yields increased and dichloronitrolysine yields decreased in the absence of hydroxyl radical scavengers, suggesting that future research should characterize the potential occurrence of such halonitroalkane analogues relative to natural radical scavenger (e.g., carbonate) concentrations. PMID:26752338

  11. Influence of stoichiometry on the electrochromiccerium-titanium oxide compounds

    SciTech Connect

    Kullman, L.; Richardson, T.; Rubin, M.; Slack, J.; von Rottkay, K.

    1997-11-01

    CeO2-TiO2 finds use as passive counter-electrode in electrochromic devices. Thin films were produced by de-sputtering in a wide range of compositions. Influence of total pressure and oxygen partial pressure on the optical constants of TiO2 was investigated. Slightly substoichiometric Ti02 films exhibit a red-shift of the bandgap. The Ti02 content in the compound essentially determines the degree of cathodical coloring upon Li+ intercalation [1]. However, pure TiO2 films with comparable visible transmittance in the clear state behave differently during electrochemical cycling depending on oxygen stoichiometry. Films that are deposited at higher total pressure are more oxygen rich and require initial formatting until current voltage cycles become stable. CeO2-Ti02 films of intermediate compositions have the relatively highest charge capacity. Comparison with atomic force microscopy indicates a correlation of small grain size with high charge capacity.

  12. Redox Chemistry in Laccase-Catalyzed Oxidation of N-Hydroxy Compounds

    PubMed Central

    Xu, Feng; Kulys, Juozas J.; Duke, Kyle; Li, Kaichang; Krikstopaitis, Kastis; Deussen, Heinz-Josef W.; Abbate, Eric; Galinyte, Vilija; Schneider, Palle

    2000-01-01

    1-Hydroxybenzotriazole, violuric acid, and N-hydroxyacetanilide are three N-OH compounds capable of mediating a range of laccase-catalyzed biotransformations, such as paper pulp delignification and degradation of polycyclic hydrocarbons. The mechanism of their enzymatic oxidation was studied with seven fungal laccases. The oxidation had a bell-shaped pH-activity profile with an optimal pH ranging from 4 to 7. The oxidation rate was found to be dependent on the redox potential difference between the N-OH substrate and laccase. A laccase with a higher redox potential or an N-OH compound with a lower redox potential tended to have a higher oxidation rate. Similar to the enzymatic oxidation of phenols, phenoxazines, phenothiazines, and other redox-active compounds, an “outer-sphere” type of single-electron transfer from the substrate to laccase and proton release are speculated to be involved in the rate-limiting step for N-OH oxidation. PMID:10788380

  13. Stimulation of elemental mercury oxidation by SH compounds

    SciTech Connect

    Yamamoto, M.; Nakamura, K.; Yasutake, A.; Fujisaki, T.; Nakano, A.; Hou, H.

    1995-03-01

    Anthropogenic mercury pollution has been a serious environmental problem. The presence of mercury in the environment has received a great deal of attention due to its highly toxic nature and translocation through the food chain. Elemental mercury released into the Amazon River basin due to gold mining activities is roughly estimated at 130 tons per year. In fact, high levels of total mercury, mostly in the form of methylmercury, in fish collected from around the gold mining areas and high levels of methylmercury in the hair of humans living in fishing villages downstream of these areas have recently been documented. These results suggest that the reaction which converts the discharged elemental mercury into mercuric mercury is present in nature before the methylation of the generated mercuric mercury. Methylation and reduction of mercuric mercury and decomposition of organomercury have been extensively studied. However, little information is available concerning the conversion of elemental mercury in aquatic ecosystems. The purpose of this study was to clarify the mechanism of oxidation of elemental mercury to mercuric mercury in the aquatic environment. 11 refs., 4 figs.

  14. Oxidation of pharmaceutically active compounds by a ligninolytic fungal peroxidase.

    PubMed

    Eibes, Gemma; Debernardi, Gianfranco; Feijoo, Gumersindo; Moreira, M Teresa; Lema, Juan M

    2011-06-01

    Pharmaceuticals are an important group of emerging pollutants with increasing interest due to their rising consumption and the evidence for ecotoxicological effects associated to trace amounts in aquatic environments. In this paper, we assessed the potential degradation of a series of pharmaceuticals: antibiotics (sulfamethoxazole), antidepressives (citalopram hydrobromide and fluoxetine hydrochloride), antiepileptics (carbamazepine), anti-inflammatory drugs (diclofenac and naproxen) and estrogen hormones (estrone, 17β-estradiol, 17α-ethinylestradiol) by means of a versatile peroxidase (VP) from the ligninolytic fungus Bjerkandera adusta. The effects of the reaction conditions: VP activity, organic acid concentration and H(2)O(2) addition rate, on the kinetics of the VP based oxidation system were evaluated. Diclofenac and estrogens were completely degraded after only 5-25 min even with a very low VP activity (10 U l(-1)). High degradation percentages (80%) were achieved for sulfamethoxazole and naproxen. Low or undetectable removal yields were observed for citalopram (up to 18%), fluoxetine (lower than 10%) and carbamazepine (not degraded). PMID:20972884

  15. Identification of an iridium-containing compound with a formal oxidation state of IX.

    PubMed

    Wang, Guanjun; Zhou, Mingfei; Goettel, James T; Schrobilgen, Gary J; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian

    2014-10-23

    One of the most important classifications in chemistry and within the periodic table is the concept of formal oxidation states. The preparation and characterization of compounds containing elements with unusual oxidation states is of great interest to chemists. The highest experimentally known formal oxidation state of any chemical element is at present VIII, although higher oxidation states have been postulated. Compounds with oxidation state VIII include several xenon compounds (for example XeO4 and XeO3F2) and the well-characterized species RuO4 and OsO4 (refs 2-4). Iridium, which has nine valence electrons, is predicted to have the greatest chance of being oxidized beyond the VIII oxidation state. In recent matrix-isolation experiments, the IrO4 molecule was characterized as an isolated molecule in rare-gas matrices. The valence electron configuration of iridium in IrO4 is 5d(1), with a formal oxidation state of VIII. Removal of the remaining d electron from IrO4 would lead to the iridium tetroxide cation ([IrO4](+)), which was recently predicted to be stable and in which iridium is in a formal oxidation state of IX. There has been some speculation about the formation of [IrO4](+) species, but these experimental observations have not been structurally confirmed. Here we report the formation of [IrO4](+) and its identification by infrared photodissociation spectroscopy. Quantum-chemical calculations were carried out at the highest level of theory that is available today, and predict that the iridium tetroxide cation, with a Td-symmetrical structure and a d(0) electron configuration, is the most stable of all possible [IrO4](+) isomers. PMID:25341786

  16. Identification of an iridium-containing compound with a formal oxidation state of IX

    NASA Astrophysics Data System (ADS)

    Wang, Guanjun; Zhou, Mingfei; Goettel, James T.; Schrobilgen, Gary J.; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian

    2014-10-01

    One of the most important classifications in chemistry and within the periodic table is the concept of formal oxidation states. The preparation and characterization of compounds containing elements with unusual oxidation states is of great interest to chemists. The highest experimentally known formal oxidation state of any chemical element is at present VIII, although higher oxidation states have been postulated. Compounds with oxidation state VIII include several xenon compounds (for example XeO4 and XeO3F2) and the well-characterized species RuO4 and OsO4 (refs 2, 3, 4). Iridium, which has nine valence electrons, is predicted to have the greatest chance of being oxidized beyond the VIII oxidation state. In recent matrix-isolation experiments, the IrO4 molecule was characterized as an isolated molecule in rare-gas matrices. The valence electron configuration of iridium in IrO4 is 5d1, with a formal oxidation state of VIII. Removal of the remaining d electron from IrO4 would lead to the iridium tetroxide cation ([IrO4]+), which was recently predicted to be stable and in which iridium is in a formal oxidation state of IX. There has been some speculation about the formation of [IrO4]+ species, but these experimental observations have not been structurally confirmed. Here we report the formation of [IrO4]+ and its identification by infrared photodissociation spectroscopy. Quantum-chemical calculations were carried out at the highest level of theory that is available today, and predict that the iridium tetroxide cation, with a Td-symmetrical structure and a d0 electron configuration, is the most stable of all possible [IrO4]+ isomers.

  17. Biodegradation of Hexahydro-1,3,5-Trinitro-1,3,5-Triazine

    PubMed Central

    McCormick, N. G.; Cornell, J. H.; Kaplan, A. M.

    1981-01-01

    Biodegradation of the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) occurs under anaerobic conditions, yielding a number of products, including: hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine, hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine, hexahydro-1,3,5-trinitroso-1,3,5-triazine, hydrazine, 1,1-dimethyl-hydrazine, 1,2-dimethylhydrazine, formaldehyde, and methanol. A scheme for the biodegradation of RDX is proposed which proceeds via successive reduction of the nitro groups to a point where destabilization and fragmentation of the ring occurs. The noncyclic degradation products arise via subsequent reduction and rearrangement reactions of the fragments. The scheme suggests the presence of several additional compounds, not yet identified. Several of the products are mutagenic or carcinogenic or both. Anaerobic treatment of RDX wastewaters, which also contain high nitrate levels, would permit the denitrification to occur, with concurrent degradation of RDX ultimately to a mixture of hydrazines and methanol. The feasibility of using an aerobic mode in the further degradation of these products is discussed. PMID:16345884

  18. CATALYTIC OXIDATION OF MALODOROUS COMPOUNDS FROM PULP AND PAPER MILLS WITH OZONE AS AN OXIDANT

    EPA Science Inventory

    Total reduced sulfer (TRS) compounds such as dimethyl sulfide, dimethyl disulfide, methanethiol and H2S are identified as major constituents of pulp and paper mill blow tank effluents. TRS compounds are calodorous and can have potentially serious impacts on environmental quality ...

  19. Oxidation of dissolved elemental mercury by thiol compounds under anoxic conditions

    SciTech Connect

    Zheng, Wang; Lin, Hui; Mann, Benjamin F; Liang, Liyuan; Gu, Baohua

    2013-01-01

    Mercuric mercury, Hg(II), forms strong complexes with thiol compounds that commonly dominate Hg(II) speciation in natural freshwater. However, reactions between dissolved elemental Hg(0) and thiols are not well understood although these processes are likely to be important in determining Hg speciation and geochemical cycling in the environment. In this study, reaction rates and mechanisms between dissolved Hg(0) and a number of selected organic ligands with varying molecular structures and sulfur (S) oxidation states were determined to assess the role of these ligands in Hg(0) redox transformation. We found that all thiols caused oxidation of Hg(0) under anoxic conditions but, contrary to expectation, compounds with higher S-oxidation states (e.g., disulfide) than thiols exhibited little or no reactivity with Hg(0) at pH 7. The rate and extent of Hg(0) oxidation varied widely, with smaller aliphatic thiols showing the greatest degree of oxidation. The mechanism of the oxidation is attributed to a two-step process involving adsorption of Hg(0) to thiols followed by the charge transfer from Hg(0) to electron acceptors. These observations demonstrate a unique thiol-induced oxidation pathway of dissolved Hg(0), with important implications for the redox transformation, speciation, and bioavailability of Hg for microbial methylation in anoxic environments.

  20. Lignin Peroxidase Oxidation of Aromatic Compounds in Systems Containing Organic Solvents

    PubMed Central

    Vazquez-Duhalt, Rafael; Westlake, Donald W. S.; Fedorak, Phillip M.

    1994-01-01

    Lignin peroxidase from Phanerochaete chrysosporium was used to study the oxidation of aromatic compounds, including polycyclic aromatic hydrocarbons and heterocyclic compounds, that are models of moieties of asphaltene molecules. The oxidations were done in systems containing water-miscible organic solvents, including methanol, isopropanol, N, N-dimethylformamide, acetonitrile, and tetrahydrofuran. Of the 20 aromatic compounds tested, 9 were oxidized by lignin peroxidase in the presence of hydrogen peroxide. These included anthracene, 1-, 2-, and 9-methylanthracenes, acenaphthene, fluoranthene, pyrene, carbazole, and dibenzothiophene. Of the compounds studied, lignin peroxidase was able to oxidize those with ionization potentials of <8 eV (measured by electron impact). The reaction products contain hydroxyl and keto groups. In one case, carbon-carbon bond cleavage, yielding anthraquinone from 9-methylanthracene, was detected. Kinetic constants and stability characteristics of lignin peroxidase were determined by using pyrene as the substrate in systems containing different amounts of organic solvent. Benzyl alkylation of lignin peroxidase improved its activity in a system containing water-miscible organic solvent but did not increase its resistance to inactivation at high solvent concentrations. PMID:16349176

  1. Lignin peroxidase oxidation of aromatic compounds in systems containing organic solvents.

    PubMed

    Vazquez-Duhalt, R; Westlake, D W; Fedorak, P M

    1994-02-01

    Lignin peroxidase from Phanerochaete chrysosporium was used to study the oxidation of aromatic compounds, including polycyclic aromatic hydrocarbons and heterocyclic compounds, that are models of moieties of asphaltene molecules. The oxidations were done in systems containing water-miscible organic solvents, including methanol, isopropanol, N, N-dimethylformamide, acetonitrile, and tetrahydrofuran. Of the 20 aromatic compounds tested, 9 were oxidized by lignin peroxidase in the presence of hydrogen peroxide. These included anthracene, 1-, 2-, and 9-methylanthracenes, acenaphthene, fluoranthene, pyrene, carbazole, and dibenzothiophene. Of the compounds studied, lignin peroxidase was able to oxidize those with ionization potentials of <8 eV (measured by electron impact). The reaction products contain hydroxyl and keto groups. In one case, carbon-carbon bond cleavage, yielding anthraquinone from 9-methylanthracene, was detected. Kinetic constants and stability characteristics of lignin peroxidase were determined by using pyrene as the substrate in systems containing different amounts of organic solvent. Benzyl alkylation of lignin peroxidase improved its activity in a system containing water-miscible organic solvent but did not increase its resistance to inactivation at high solvent concentrations. PMID:16349176

  2. COST ANALYSIS OF ACTIVATED CARBON VERSUS PHOTOCATALYTIC OXIDATION FOR REMOVING ORGANIC COMPOUNDS FROM INDOOR AIR

    EPA Science Inventory

    A cost comparison has been conducted of 1 m3/s indoor air cleaners using granular activated carbon (GAC) vs. photocatalytic oxidation (PCO) for treating a steady-state inlet volatile organic compound (VOC) concentration of 0.3 mg/m3. The commercial GAC unit was costed assuming t...

  3. Screening SIRT1 Activators from Medicinal Plants as Bioactive Compounds against Oxidative Damage in Mitochondrial Function

    PubMed Central

    Wang, Yi; Liang, Xinying; Chen, Yaqi; Zhao, Xiaoping

    2016-01-01

    Sirtuin type 1 (SIRT1) belongs to the family of NAD+ dependent histone deacetylases and plays a critical role in cellular metabolism and response to oxidative stress. Traditional Chinese medicines (TCMs), as an important part of natural products, have been reported to exert protective effect against oxidative stress in mitochondria. In this study, we screened SIRT1 activators from TCMs and investigated their activities against mitochondrial damage. 19 activators were found in total by in vitro SIRT1 activity assay. Among those active compounds, four compounds, ginsenoside Rb2, ginsenoside F1, ginsenoside Rc, and schisandrin A, were further studied to validate the SIRT1-activation effects by liquid chromatography-mass spectrometry and confirm their activities against oxidative damage in H9c2 cardiomyocytes exposed to tert-butyl hydroperoxide (t-BHP). The results showed that those compounds enhanced the deacetylated activity of SIRT1, increased ATP content, and inhibited intracellular ROS formation as well as regulating the activity of Mn-SOD. These SIRT1 activators also showed moderate protective effects on mitochondrial function in t-BHP cells by recovering oxygen consumption and increasing mitochondrial DNA content. Our results suggested that those compounds from TCMs attenuated oxidative stress-induced mitochondrial damage in cardiomyocytes through activation of SIRT1. PMID:26981165

  4. KINETICS AND SELECTIVITY OF DEEP CATALYTIC OXIDATION OF VOLATILE ORGANIC COMPOUND MIXTURES

    EPA Science Inventory

    The paper gives results of a fundamental study of low-temperature deep (complete) oxidation of n-hexane, benzene, and ethyl-acetate over a 0.1% Pt, 3% Ni/gamma-AL203 catalyst. (NOTE: Deep catalytic combustion of volatile organic compounds--VOCs--is emerging as an important emissi...

  5. Bioleaching of pyrite by Thiobacillus ferrooxidans: fixed grains electrode to study superficial oxidized compounds

    NASA Astrophysics Data System (ADS)

    Toniazzo, Valérie; Lazaro, Isabelle; Humbert, Bernard; Mustin, Christian

    1999-04-01

    An electrode with fixed pyrite grains on a graphite and silicon paste has been used to study the electrochemical processes at the surface of powdered pyrite during bioleaching by Thiobacillus ferrooxidans. The study of an air-oxidized pyrite shows that the fixed grains electrode (FGE) is more sensitive than the classical Carbon Paste Electrode (CPE) already used by different authors to characterize various oxides and sulfurs. On the other hand, the concommitant Raman and electrochemical analysis of autoclaved pyrite shows that the cleaned mineral FeS 2 has no electrochemical reactivity, and points out that the electrochemical response of the oxidized mineral is exclusively due to the chemical compounds present at its surface. Therefore, the electrode acts as an efficient sensor for pyrite superficial oxidized phases, which are fundamental for the biooxidation process and is consequently very well adapted for the control of the oxidation state of pyrite powder during bioleaching by Thiobacillus ferrooxidans.

  6. Thermal diffusivity of oxide perovskite compounds at elevated temperature

    NASA Astrophysics Data System (ADS)

    Hofmeister, Anne M.

    2010-05-01

    The phonon component of thermal diffusivity (D) for eleven compounds (synthetic SrTiO3, SrTiO3:Fe3+, BaTiO3, KTaO3, KNbO3, NdGaO3, YAlO3, YAlO3:Tm, LaAlO3, La0.29Sr0.66Al0.65Ta0.35O3, and natural Ca1.01Mn0.001Fe0.007Ti0.99O3) with various perovskite structures was measured from ambient temperature (T) up to ˜2000 K using contact-free, laser-flash analysis, from which effects of ballistic radiative transfer were removed. Structural transitions (e.g., orthorhombic to tetragonal) below 800 K were manifest as sharp steps in 1/D. Above 800 K, structural transitions occur over intervals of ˜150 K. Similarly broad peaks accompany changes from colorless to black, attributable to partial reduction in Ti, Nb, or Ta from contact with graphite coatings. Otherwise, D decreases with increasing T and, if substitutional disorder exists, approaches a constant (Dsat) near 1600 K. Our data are best described as D-1 following a low order polynomial in T. Ordered, cubic perovskites occupy a single trend for D(T )-1, defining the contribution of the ideal lattice. Distortion, disorder, and polymorphism affect D-1 in a manner that is consistent with the damped harmonic oscillator-phonon gas model which relates phonon lifetimes to infrared peak widths. Calculated D-values at ambient and high T agree with measurements. The behavior of D is simple compared to that of thermal conductivity, k =ρCPD, where ρ is density and CP is heat capacity. Combining our data with cryogenic measurements of YAlO3 and LaAlO3 shows that D-1 depends on T similarly to CP, consistent with phonon lifetime depending on the density of states but, the best description for D-1(T) is a proportionality to αT from ˜0 K up to the limit of measurements, where α is thermal expansivity, a strongly anharmonic property. At low T, D-1 due to phonon scattering follows that of CP, generally∝T3, so klat=k0+k1T. Defects being present preclude scattering at sample walls, adding a small constant D0-1 ˜0.0001 mm-2 s as T

  7. Influence of a reaction medium on the oxidation of aromatic nitrogen-containing compounds by peroxyacids

    NASA Astrophysics Data System (ADS)

    Dutka, V. S.; Matsyuk, N. V.; Dutka, Yu. V.

    2011-01-01

    The influence of different solvents on the oxidation reaction rate of pyridine (Py), quinoline (QN), acridine (AN), α-oxyquinoline (OQN) and α-picolinic acid (APA) by peroxydecanoic acid (PDA) was studied. It was found that the oxidation rate grows in the series Py < QN < AN, and the rate of the oxidation reaction of compounds containing a substituent in the α position from a reactive center is significantly lower than for unsubstituted analogues. The effective energies of activation of the oxidation reaction were found. It was shown that in the first stage, the reaction mechanism includes the rapid formation of an intermediate complex nitrogen-containing compound, peroxyacid, which forms products upon decomposing in the second stage. A kinetic equation that describes the studied process is offered. The constants of equilibrium of the intermediate complex formation ( K eq) and its decomposition constant ( k 2) in acetone and benzene were calculated. It was shown that the nature of the solvent influences the numerical values of both K p and k 2. It was established that introduction of acetic acid (which is able to form compounds with Py) into the reaction medium slows the rate of the oxidation process drastically. Correlation equations linking the polarity, polarizability, electrophilicity, and basicity of solvents with the constant of the PDA oxidation reaction rate for Py were found. It was concluded that the basicity and polarity of the solvent have a decisive influence on the oxidation reaction rate, while the polarizability and electrophilicity of the reaction medium do not influence the oxidation reaction rate.

  8. Integration of advanced oxidation processes at mild conditions in wet scrubbers for odourous sulphur compounds treatment.

    PubMed

    Vega, Esther; Martin, Maria J; Gonzalez-Olmos, Rafael

    2014-08-01

    The effectiveness of different advanced oxidation processes on the treatment of a multicomponent aqueous solution containing ethyl mercaptan, dimethyl sulphide and dimethyl disulphide (0.5 mg L(-1) of each sulphur compound) was investigated with the objective to assess which one is the most suitable treatment to be coupled in wet scrubbers used in odour treatment facilities. UV/H2O2, Fenton, photo-Fenton and ozone treatments were tested at mild conditions and the oxidation efficiency obtained was compared. The oxidation tests were carried out in magnetically stirred cylindrical quartz reactors using the same molar concentration of oxidants (hydrogen peroxide or ozone). The results show that ozone and photo-Fenton are the most efficient treatments, achieving up to 95% of sulphur compounds oxidation and a mineralisation degree around 70% in 10 min. Furthermore, the total costs of the treatments taking into account the capital and operational costs were also estimated for a comparative purpose. The economic analysis revealed that the Fenton treatment is the most economical option to be integrated in a wet scrubber to remove volatile organic sulphur compounds, as long as there are no space constraints to install the required reactor volume. In the case of reactor volume limitation or retrofitting complexities, the ozone and photo-Fenton treatments should be considered as viable alternatives. PMID:24873715

  9. Generation of free radical intermediates from foreign compounds by neutrophil-derived oxidants.

    PubMed Central

    Kalyanaraman, B; Sohnle, P G

    1985-01-01

    A large number of foreign compounds, including many drugs, industrial pollutants, and environmental chemicals, can be oxidized under appropriate conditions to potentially toxic free radical intermediates. We evaluated the ability of the oxidants produced by the neutrophil myeloperoxidase system to generate free radical intermediates from several such compounds. Sodium hypochlorite or hypochlorous acid produced by human peripheral blood neutrophils and trapped in the form of taurine chloramine were both found to be capable of producing free radicals from chlorpromazine, aminopyrine, and phenylhydrazine. These radical intermediates were demonstrated by visible light spectroscopy and by direct electron spin resonance (for the chlorpromazine and aminopyrine radicals) or by spin-trapping (for the phenyl radical generated from phenylhydrazine). Stable oxidants produced by the neutrophils (i.e., those present in the supernatants of stimulated neutrophils in the absence of added taurine) also were found to be capable of generating free radical intermediates. The production of the oxidants and the ability of neutrophil supernatants to generate these radicals were almost completely eliminated by sodium azide, a myeloperoxidase inhibitor. We suggest that the oxidation by neutrophils of certain chemical compounds to potentially damaging electrophilic free radical forms may represent a new metabolic pathway for these substances and could be important in the processes of drug toxicity and chemical carcinogenesis. PMID:2987307

  10. Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes.

    PubMed

    Huang, Li-Zhi; Hansen, Hans Christian B; Bjerrum, Morten Jannik

    2016-04-01

    Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes. A reduction current density of 10 to 30μAcm(-2) was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400μM of the nitroaromatic compound at a potential of -0.7V vs. SHE. Fast mass transfer favors the initial reduction of the nitroaromatic compound which is well explained by a diffusion layer model. Reduction was found to comprise two consecutive reactions: a fast four-electron first-order reduction of the nitro-group to the hydroxylamine-intermediate (rate constant=0.28h(-1)) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant=6.9μM h(-1)). The zero-order of the latter reduction was attributed to saturation of the electrode surface with hydroxylamine-intermediates which have a more negative half-wave potential than the parent compound. For reduction of nitroaromatic compounds, the SSI electrode is found superior to metal electrodes due to low cost and high stability, and superior to carbon-based electrodes in terms of high coulombic efficiency and low over potential. PMID:26716570

  11. Aromatic amine N-oxide organometallic compounds: searching for prospective agents against infectious diseases.

    PubMed

    Rodríguez Arce, Esteban; Mosquillo, M Florencia; Pérez-Díaz, Leticia; Echeverría, Gustavo A; Piro, Oscar E; Merlino, Alicia; Coitiño, E Laura; Maríngolo Ribeiro, Camila; Leite, Clarice Q F; Pavan, Fernando R; Otero, Lucía; Gambino, Dinorah

    2015-08-28

    In search of prospective agents against infectious diseases, 1,1'-bis(diphenylphosphino)ferrocene pyridine-2-thiolato-1-oxide M(ii) hexafluorophosphate compounds [M(mpo)(dppf)](PF6), where M = palladium or platinum, were synthesized and fully characterized in the solid state and in solution using experimental and DFT computational techniques. The compounds are isomorphous and the M(ii) transition metal ions are in a nearly planar trapezoidal cis-coordination bound to the pyridine-2-thiolato-1-oxide (mpo) and to the 1,1'-bis(diphenylphosphino)ferrocene molecules, both acting as bidentate ligands. Both compounds showed high cytotoxic activity on Trypanosoma cruzi and Mycobacterium tuberculosis (MTB) and acceptable selectivities towards MTB, but good to excellent selectivity index values as anti-T. cruzi compounds. The inclusion of the ferrocene moiety (dppf ligand) improved the selectivity towards the parasite when compared to the previously reported [M(mpo)2] complexes. Related to the probable mechanism of action of the complexes, molecular docking studies on modelled T. cruzi NADH-fumarate reductase (TcFR) predicted that both be very good inhibitors of the enzyme. The effect of the compounds on the enzyme activity was experimentally confirmed using T. cruzi protein extracts. According to all obtained results, both [M(mpo)(dppf)](PF6) compounds could be considered prospective anti-trypanosomal agents that deserve further research. PMID:26203896

  12. 1,3,5-Trinitrobenzene

    Integrated Risk Information System (IRIS)

    1,3,5 - Trinitrobenzene ; CASRN 99 - 35 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcino

  13. The high pressure structure and equation of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) up to 20 GPa: X-ray diffraction measurements and first principles molecular dynamics simulations

    SciTech Connect

    Stavou, Elissaios; Manaa, M. Riad; Zaug, Joseph M.; Kuo, I-Feng W.; Pagoria, Philip F.; Crowhurst, Jonathan C.; Armstrong, Michael R.; Kalkan, Bora

    2015-10-14

    Recent theoretical studies of 2,6-diamino-3,5-dinitropyrazine-1-oxide (C4H4N6O5 Lawrence Livermore Molecule No. 105, LLM-105) report unreacted high pressure equations of state that include several structural phase transitions, between 8 and 50 GPa, while one published experimental study reports equation of state (EOS) data up to a pressure of 6 GPa with no observed transition. Here we report the results of a synchrotron-based X-ray diffraction study and also ambient temperature isobaric-isothermal atomistic molecular dynamics simulations of LLM-105 up to 20 GPa. We find that the ambient pressure phase remains stable up to 20 GPa; there is no indication of a pressure induced phase transition. We do find a prominent decrease in b-axis compressibility starting at approximately 13 GPa and attribute the stiffening to a critical length where inter-sheet distance becomes similar to the intermolecular distance within individual sheets. The ambient temperature isothermal equation of state was determined through refinements of measured X-ray diffraction patterns. The pressure-volume data were fit using various EOS models to yield bulk moduli with corresponding pressure derivatives. As a result, we find very good agreement between the experimental and theoretically derived EOS.

  14. The high pressure structure and equation of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) up to 20 GPa: X-ray diffraction measurements and first principles molecular dynamics simulations

    DOE PAGESBeta

    Stavou, Elissaios; Manaa, M. Riad; Zaug, Joseph M.; Kuo, I-Feng W.; Pagoria, Philip F.; Crowhurst, Jonathan C.; Armstrong, Michael R.; Kalkan, Bora

    2015-10-14

    Recent theoretical studies of 2,6-diamino-3,5-dinitropyrazine-1-oxide (C4H4N6O5 Lawrence Livermore Molecule No. 105, LLM-105) report unreacted high pressure equations of state that include several structural phase transitions, between 8 and 50 GPa, while one published experimental study reports equation of state (EOS) data up to a pressure of 6 GPa with no observed transition. Here we report the results of a synchrotron-based X-ray diffraction study and also ambient temperature isobaric-isothermal atomistic molecular dynamics simulations of LLM-105 up to 20 GPa. We find that the ambient pressure phase remains stable up to 20 GPa; there is no indication of a pressure induced phasemore » transition. We do find a prominent decrease in b-axis compressibility starting at approximately 13 GPa and attribute the stiffening to a critical length where inter-sheet distance becomes similar to the intermolecular distance within individual sheets. The ambient temperature isothermal equation of state was determined through refinements of measured X-ray diffraction patterns. The pressure-volume data were fit using various EOS models to yield bulk moduli with corresponding pressure derivatives. As a result, we find very good agreement between the experimental and theoretically derived EOS.« less

  15. The high pressure structure and equation of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) up to 20 GPa: X-ray diffraction measurements and first principles molecular dynamics simulations.

    PubMed

    Stavrou, Elissaios; Riad Manaa, M; Zaug, Joseph M; Kuo, I-Feng W; Pagoria, Philip F; Kalkan, Bora; Crowhurst, Jonathan C; Armstrong, Michael R

    2015-10-14

    Recent theoretical studies of 2,6-diamino-3,5-dinitropyrazine-1-oxide (C4H4N6O5 Lawrence Livermore Molecule No. 105, LLM-105) report unreacted high pressure equations of state that include several structural phase transitions, between 8 and 50 GPa, while one published experimental study reports equation of state (EOS) data up to a pressure of 6 GPa with no observed transition. Here we report the results of a synchrotron-based X-ray diffraction study and also ambient temperature isobaric-isothermal atomistic molecular dynamics simulations of LLM-105 up to 20 GPa. We find that the ambient pressure phase remains stable up to 20 GPa; there is no indication of a pressure induced phase transition. We do find a prominent decrease in b-axis compressibility starting at approximately 13 GPa and attribute the stiffening to a critical length where inter-sheet distance becomes similar to the intermolecular distance within individual sheets. The ambient temperature isothermal equation of state was determined through refinements of measured X-ray diffraction patterns. The pressure-volume data were fit using various EOS models to yield bulk moduli with corresponding pressure derivatives. We find very good agreement between the experimental and theoretically derived EOS. PMID:26472388

  16. The high pressure structure and equation of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) up to 20 GPa: X-ray diffraction measurements and first principles molecular dynamics simulations

    SciTech Connect

    Stavrou, Elissaios Riad Manaa, M. Zaug, Joseph M.; Kuo, I-Feng W.; Pagoria, Philip F.; Crowhurst, Jonathan C.; Armstrong, Michael R.; Kalkan, Bora

    2015-10-14

    Recent theoretical studies of 2,6-diamino-3,5-dinitropyrazine-1-oxide (C{sub 4}H{sub 4}N{sub 6}O{sub 5} Lawrence Livermore Molecule No. 105, LLM-105) report unreacted high pressure equations of state that include several structural phase transitions, between 8 and 50 GPa, while one published experimental study reports equation of state (EOS) data up to a pressure of 6 GPa with no observed transition. Here we report the results of a synchrotron-based X-ray diffraction study and also ambient temperature isobaric-isothermal atomistic molecular dynamics simulations of LLM-105 up to 20 GPa. We find that the ambient pressure phase remains stable up to 20 GPa; there is no indication of a pressure induced phase transition. We do find a prominent decrease in b-axis compressibility starting at approximately 13 GPa and attribute the stiffening to a critical length where inter-sheet distance becomes similar to the intermolecular distance within individual sheets. The ambient temperature isothermal equation of state was determined through refinements of measured X-ray diffraction patterns. The pressure-volume data were fit using various EOS models to yield bulk moduli with corresponding pressure derivatives. We find very good agreement between the experimental and theoretically derived EOS.

  17. The high pressure structure and equation of state of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) up to 20 GPa: X-ray diffraction measurements and first principles molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Stavrou, Elissaios; Riad Manaa, M.; Zaug, Joseph M.; Kuo, I.-Feng W.; Pagoria, Philip F.; Kalkan, Bora; Crowhurst, Jonathan C.; Armstrong, Michael R.

    2015-10-01

    Recent theoretical studies of 2,6-diamino-3,5-dinitropyrazine-1-oxide (C4H4N6O5 Lawrence Livermore Molecule No. 105, LLM-105) report unreacted high pressure equations of state that include several structural phase transitions, between 8 and 50 GPa, while one published experimental study reports equation of state (EOS) data up to a pressure of 6 GPa with no observed transition. Here we report the results of a synchrotron-based X-ray diffraction study and also ambient temperature isobaric-isothermal atomistic molecular dynamics simulations of LLM-105 up to 20 GPa. We find that the ambient pressure phase remains stable up to 20 GPa; there is no indication of a pressure induced phase transition. We do find a prominent decrease in b-axis compressibility starting at approximately 13 GPa and attribute the stiffening to a critical length where inter-sheet distance becomes similar to the intermolecular distance within individual sheets. The ambient temperature isothermal equation of state was determined through refinements of measured X-ray diffraction patterns. The pressure-volume data were fit using various EOS models to yield bulk moduli with corresponding pressure derivatives. We find very good agreement between the experimental and theoretically derived EOS.

  18. Stereoselective formation of the varietal aroma compound rose oxide during alcoholic fermentation.

    PubMed

    Koslitz, Stephan; Renaud, Lauren; Kohler, Marcel; Wüst, Matthias

    2008-02-27

    The potent aroma compound rose oxide was quantified in several white wines by a headspace solid-phase microextration stable isotope dilution assay (HS-SPME-SIDA) and the enantiomeric ratios of the cis diastereomers were determined by enantioselective capillary GC. The most odor-active stereoisomer (23)-cis-rose oxide was detectable in all investigated white wines ranging from 0.2 to 12 microg/L. However, its contribution to the overall aroma in some white wine varieties can be neglected as indicated by a low odor activity value (OAV). The highest concentrations were found in Gewürztraminer wines, confirming the importance of rose oxide as a varietal aroma compound in this variety. Surprisingly, the enantiomeric ratio of cis-rose oxide in all investigated wines was substantially lower than in nonfermented musts and in some wines almost racemic cis-rose oxide was detected. Fermentation studies with a model must that contained deuterated water revealed that yeast is capable of reducing the precursor 3,7-dimethyl octa-2,5-dien-1,7-diol (geranyl diol I) yielding 3,7-dimethyl-5-octen-1,7-diol (citronellyl diol I) that gives rise to cis- and trans-rose oxide after acid catalyzed cylization. The deuterium labeling pattern of the resulting rose oxide stereoisomers and a clearly detectable kinetic isotope effect indicate that at least two different reductive pathways in yeast exist that yield cis-rose oxide with different enantiomeric ratios altering the genuine enantiomeric ratio in grape musts. The presence of (+)-cis-rose oxides in wines can therefore be attributed to the reductive yeast metabolism during fermentation. This observation corroborates recent findings that the modification of terpene derived varietal aroma is an integral part of yeast metabolism and not only a simple hydrolytical process. PMID:18247534

  19. Manganese Compounds as Water-Oxidizing Catalysts: From the Natural Water-Oxidizing Complex to Nanosized Manganese Oxide Structures.

    PubMed

    Najafpour, Mohammad Mahdi; Renger, Gernot; Hołyńska, Małgorzata; Moghaddam, Atefeh Nemati; Aro, Eva-Mari; Carpentier, Robert; Nishihara, Hiroshi; Eaton-Rye, Julian J; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2016-03-01

    All cyanobacteria, algae, and plants use a similar water-oxidizing catalyst for water oxidation. This catalyst is housed in Photosystem II, a membrane-protein complex that functions as a light-driven water oxidase in oxygenic photosynthesis. Water oxidation is also an important reaction in artificial photosynthesis because it has the potential to provide cheap electrons from water for hydrogen production or for the reduction of carbon dioxide on an industrial scale. The water-oxidizing complex of Photosystem II is a Mn-Ca cluster that oxidizes water with a low overpotential and high turnover frequency number of up to 25-90 molecules of O2 released per second. In this Review, we discuss the atomic structure of the Mn-Ca cluster of the Photosystem II water-oxidizing complex from the viewpoint that the underlying mechanism can be informative when designing artificial water-oxidizing catalysts. This is followed by consideration of functional Mn-based model complexes for water oxidation and the issue of Mn complexes decomposing to Mn oxide. We then provide a detailed assessment of the chemistry of Mn oxides by considering how their bulk and nanoscale properties contribute to their effectiveness as water-oxidizing catalysts. PMID:26812090

  20. Detection and quantification of gas-phase oxidized mercury compounds by GC/MS

    NASA Astrophysics Data System (ADS)

    Jones, Colleen P.; Lyman, Seth N.; Jaffe, Daniel A.; Allen, Tanner; O'Neil, Trevor L.

    2016-05-01

    Most mercury pollution is emitted to the atmosphere, and the location and bioavailability of deposited mercury largely depends on poorly understood atmospheric chemical reactions that convert elemental mercury into oxidized mercury compounds. Current measurement methods do not speciate oxidized mercury, leading to uncertainty about which mercury compounds exist in the atmosphere and how oxidized mercury is formed. We have developed a gas chromatography/mass spectrometry (GC-MS)-based system for identification and quantification of atmospheric oxidized mercury compounds. The system consists of an ambient air collection device, a thermal desorption module, a cryofocusing system, a gas chromatograph, and an ultra-sensitive mass spectrometer. It was able to separate and identify mercury halides with detection limits low enough for ambient air collection (90 pg), but an improved ambient air collection device is needed. The GC/MS system was unable to quantify HgO or Hg(NO3)2, and data collected cast doubt upon the existence of HgO in the gas phase.

  1. Crystal structure of [NaZn(BTC)(H2O)4]·1.5H2O (BTC = benzene-1,3,5-tri-carb-oxy-l-ate): a heterometallic coordination compound.

    PubMed

    Ni, Min; Li, Quanle; Chen, Hao; Li, Shengqing

    2015-07-01

    The title coordination polymer, poly[[μ-aqua-tri-aqua-(μ3-benzene-1,3,5-tri-carboxyl-ato)sodiumzinc] sesquihydrate], {[NaZn(C9H3O6)(H2O)4]·1.5H2O} n , was obtained in ionic liquid microemulsion at room temperture by the reaction of benzene-1,3,5-tri-carb-oxy-lic acid (H3BTC) with Zn(NO3)2·6H2O in the presence of NaOH. The asymmetric unit comprises two Na(+) ions (each located on an inversion centre), one Zn(2+) ion, one BTC ligand, four coordinating water mol-ecules and two solvent water molecules, one of which is disordered about an inversion centre and shows half-occupation. The Zn(2+) cation is five-coordinated by two carboxyl-ate O atoms from two different BTC ligands and three coordinating H2O mol-ecules; the Zn-O bond lengths are in the range 1.975 (2)-2.058 (3) Å. The Na(+) cations are six-coordinated but have different arrangements of the ligands: one is bound to two carboxyl-ate O atoms of two BTC ligands and four O atoms from four coordinating H2O mol-ecules while the other is bound by four carboxyl-ate O atoms from four BTC linkers and two O atoms of coordinating H2O mol-ecules. The completely deprotonated BTC ligand acts as a bridging ligand binding the Zn(2+) atom and Na(+) ions, forming a layered structure extending parallel to (100). An intricate network of O-H⋯O hydrogen bonds is present within and between the layers. PMID:26279893

  2. Crystal structure of [NaZn(BTC)(H2O)4]·1.5H2O (BTC = benzene-1,3,5-tri­carb­oxy­l­ate): a heterometallic coordination compound

    PubMed Central

    Ni, Min; Li, Quanle; Chen, Hao; Li, Shengqing

    2015-01-01

    The title coordination polymer, poly[[μ-aqua-tri­aqua­(μ3-benzene-1,3,5-tri­carboxyl­ato)sodiumzinc] sesquihydrate], {[NaZn(C9H3O6)(H2O)4]·1.5H2O}n, was obtained in ionic liquid microemulsion at room temperture by the reaction of benzene-1,3,5-tri­carb­oxy­lic acid (H3BTC) with Zn(NO3)2·6H2O in the presence of NaOH. The asymmetric unit comprises two Na+ ions (each located on an inversion centre), one Zn2+ ion, one BTC ligand, four coordinating water mol­ecules and two solvent water molecules, one of which is disordered about an inversion centre and shows half-occupation. The Zn2+ cation is five-coordinated by two carboxyl­ate O atoms from two different BTC ligands and three coordinating H2O mol­ecules; the Zn—O bond lengths are in the range 1.975 (2)–2.058 (3) Å. The Na+ cations are six-coordinated but have different arrangements of the ligands: one is bound to two carboxyl­ate O atoms of two BTC ligands and four O atoms from four coordinating H2O mol­ecules while the other is bound by four carboxyl­ate O atoms from four BTC linkers and two O atoms of coordinating H2O mol­ecules. The completely deprotonated BTC ligand acts as a bridging ligand binding the Zn2+ atom and Na+ ions, forming a layered structure extending parallel to (100). An intricate network of O—H⋯O hydrogen bonds is present within and between the layers. PMID:26279893

  3. Laser Cavity Ringdown Studies of Peroxy Radical Intermediates in the Oxidation of Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Okumura, M.; Takematsu, K.; Eddingsaas, N. C.; Dodson, L. G.; Voss, M.; Nishimura, A.

    2012-12-01

    The detection of reactive intermediates in laboratory kinetics experiments provides a powerful method for determining reaction pathways in the oxidation of Volatile Organic Compounds (VOCs). Many Biogenic VOCs (BVOCs) such as isoprene are unsaturated, and their oxidation can proceed through initial addition of an OH, Cl or NO3 radicals, followed by addition of O2 to form peroxy radicals. We have used cavity ringdown spectroscopy to directly detect substituted peroxy radical intermediates formed in the initial oxidation of a number of unsaturated species, including ethene, propene, butene, butadiene, MBO-232, and MPAN. These experiments have allowed us to identify specific pathways in the oxidation of the parent unsaturated VOC species and to begin studying the rates of subsequent peroxy radical reactions. These studies shed light on the possible pathways for OVOC formation and likely impact on secondary aerosol formation.

  4. Understanding the role of manganese dioxide in the oxidation of phenolic compounds by aqueous permanganate.

    PubMed

    Jiang, Jin; Gao, Yuan; Pang, Su-Yan; Lu, Xue-Ting; Zhou, Yang; Ma, Jun; Wang, Qiang

    2015-01-01

    Recent studies have shown that manganese dioxide (MnO2) can significantly accelerate the oxidation kinetics of phenolic compounds such as triclosan and chlorophenols by potassium permanganate (Mn(VII)) in slightly acidic solutions. However, the role of MnO2 (i.e., as an oxidant vs catalyst) is still unclear. In this work, it was demonstrated that Mn(VII) oxidized triclosan (i.e., trichloro-2-phenoxyphenol) and its analogue 2-phenoxyphenol, mainly generating ether bond cleavage products (i.e., 2,4-dichlorophenol and phenol, respectively), while MnO2 reacted with them producing appreciable dimers as well as hydroxylated and quinone-like products. Using these two phenoxyphenols as mechanistic probes, it was interestingly found that MnO2 formed in situ or prepared ex situ greatly accelerated the kinetics but negligibly affected the pathways of their oxidation by Mn(VII) at acidic pH 5. The yields (R) of indicative products 2,4-dichlorophenol and phenol from their respective probes (i.e., molar ratios of product formed to probe lost) under various experimental conditions were quantified. Comparable R values were obtained during the treatment by Mn(VII) in the absence vs presence of MnO2. Meanwhile, it was confirmed that MnO2 could accelerate the kinetics of Mn(VII) oxidation of refractory nitrophenols (i.e., 2-nitrophenol and 4-nitrophenol), which otherwise showed negligible reactivity toward Mn(VII) and MnO2 individually, and the effect of MnO2 was strongly dependent upon its concentration as well as solution pH. These results clearly rule out the role of MnO2 as a mild co-oxidant and suggest a potential catalytic effect on Mn(VII) oxidation of phenolic compounds regardless of their susceptibility to oxidation by MnO2. PMID:25437924

  5. Optical properties across the insulator to metal transitions in vanadium oxide compounds.

    PubMed

    Perucchi, A; Baldassarre, L; Postorino, P; Lupi, S

    2009-08-12

    We review the optical properties of three vanadium oxide compounds V(2)O(3), VO(2) and V(3)O(5), belonging to the so-called Magnéli phase. Their electrodynamics across a metal to insulator transition is investigated as a function of both temperature and pressure. We analyse thoroughly the optical results, with a special emphasis on the infrared spectral weight. This allows us to discuss the nature of the mechanisms driving the phase transitions in the three compounds, pointing out the role of electron-electron and electron-phonon interactions in the various cases. PMID:21693963

  6. Method of making metal oxide ceramic powders by using a combustible amino acid compound

    DOEpatents

    Pederson, L.R.; Chick, L.A.; Exarhos, G.J.

    1992-05-19

    This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

  7. Method of making metal oxide ceramic powders by using a combustible amino acid compound

    DOEpatents

    Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

    1992-01-01

    This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

  8. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    DOE PAGESBeta

    Ramasamy, Karthikeyan K.; Gray, Michel; Job, Heather; Smith, Colin; Wang, Yong

    2016-02-03

    Here, a highly versatile ethanol conversion process to selectively generate high value compounds is presented here. By changing the reaction temperature, ethanol can be selectively converted to >C2 alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3 catalyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensation or the acetone formation is the path taken in changing the product composition. This article contains the catalytic activity comparison between the mono-functional and physical mixture counterpart to the hydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  9. Electrocatalytic Materials and Techniques for the Anodic Oxidation of Various Organic Compounds

    SciTech Connect

    Stephen Everett Treimer

    2002-06-27

    The focus of this thesis was first to characterize and improve the applicability of Fe(III) and Bi(V) doped PbO{sub 2} film electrodes for use in anodic O-transfer reactions of toxic and waste organic compounds, e.g. phenol, aniline, benzene, and naphthalene. Further, they investigated the use of alternative solution/electrode interfacial excitation techniques to enhance the performance of these electrodes for remediation and electrosynthetic applications. Finally, they have attempted to identify a less toxic metal oxide film that may hold promise for future studies in the electrocatalysis and photoelectrocatalysis of O-transfer reactions using metal oxide film electrodes.

  10. Physical Characterization of RX-55-AE-5 a Formulation of 97.5 % 2,6-Diamino-3,5-Dinitropyrazine-1-Oxide (LLM-105) and 2.5% Viton A

    SciTech Connect

    Weese, R K; Burnham, A K; Turner, H C; Tran, T D

    2005-07-28

    With the use of modern tools such as molecular modeling on increasingly powerful computers, new materials can be evaluated by their structural activity relationships, SAR, and their approximate physical and chemical properties can be calculated in some cases with surprising accuracy. These new capabilities enable streamlined synthetic routes based on safety, performance and processing requirements, to name a few [1]. Current work includes both understanding properties of old explosives and measuring properties of new ones. The necessity to know and understand the properties of energetic materials is driven by the need to improve performance and enhance stability to various stimuli, such as thermal, friction and impact insult. This review will concentrate on the physical properties of RX-55-AE-5, which is formulated from heterocyclic explosive, 2,6-diamino-3,5-dinitropyrazine-1-oxide, LLM-105, and 2.5% Viton A. Differential scanning calorimetry, DSC, was used to measure a specific heat capacity, C{sub p}, of {approx} 0.950 J/g {center_dot} C, and a thermal conductivity, {kappa}, of {approx} 0.160 W/m {center_dot} C. The Lawrence Livermore National Laboratory (LLNL) code Kinetics05 and the Advanced Kinetics and Technology Solutions (AKTS) code Thermokinetics were both used to calculate Arrhenius kinetics for decomposition of LLM-105. Both obtained an activation energy barrier E {approx} 180 kJ mol{sup -1} for mass loss in an open pan. Thermal mechanical analysis, TMA, was used to measure the coefficient of thermal expansion, CTE. The CTE for this formulation was calculated to be {approx} 61 {micro}m/m {center_dot} C. Impact, spark, friction and evolved gases are also reported.

  11. Physical Characterization of RX-55-AE-5 A formulation of 97.5 % 2, 6-diamino-3, 5-dinitropyrazine-1-oxide (LLM 105) and 2.5 % Viton A

    SciTech Connect

    Weese, R K; Burnham, A K; Turner, H C; Tran, T

    2005-06-08

    With the use of modern tools such as molecular modeling on increasingly powerful computers, new materials can be evaluated by their structural activity relationships, SAR, and their approximate physical and chemical properties can be calculated in some cases with surprising accuracy. These new capabilities enable streamlined synthetic routes based on safety, performance and processing requirements, to name a few [1]. Current work includes both understanding properties of old explosives and measuring properties of new ones. The necessity to know and understand the properties of energetic materials is driven by the need to improve performance and enhance stability to various stimuli, such as thermal, friction and impact insult. This review will concentrate on the physical properties of RX-55-AE-5, which is formulated from heterocyclic explosive, 2,6-diamino-3,5-dinitropyrazine-1-oxide, LLM-105, and 2.5% Viton A. Differential scanning calorimetry, DSC, was used to measure a specific heat capacity, C{sub p}, of {approx} 0.950 J/g{center_dot} C, and a thermal conductivity, {kappa}, of {approx} 0.160 W/m{center_dot} C. The Lawrence Livermore National Laboratory (LLNL) code ''Kinetics05'' and the Advanced Kinetics and Technology Solutions (AKTS) code ''Thermokinetics'' were both used to calculate Arrhenius kinetics for decomposition of LLM-105. Both obtained an activation energy barrier E {approx} 180 kJ mol{sup -1} for mass loss in an open pan. Thermal mechanical analysis, TMA, was used to measure the coefficient of thermal expansion, CTE. The CTE for this formulation was calculated to be {approx} 61 {micro}m/m{center_dot} C. Impact, spark, friction and evolved gases are also reported.

  12. Identification of Oxidation Compounds of 1-Stearoyl-2-linoleoyl-sn-glycero-3-phosphoethanolamine during Thermal Oxidation.

    PubMed

    Zhou, Li; Zhao, Minjie; Bindler, Françoise; Marchioni, Eric

    2015-11-01

    Heat-induced oxidative modification of phosphatidylethanolamine molecular species as potential functional food components was investigated. 1-Stearoyl-2-linoleoyl-sn-glycero-3-phosphoethanolamine (SLPE) was chosen as a model. The optimal temperature for hydroperoxide formation was determined by mass spectrometry. The maximal level of formation of this compound was obtained at 125 °C. The structures of nonvolatile organic compounds (non-VOCs) were identified using liquid chromatography-electrospray ionization mass spectrometry combined with an acid treatment. Kinetics of formation of non-VOCs was monitored over time. Results showed that the level of the SLPE precursor rapidly decreased during thermal oxidation and oxygenated products, such as hydroxyl, oxo, or epoxy groups, were formed. The VOCs formed from oxidized SLPE were determined by headspace solid-phase microextraction followed by gas chromatography-mass spectrometry analysis. The result showed that a saturated methyl ketone (2-heptanone) was the most predominant VOC of SLPE. Kinetics indicated that the formation of VOCs was related not only to the decomposition of hydroperoxides but also to the further decomposition of non-VOCs. PMID:26478449

  13. Identificaton of 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one isolated from Lactobacillus pentosus strain S-PT84 culture supernatants as a compound that stimulates autonomic nerve activities in rats.

    PubMed

    Beppu, Yoshinori; Komura, Hajime; Izumo, Takayuki; Horii, Yuko; Shen, Jiao; Tanida, Mamoru; Nakashima, Toshihiro; Tsuruoka, Nobuo; Nagai, Katsuya

    2012-11-01

    Intestinal administration of various lactobacilli has been reported to affect autonomic neurotransmission, blood pressure, and body weight in rats. In this study, three molecules (peaks A, B, and C) were isolated from Lactobacillus pentosus strain S-PT84 (S-PT 84) culture supernatants. Intraduodenal (ID) injection of these molecules increased or inhibited renal sympathetic nerve activity (RSNA) in rats as follows: peak A, 134%; peak B, 40.1%; peak C, 408%. Furthermore, we identified peak C as 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP). ID injection of DDMP increased brown adipose tissue sympathetic nerve activity (BAT-SNA; 118 ± 15.3%), whereas intraoral injection of DDMP increased the body temperature above the interscapular brown adipose tissue (BAT-T; 0.72 ± 0.13 °C) in rats. These data suggest that S-PT84 produces molecules that modulate autonomic nerve activity. In addition, DDMP increased BAT-SNA and BAT-T, and these changes in BAT-T may be caused by changes in BAT-SNA. PMID:23082723

  14. Nonlinear optical properties and optical limiting measurements of graphene oxide - Ag@TiO2 compounds

    NASA Astrophysics Data System (ADS)

    Ebrahimi, M.; Zakery, A.; Karimipour, M.; Molaei, M.

    2016-07-01

    In this work Graphene Oxide (GO), Ag@TiO2 core-shells and GO-Ag@TiO2 compounds were prepared and experimentally verified. Using a low power laser diode with 532 nm wavelength, the magnitude and the sign of the nonlinear refractive index and nonlinear absorption were determined by the Z-scan technique. It was observed that the nonlinear absorption of GO-Ag@TiO2 mixture was higher than pure GO. The optical limiting effect of these samples was also investigated using the 2nd harmonics of a pulsed Nd-YAG laser at 532 nm. Our results showed that the sole Ag@TiO2 didn't show any appreciable optical limiting effect, however after just mixing with graphene oxide the threshold of optical limiting was increased and the compound showed an enhancement of optical limiting behavior compared to GO itself. The presented results are discussed and compared with other literature reports.

  15. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues—Model Compounds Targeting Oxidative Stress

    PubMed Central

    Velena, Astrida; Zarkovic, Neven; Gall Troselj, Koraljka; Bisenieks, Egils; Krauze, Aivars; Poikans, Janis; Duburs, Gunars

    2016-01-01

    Many 1,4-dihydropyridines (DHPs) possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS) and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA). Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL), mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry. PMID:26881016

  16. 1,4-Dihydropyridine Derivatives: Dihydronicotinamide Analogues-Model Compounds Targeting Oxidative Stress.

    PubMed

    Velena, Astrida; Zarkovic, Neven; Gall Troselj, Koraljka; Bisenieks, Egils; Krauze, Aivars; Poikans, Janis; Duburs, Gunars

    2016-01-01

    Many 1,4-dihydropyridines (DHPs) possess redox properties. In this review DHPs are surveyed as protectors against oxidative stress (OS) and related disorders, considering the DHPs as specific group of potential antioxidants with bioprotective capacities. They have several peculiarities related to antioxidant activity (AOA). Several commercially available calcium antagonist, 1,4-DHP drugs, their metabolites, and calcium agonists were shown to express AOA. Synthesis, hydrogen donor properties, AOA, and methods and approaches used to reveal biological activities of various groups of 1,4-DHPs are presented. Examples of DHPs antioxidant activities and protective effects of DHPs against OS induced damage in low density lipoproteins (LDL), mitochondria, microsomes, isolated cells, and cell cultures are highlighted. Comparison of the AOA of different DHPs and other antioxidants is also given. According to the data presented, the DHPs might be considered as bellwether among synthetic compounds targeting OS and potential pharmacological model compounds targeting oxidative stress important for medicinal chemistry. PMID:26881016

  17. New tracer compounds for secondary organic aerosol formation from β-caryophyllene oxidation

    NASA Astrophysics Data System (ADS)

    van Eijck, Anna; Opatz, Till; Taraborrelli, Domenico; Sander, Rolf; Hoffmann, Thorsten

    2013-12-01

    Five products from β-caryophyllene oxidation (β-caryophyllonic acid (I), 3,3-dimethyl-2-(3-oxobutyl)cyclobutanecarboxylic acid (βCA198) (II), β-nocaryophyllonic acid (III), β-caryophyllinic acid (IV), and 2-(2-carboxyethyl)-3,3-dimethylcyclobutanecarboxylic acid (βCA200) (V)) were synthesized and their structures confirmed by nuclear magnetic resonance spectroscopy. Reaction chamber experiments with β-caryophyllene at two different ozone mixing ratios were performed and the carboxylic acid oxidation products in the particle phase were characterized by APCI-MS and HPLC-ESI-MS. All five synthesized acids were found as β-caryophyllene oxidation products in the reaction chamber aerosol. The main oxidation products of the reaction chamber experiments were β-14-hydroxynocaryophyllonic acid, β-nocaryophyllonic acid (III) and βCA198 (II). Product yields of the acids were estimated based on the chamber experiments and the application of the atmospheric chemistry box model CAABA/MECCA. Finally, ambient aerosol samples taken during the HUMPPA campaign in Hyytiälä, Finland in summer 2010 were analysed for the carboxylic acid β-caryophyllene oxidation products. All five synthesized compounds were detected and were quantified in the ambient aerosol samples. The major β-caryophyllene carboxylic acid oxidation products in the ambient air samples were β-nocaryophyllonic acid (III) and βCA198 (II) with concentrations in the range of about 0.2-14 ng m-3 and 0.8-6.8 ng m-3. The fact that the concentrations of these two acids in ambient aerosol are generally higher than the concentration of β-caryophyllinic acid (IV) (often used in previous studies as oxidation tracer) with a concentration of about 0.16 ng m-3 leads to the conclusion that these two acids are better suited as tracer compounds for β-caryophyllene secondary organic aerosol formation.

  18. Biotransformations Utilizing β-Oxidation Cycle Reactions in the Synthesis of Natural Compounds and Medicines

    PubMed Central

    Œwizdor, Alina; Panek, Anna; Milecka-Tronina, Natalia; Kołek, Teresa

    2012-01-01

    β-Oxidation cycle reactions, which are key stages in the metabolism of fatty acids in eucaryotic cells and in processes with a significant role in the degradation of acids used by microbes as a carbon source, have also found application in biotransformations. One of the major advantages of biotransformations based on the β-oxidation cycle is the possibility to transform a substrate in a series of reactions catalyzed by a number of enzymes. It allows the use of sterols as a substrate base in the production of natural steroid compounds and their analogues. This route also leads to biologically active compounds of therapeutic significance. Transformations of natural substrates via β-oxidation are the core part of the synthetic routes of natural flavors used as food additives. Stereoselectivity of the enzymes catalyzing the stages of dehydrogenation and addition of a water molecule to the double bond also finds application in the synthesis of chiral biologically active compounds, including medicines. Recent advances in genetic, metabolic engineering, methods for the enhancement of bioprocess productivity and the selectivity of target reactions are also described. PMID:23443116

  19. Biotransformations utilizing β-oxidation cycle reactions in the synthesis of natural compounds and medicines.

    PubMed

    Swizdor, Alina; Panek, Anna; Milecka-Tronina, Natalia; Kołek, Teresa

    2012-01-01

    β-Oxidation cycle reactions, which are key stages in the metabolism of fatty acids in eucaryotic cells and in processes with a significant role in the degradation of acids used by microbes as a carbon source, have also found application in biotransformations. One of the major advantages of biotransformations based on the β-oxidation cycle is the possibility to transform a substrate in a series of reactions catalyzed by a number of enzymes. It allows the use of sterols as a substrate base in the production of natural steroid compounds and their analogues. This route also leads to biologically active compounds of therapeutic significance. Transformations of natural substrates via β-oxidation are the core part of the synthetic routes of natural flavors used as food additives. Stereoselectivity of the enzymes catalyzing the stages of dehydrogenation and addition of a water molecule to the double bond also finds application in the synthesis of chiral biologically active compounds, including medicines. Recent advances in genetic, metabolic engineering, methods for the enhancement of bioprocess productivity and the selectivity of target reactions are also described. PMID:23443116

  20. Theoretical study for high-energy-density compounds derived from cyclophosphazene. IV. DFT studies on 1,1-diamino-3,3,5,5,7,7-hexaazidocyclotetraphosphazene and its isomers.

    PubMed

    Zhang, Jianguo; Zheng, Huihui; Zhang, Tonglai; Wu, Man

    2009-01-01

    In the present study, a theoretical study of 1,1-diaminohexaazidocyclotetraphophazene (DAHA) and its isomers has been performed, using quantum computational density functional theory (B3LYP and B3PW91 methods) with 6-31G* and 6-31G** basis sets implemented in Gaussian 03 program suite. Molecular structure and bonding, vibrational frequencies, Milliken population analysis, and natural bond orbit (NBO) have been studied. The heats of formation from atomization energies have also been calculated based on the optimized geometry. The obtained heats of formation data are compared with their homologous cyclophosphazene in order to demonstrate the accuracy of the methods, which indicate that the studied compounds might be potentially used as high energetic materials. In addition, the relative stability of five isomers have been deduced based on the total energy and the gap of frontier orbital energies. PMID:19756156

  1. Effect of different cooking methods on lipid oxidation and formation of volatile compounds in foal meat.

    PubMed

    Domínguez, Rubén; Gómez, María; Fonseca, Sonia; Lorenzo, José M

    2014-06-01

    The influence of four different cooking methods (roasting, grilling, microwaving and frying) on cooking loss, lipid oxidation and volatile profile of foal meat was studied. Cooking loss were significantly (P<0.001) affected by thermal treatment, being higher (32.5%) after microwaving and lower after grilling (22.5%) and frying (23.8%). As expected, all the cooking methods increased TBARs content, since high temperature during cooking causes increased oxidation in foal steaks, this increase was significantly (P<0.001) higher when foal steaks were microwaved or roasted. The four different cooking methods led to increased total volatile compounds (between 366.7 and 633.1AU×10(6)/g dry matter) compared to raw steaks (216.4AU×10(6)/g dry matter). The roasted steaks showed the highest volatile content, indicating that increased cooking temperature increases the formation of volatile compounds. Aldehydes were the most abundant compounds in cooked samples, with amounts of 217.2, 364.5, 283.5 and 409.1AU×10(6)/g dry matter in grilled, microwaved, fried and roasted samples, respectively, whereas esters were the most abundant compounds in raw samples, with mean amounts of 98.8AU×10(6)/g dry matter. PMID:24583332

  2. Vascular pharmacology of a novel cannabinoid-like compound, 3-(5-dimethylcarbamoyl-pent-1-enyl)-N-(2-hydroxy-1-methyl-ethyl)benzamide (VSN16) in the rat

    PubMed Central

    Hoi, P M; Visintin, C; Okuyama, M; Gardiner, S M; Kaup, S S; Bennett, T; Baker, D; Selwood, D L; Hiley, C R

    2007-01-01

    Background and purpose: A putative novel cannabinoid receptor mediates vasorelaxation to anandamide and abnormal-cannabidiol and is blocked by O-1918 and by high concentrations of rimonabant. This study investigates VSN16, a novel water-soluble agonist, as a vasorelaxant potentially acting at non-CB1, non-CB2 cannabinoid receptors in the vasculature. Experimental approach: VSN16 and some analogues were synthesized and assayed for vasodilator activity in the rat third generation mesenteric artery using wire myography. Also carried out with VSN16 were haemodynamic studies in conscious rats and binding studies to CB1 receptors of rat cerebellum. Key results: VSN16 relaxed mesenteric arteries in an endothelium-dependent manner. The vasorelaxation was antagonized by high concentrations of the classical cannabinoid antagonists, rimonabant and AM 251, as well as by O-1918, an antagonist at the abnormal-cannabidiol receptor but not at CB1 or CB2 receptors. It did not affect [3H]CP55,940 binding to CB1 receptors in rat cerebellum. The vasorelaxation was not pertussis toxin-sensitive but was reduced by inhibition of nitric oxide synthesis, Ca2+-sensitive K+ channels (KCa) and TRPV1 receptors. In conscious rats VSN16 transiently increased blood pressure and caused a longer-lasting increase in mesenteric vascular conductance. Structure-activity studies on vasorelaxation showed a stringent interaction with the target receptor. Conclusions and implications: VSN16 is an agonist at a novel cannabinoid receptor of the vasculature. It acts on the endothelium to release nitric oxide and activate KCa and TRPV1. As it is water-soluble it might be useful in bringing about peripheral cannabinoid-like effects without accompanying central or severe cardiovascular responses. PMID:17891160

  3. Oxidation behavior of plasma sintered beryllium-titanium intermetallic compounds as an advanced neutron multiplier

    NASA Astrophysics Data System (ADS)

    Kim, Jae-Hwan; Nakamichi, Masaru

    2013-07-01

    Beryllium intermetallic compounds (beryllides) such as Be12Ti are very promising candidates for advanced neutron multiplier materials in a demonstration fusion power reactor (DEMO). However, beryllides are too brittle to be fabricated either into pebble-type or rod-type shapes via conventional methods (i.e. arc melting and hot isostatic pressing). We have proposed a plasma sintering technique as a new method for beryllide fabrication, and our studies on the properties of plasma sintered beryllides are ongoing. In the present work, the oxidation properties of plasma sintered beryllides were investigated at 1273 K for 24 h in a dry air atmosphere to evaluate the high temperature properties of this material. Thermal gravimetry measurements indicate that specimens with larger fractions of Be12Ti phase corresponding to samples that have been sintered for longer time periods, exhibit superior oxidation properties. Our evaluation of the oxidation behavior of each phase in our beryllide samples is as follows: Be12Ti and Be17Ti2 both have good oxidation resistance, owing to the formation of dense and protective scales, while the Be and Be2Ti phases are mainly responsible for thermal-gravimetry (TG) weight gains, which is indicative of severe oxidation. We attribute the degradation in oxidation resistance specifically to Be2Ti that transforms into TiO2, and also find this phase to be the cause of deterioration in the mechanical properties of samples, owing to cracks near Be2Ti phase conglomerates.

  4. The Oxidation of Sulfur-Containing Compounds Using Heterogeneous Catalysts of Transition Metal Oxides Deposited on the Polymeric Matrix

    NASA Astrophysics Data System (ADS)

    Dinh Vu, Ngo; Dinh Bui, Nhi; Thi Minh, Thao; Thi Thanh Dam, Huong; Thi Tran, Hang

    2016-05-01

    We investigate the activity of heterogeneous catalysts of transition metal oxides deposited on the polymeric matrix in the oxidation of sulfur-containing compounds. It is shown that MnO2-10/CuO-10 has the highest catalytic activity. The physicomechanical properties of polymeric heterogeneous catalysts of transition-metal oxides, including the specific surface area, elongation at break and breaking strength, specific electrical resistance, and volume resistivity were studied by using an Inspekt mini 3 kN universal tensile machine in accordance with TCVN 4509:2006 at a temperature of 20 ± 2°C. Results show that heterogeneous polymeric catalysts were stable under severe reaction conditions. Scanning electron microscopy, and energy-dispersive analysis are used to study the surfaces of the catalysts. Microstructural characterization of the catalysts is performed by using x-ray computed tomography. We demonstrate the potential application of polymeric heterogeneous catalysts of transition-metal oxides in industrial wastewater treatment.

  5. Pioneering Metal-Free Oxidative Coupling Strategy of Aromatic Compounds Using Hypervalent Iodine Reagents.

    PubMed

    Kita, Yasuyuki; Dohi, Toshifumi

    2015-10-01

    We started our hypervalent iodine research about 30 years ago in the mid-1980s. We soon successfully developed the single-electron-transfer oxidation ability of a hypervalent iodine reagent, specifically, phenyliodine(III) bis(trifluoroacetate) (PIFA), toward aromatic rings of phenyl ethers for forming aromatic cation radicals. This was one of the exciting and unexpected events in our research studies so far, and the discovery was reported in 1991. It also led to the next challenge, developing the metal-free oxidative couplings for C-H functionalizations and direct couplings between the C-H bonds of valuable aromatic compounds in organic synthesis. In order to realize the effective oxidative coupling, pioneering new aromatic ring activations was essential and several useful methodologies have been found for oxidizable arenes. The achievements regarding this objective obtained in our continuous research are herein summarized with classification of the aromatic ring activation strategies. PMID:26223195

  6. Experimental study of effect of nitrogenous compounds in fuel on the emission of oxides of nitrogen from gas turbines

    SciTech Connect

    Svinukhov, V.P.; Filippova, E.M.

    1987-11-01

    Results of a study are presented on the relation between the output of nitric oxide and nitrogen dioxide in the exhaust gas of a gas turbine and the combined nitrogen content of the fuel to which organic nitrogen compounds, including piperidine, pyridine, and analine, have been added. The exhaust gases were analyzed continuously for nitric oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, and unburnt hydrocarbons. Nitric oxide and nitrogen dioxide were assessed by chemiluminescence analysis. The nitrogen compounds used were selected because of the presence of similar high molecular structure compounds in petroleum and cracking distillates and also in coal liquefaction products.

  7. Thermal and oxidation stability of organo-fluorine compound-mixed electrolyte solutions for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Nishikawa, Daiki; Nakajima, Tsuyoshi; Ohzawa, Yoshimi; Koh, Meiten; Yamauchi, Akiyoshi; Kagawa, Michiru; Aoyama, Hirokazu

    2013-12-01

    Thermal and oxidation stability of fluorine compound-mixed electrolyte solutions have been investigated. Charge/discharge behavior of natural graphite electrode has been also examined in the same electrolyte solutions. Fluorine compounds demonstrate much lower reactivity with metallic Li than ethylene carbonate/dimethyl carbonate. Fluorine compound-mixed electrolyte solutions show the lower reactivity with LiC6 and the smaller exothermic peaks due to decomposition of electrolyte solutions and surface films than original solutions without fluorine compound. Oxidation currents are also smaller in fluorine compound-mixed electrolyte solutions than in original ones. First coulombic efficiencies in fluorine compound-mixed electrolyte solutions are similar to those in original ethylene carbonate-based solutions except one case. Mixing of fluorine compounds highly increase first coulombic efficiencies of natural graphite electrode in propylene carbonate-containing solution.

  8. Effects of inhibitors and NaCl on the oxidation of reduced inorganic sulfur compounds by a marine acidophilic, sulfur-oxidizing bacterium, Acidithiobacillus thiooxidans strain SH.

    PubMed

    Kamimura, Kazuo; Higashino, Emi; Kanao, Tadayoshi; Sugio, Tsuyoshi

    2005-02-01

    The effect of NaCl and the pathways of the oxidation of reduced inorganic sulfur compounds were studied using resting cells and cell-free extracts of Acidithiobacillus thiooxidans strain SH. This isolate specifically requires NaCl for growth. The oxidation of sulfur and sulfite by resting cells was strongly inhibited by 2-heptyl-4-hydroxyquinoline-N-oxide. Carbonylcyanide m-chlorophenyl-hydrazone and monensin were also relatively strong inhibitors. Thiosulfate-oxidizing activity was not inhibited by these uncouplers. Valinomycin did not inhibit the oxidation of sulfur compounds. NaCl stimulated the sulfur- and sulfite-oxidizing activities in resting cells but not in cell-free extracts. The tetrathionate-oxidizing activity in resting cells was slightly stimulated by NaCl, whereas it did not influence the thiosulfate-oxidizing activity. Sulfide oxidation was biphasic, suggesting the formation of intermediate sulfur. The initial phase of sulfide oxidation was not affected by NaCl, whereas the subsequent oxidation of sulfur in the second phase was Na+-dependent. A model is proposed for the role of NaCl in the metabolism of reduced sulfur compounds in A. thiooxidans strain SH. PMID:15375674

  9. Ozone reactivity of biogenic volatile organic compound (BVOC) emissions during the Southeast Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Park, J.; Guenther, A. B.; Helmig, D.

    2013-12-01

    Recent studies on atmospheric chemistry in the forest environment showed that the total reactivity by biogenic volatile organic compound (BVOC) emission is still not well understood. During summer 2013, an intensive field campaign (Southeast Oxidant and Aerosol Study - SOAS) took place in Alabama, U.S.A. In this study, an ozone reactivity measurement system (ORMS) was deployed for the direct determination of the reactivity of foliage emissions. The ORMS is a newly developed measurement approach, in which a known amount of ozone is added to the ozone-free air sample stream, with the ORMS measuring ozone concentration difference between before and after a glass flask flow tube reaction vessel (2-3 minutes of residence time). Emissions were also collected onto adsorbent cartridges to investigate the discrepancy between total ozone reactivity observation and reactivity calculated from identified BVOC. Leaf and canopy level experiments were conducted by deploying branch enclosures on the three dominant tree species at the site (i.e. liquidambar, white oak, loblolly pine) and by sampling ambient air above the forest canopy. For the branch enclosure experiments, BVOC emissions were sampled from a 70 L Teflon bag enclosure, purged with air scrubbed for ozone, nitrogen oxides. Each branch experiment was performed for 3-5 days to collect at least two full diurnal cycle data. In addition, BVOCs were sampled using glass tube cartridges for 2 hours during daytime and 3 - 4 hours at night. During the last week of campaign, the inlet for the ORMS was installed on the top of scaffolding tower (~30m height). The ozone loss in the reactor showed distinct diurnal cycle for all three tree species investigated, and ozone reactivity followed patterns of temperature and light intensity.

  10. Evaluation of the protective effect of chemical additives in the oxidation of phenolic compounds catalysed by peroxidase.

    PubMed

    Torres, Juliana Arriel; Chagas, Pricila Maria Batista; Silva, Maria Cristina; Dos Santos, Custódio Donizete; Corrêa, Angelita Duarte

    2016-01-01

    The use of oxidoredutive enzymes in removing organic pollutants has been the subject of much research. The oxidation of phenolic compounds in the presence of chemical additives has been the focus of this study. In this investigation, the influence of the additives polyethylene glycol and Triton X-100 was evaluated in the phenol oxidation, caffeic acid, chlorogenic acid and total phenolic compounds present in coffee processing wastewater (CPW) at different pH values, performed by turnip peroxidase and peroxidase extracted from soybean seed hulls. The influence of these additives was observed only in the oxidation of phenol and caffeic acid. In the oxidation of other studied phenolic compounds, the percentage of oxidation remained unchanged in the presence of these chemical additives. In the oxidation of CPW in the presence of additives, no change in the oxidation of phenolic compounds was observed. Although several studies show the importance of evaluating the influence of additives on the behaviour of enzymes, this study found a positive response from the economic point of view for the treatment of real wastewater, since the addition of these substances showed no influence on the oxidation of phenolic compounds, which makes the process less costly. PMID:26502790

  11. Oxidation of diesel-generated volatile organic compounds in the selective catalytic reduction process

    SciTech Connect

    Koebel, M.; Elsener, M.

    1998-10-01

    The main part of the VOCs (volatile organic compounds) contained in diesel exhaust ({approx}80%) is oxidized to CO and CO{sub 2} over an SCR (selective catalytic reduction) catalyst. CO is the major product of this oxidation, representing about 50--70% of the formed products (CO + CO{sub 2}). This preferential formation of CO leads to a pronounced increase of CO emissions when an SCR process is added to a diesel engine. A small fraction of the VOCs is selectively oxidized to carboxylic acids over the SCR catalyst. This selectivity is due to the acidic properties of the catalyst causing the preferential desorption at the oxidation state of the acid. The main products of these oxidation reactions are the lower monocarboxylic acids and some dicarboxylic acids forming stable anhydrides, especially maleic and phthalic acid. The highest emissions of these acids are found at low temperatures; they decrease at higher temperatures. Formic acid is preferentially decomposed into carbon monoxide and water. It must therefore be assumed that the strong increase of CO mentioned above is due to a mechanism involving the thermal decomposition of formic acid formed from various primary VOCs.

  12. Integration of MEMS with nanostructured metal-oxide materials for improved sensors for volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Chandra, Sudhir; Pandya, Hardik; Vyas, Anoop

    2012-10-01

    The primary aim of the present work is to lower the operating temperature of the metal-oxide based sensors for detection of volatile organic compounds (VOCs) without compromising the sensitivity of the device. For this purpose, nanostructured oxides of ITO, Cu and Zn have been explored. The oxides of Cu and Zn have been synthesized by a novel process of thermal oxidation of the respective metal layers in air ambient without using any seed or catalyst layer. On the other hand, nanostructured ITO was obtained by RF magnetron sputtering process. For the heating of the sensing layer, a Ni microheater has been integrated on the sensor chip. Micro-electro-mechanical Systems (MEMS) technology has been adopted for the fabrication of the complete sensor for achieving the desired operating temperature at reduced power level. The sensor was extensively tested for a variety of VOCs such as acetone, methanol, ethanol and IPA. The issues involved in integrating nanostructured oxides with MEMS technology are also addressed.

  13. Protective effects of novel organic selenium compounds against oxidative stress in the nematode Caenorhabditis elegans

    PubMed Central

    Stefanello, Sílvio Terra; Gubert, Priscila; Puntel, Bruna; Mizdal, Caren Rigon; de Campos, Marli Matiko Anraku; Salman, Syed M.; Dornelles, Luciano; Avila, Daiana Silva; Aschner, Michael; Soares, Félix Alexandre Antunes

    2015-01-01

    Organic selenium compounds possess numerous biological properties, including antioxidant activity. Yet, the high toxicity of some of them, such as diphenyl diselenide (DPDS), is a limiting factor in their current usage. Accordingly, we tested four novel organic selenium compounds in the non-parasite nematode Caenorhabditis elegans and compared their efficacy to DPDS. The novel organic selenium compounds are β-selenoamines (1-phenyl-3-(p-tolylselanyl)propan-2-amine (C1) and 1-(2-methoxyphenylselanyl)-3-phenylpropan-2-amine (C2) and analogs of DPDS (1,2-bis (2-methoxyphenyl) diselenide (C3) and 1,2-bisp-tolyldiselenide (C4). Synchronized worms at the L4 larval stage were exposed for one hour in M9 buffer to these compounds. Oxidative stress conditions were induced by juglone (200 μM) and heat shock (35 °C). Moreover, we evaluated Caenorhabditis elegans behavior, GST-4::GFP (glutathione S-transferase) expression and the activity of acetylcholinesterase (AChE). All tested compounds efficiently restored viability in juglone stressed worms. However, DPDS, C2, C3 and C4 significantly decreased the defecation cycle time. Juglone-induced GST-4::GFP expression was not attenuated in worms pretreated with the novel compounds, except with C2. Finally, AChE activity was reduced by DPDS, C2, C3 and C4. To our knowledge, this is study firstly showed the effects of C1, C2, C3 and C4 selenium-derived compounds in Caenorhabditis elegans. Low toxic effects were noted, except for reduction in the defecation cycle, which is likely associated with AChE inhibition. The juglone-induced stress (reduced viability) was fully reversed by compounds to control animal levels. C2 was also efficient in reducing the juglone-induced GST-4::GFP expression, suggesting the latter may mediate the stress induced by this compound. Future studies could be profitably directed at addressing additional molecular mechanisms that mediate the protective effects of these novel organic selenium compounds. PMID

  14. Block of the Mevalonate Pathway Triggers Oxidative and Inflammatory Molecular Mechanisms Modulated by Exogenous Isoprenoid Compounds

    PubMed Central

    Tricarico, Paola Maura; Kleiner, Giulio; Valencic, Erica; Campisciano, Giuseppina; Girardelli, Martina; Crovella, Sergio; Knowles, Alessandra; Marcuzzi, Annalisa

    2014-01-01

    Deregulation of the mevalonate pathway is known to be involved in a number of diseases that exhibit a systemic inflammatory phenotype and often neurological involvements, as seen in patients suffering from a rare disease called mevalonate kinase deficiency (MKD). One of the molecular mechanisms underlying this pathology could depend on the shortage of isoprenoid compounds and the subsequent mitochondrial damage, leading to oxidative stress and pro-inflammatory cytokines’ release. Moreover, it has been demonstrated that cellular death results from the balance between apoptosis and pyroptosis, both driven by mitochondrial damage and the molecular platform inflammasome. In order to rescue the deregulated pathway and decrease inflammatory markers, exogenous isoprenoid compounds were administered to a biochemical model of MKD obtained treating a murine monocytic cell line with a compound able to block the mevalonate pathway, plus an inflammatory stimulus. Our results show that isoprenoids acted in different ways, mainly increasing the expression of the evaluated markers [apoptosis, mitochondrial dysfunction, nucleotide-binding oligomerization-domain protein-like receptors 3 (NALP3), cytokines and nitric oxide (NO)]. Our findings confirm the hypothesis that inflammation is triggered, at least partially, by the shortage of isoprenoids. Moreover, although further studies are necessary, the achieved results suggest a possible role for exogenous isoprenoids in the treatment of MKD. PMID:24758928

  15. Chloride promoted room temperature preparation of silver nanoparticles on two dimensional tungsten oxide nanoarchitectures for the catalytic oxidation of tertiary N-compounds to N-oxides

    NASA Astrophysics Data System (ADS)

    Ghosh, Shilpi; Acharyya, Shankha S.; Kumar, Malika; Bal, Rajaram

    2015-09-01

    A halide ion promoted two dimensional silver tungsten-based nanomaterial was synthesized by a facile one-pot synthesis protocol at room temperature. The 2D morphology features high activity and selectivity for the oxidation of a wide range of tertiary N-compounds to their corresponding N-oxides. The morphology of Ag/WO3 materials can be varied by changing the synthesis parameters. The unique 2D plate like morphology of tungsten oxide increases adsorption sites of the support, leading to less sintering and higher dispersion of silver nanoparticles, resulting in significantly enhanced activity for the reaction. The influence of reaction parameters such as temperature, substrate to oxidant molar ratio, reaction time, etc. was investigated in detail. The catalyst was characterized by XRD, XPS, ICP-AES, TGA, FT-IR, UV-vis, Raman, SEM, TEM and STEM. Raman studies further provide mechanistic insight which proves that the formation of peroxo tungsten species is responsible for the N-oxidation reaction. High stability and recyclability of the 2D Ag/WO3 nanoplates are also observed under the investigated conditions.A halide ion promoted two dimensional silver tungsten-based nanomaterial was synthesized by a facile one-pot synthesis protocol at room temperature. The 2D morphology features high activity and selectivity for the oxidation of a wide range of tertiary N-compounds to their corresponding N-oxides. The morphology of Ag/WO3 materials can be varied by changing the synthesis parameters. The unique 2D plate like morphology of tungsten oxide increases adsorption sites of the support, leading to less sintering and higher dispersion of silver nanoparticles, resulting in significantly enhanced activity for the reaction. The influence of reaction parameters such as temperature, substrate to oxidant molar ratio, reaction time, etc. was investigated in detail. The catalyst was characterized by XRD, XPS, ICP-AES, TGA, FT-IR, UV-vis, Raman, SEM, TEM and STEM. Raman studies

  16. Phenolic compounds and browning in sherry wines subjected to oxidative and biological aging.

    PubMed

    Fabios, M; Lopez-Toledano, A; Mayen, M; Merida, J; Medina, M

    2000-06-01

    The composition in hydroxybenzoic and hydroxycinnamic acids, hydroxycinnamic esters, tyrosol, syringaldehyde, and flavan-3-ol derivatives of three different types of sherry wine obtained by aging of the same starting wine under different conditions was studied. So-called "fino" wine was obtained by biological aging under flor yeasts, "oloroso" wine by oxidative aging, and "amontillado" wine by a first stage of biological aging followed by a second oxidative step. On the basis of the results, the wines subjected to oxidative aging exhibited higher phenol contents, in addition to scarcely polar compounds absorbing at 420 nm that were absent in the wines obtained by biological aging. Taking into account that flavan-3-ol derivatives play an important role in wine browning, a model catechin solution was inoculated with flor yeast which, contrary to the findings of other authors in the absence of yeasts, formed no colored compounds. This different behavior may account for the resistance to browning of pale sherry wines in the presence of flor yeasts. PMID:10888514

  17. Effective medium approximation of the optical properties of electrochromic cerium-titanium oxide compounds

    SciTech Connect

    Rottkay, K. von; Richardson, T.; Rubin, M.; Slack, J.

    1997-07-01

    Cerium titanium oxide samples derived from a solution have been compared against sputtered films over a wide range of different compositions. X-ray diffraction was used to investigate the structural properties of the compound material existing in a two-phase mixture M{sub A}O{sub 2}-M{sub B}O{sub 2}. The optical properties were evaluated over the whole solar spectrum by variable angle spectroscopic ellipsometry combined with spectrophotometry. The spectral complex refractive index was determined for CeO{sub 2} and TiO{sub 2}, as well as for their compounds. To reduce the large number of permutations in composition of multi-component oxides it would be useful to be able to predict the properties of the mixtures from the pure oxide components. Therefore these results were compared to those obtained by effective medium theory utilizing the optical constants of CeO{sub 2} and TiO{sub 2}. In order to investigate the performance as passive counter-electrode in Li{sup +} based electrochromic devices the films were tested by cyclic voltammetry with in-situ transmission control. Chemical composition was measured by Rutherford backscattering spectrometry. Surface morphology was analyzed by atomic force microscopy.

  18. Activation of human peripheral blood mononuclear cells by nitric oxide-generating compounds

    SciTech Connect

    Lander, H.M.; Sehajpal, P.; Levine, D.M.; Novogrodsky, A. )

    1993-02-15

    Recent work in this laboratory has identified immune-stimulatory properties of the oxidant hemin. In this study, the authors examined whether the nitrogen-based oxidant nitric oxide (NO) had inductive effects on human lymphocytes. They found that the NO-generating compounds sodium nitroprusside and S-nitroso-N acetylpenicillamine rapidly enhanced the rate of glucose transport in resting human PBMC. In addition, NF-[kappa]B binding activity was induced by these agents as was the secretion of TNF-[alpha]. The data suggest that a cGMP-independent mechanism is involved as the cell permeant cGMP analogue, 8-Br-cGMP, had no effect in eliciting these inductive events. Activation of lymphocytes by these NO-generating compounds may be mediated through the protein tyrosine phosphorylation signal transduction pathway. It was found that membrane-associated protein tyrosine phosphatase activity was enhanced in PBMC treated with sodium nitroprusside or S-nitroso-N-acetylpenicillamine and that the src family protein tyrosine kinase p56[sup lck] was activated in these cells. Inasmuch as p56[sup lck] activity is negatively controlled by tyrosine phosphorylation, its activation may be related to the enhancement of protein tyrosine phosphatase activity. 8Br-cGMP had no effect on these enzymes. Taken together, these data suggest that NO may have immune-stimulatory properties and may signal through a hitherto undescribed cGMP-independent pathway. 30 refs., 9 figs., 2 tabs.

  19. Effective medium approximation of the optical properties of electrochromic cerium-titanium oxide compounds

    NASA Astrophysics Data System (ADS)

    von Rottkay, Nik; Richardson, Terry J.; Rubin, Michael; Slack, J.; Masetti, Enrico; Dautzenberg, G.

    1997-10-01

    Cerium titanium oxide samples produced by sol-gel have been compared against sputtered and pulsed laser deposited films over a wide range of different compositions. X-ray diffraction was used to investigate the structural properties of the compound material existing in a two-phase mixture MAO2-MBO2. The optical properties were evaluated over the whole solar spectrum by variable angle spectroscopic ellipsometry combined with spectrophotometry. The spectral complex refractive index was determined for CeO2 and TiO2, as well as for their compounds. To reduce the large number of permutations in composition of multi-component oxides it would be useful to be able to predict the properties of the mixtures from the pure oxide components. Therefore these results were compared to those obtained by effective medium theory utilizing the optical constants of CeO2 and TiO2. In order to investigate the performance as passive counter-electrode in Li+ based electrochromic devices the films were tested by cyclic voltammetry with in-situ transmission control. Chemical composition was measured by Rutherford backscattering spectrometry. Surface morphology was analyzed by atomic force microscopy.

  20. Compounds between the dioxides of hafnium and zirconium and the oxides of strontium and barium

    SciTech Connect

    Gerasimyuk, G.I.; Lopato, L.M.; Shevchenko, A.V.; Zaitseva, Z.A.

    1985-12-01

    The goal of the paper is the synthesis and study of the properties of compounds in the system HfO/sub 2/ (ZrO2)-SrO(BaO). These compounds form in the region of high alkaline-earth content. The phase composition of the samples was studied by x-ray and petrographic analyses on a DRON-1.5 unit at room temperature. It was established from the studies that, independent of the means of sample preparation, there form on interaction of the dioxides of hafnium and zirconium with the oxides of strontium in the region of high SrO content the compounds Sr/sub 4/HF/sub 3/O/sub 10/, Sr/sub 4/Zr/sub 3/O/sub 10/, Sr/sub 3/Hf/sub 2/O/sub 7/, Sr/sub 3/Zr/sub 2/O/sub 7/, Sr/sub 2/HfO/sub 4/, and Sr/sub 2/ZrO/sub 4/. The unit-cell parameters and crystal-optical characteristics of the compounds synthesized were determined.

  1. Synthesis of Oligosilanyl Compounds of Group 4 Metallocenes with the Oxidation State +3

    PubMed Central

    2012-01-01

    Recently, we showed that titanocene silyls are much more stable with Ti in the oxidation state +3. The current study demonstrates that analogous Zr and Hf compounds can also be obtained by reaction of a suitable metalate precursor with an oligosilanyl dianion. As the obtained complexes formally possess a d1 electron configuration, they were investigated using EPR spectroscopy. The corresponding spectra indicate that the compounds can be considered to also exhibit some cyclosilanyl radical anion character. In order to understand the strong preference of disilylated titan(IV)ocenes for reductive elimination, a theoretical study of the thermodynamics of these reactions was conducted, revealing that this behavior is essentially caused by the weak Si–Ti(IV) bond. PMID:22723723

  2. Photocatalytic: oxidation of volatile organic compounds present in airborne environment adjacent to sewage treatment plants.

    PubMed

    Raillard, C; Héquet, V; Le Cloirec, P; Legrand, J

    2004-01-01

    Emissions of volatile organic compounds (VOCs) from wastewater in municipal sewage or industrial wastewater treatment plants are often overlooked as sources of exposure to hazardous substances. The impact of such emissions on local airborne environments represents a growing source of scientific, toxicological and public health interest. Actually, VOCs are suspected to be quite dangerous for human health. Some of them belong to the family of odorous compounds and can cause serious annoyance in the neighbourhood of the emission sources. A way to remove VOCs released from sewers and wastewater treatment facilities could be to degrade them by photocatalytic oxidation. TiO2-based photocatalysts are known to be efficient for this kind of application. In the present work TiO2 P25 Degussa was deposited on glass supports. These materials were tested for the degradation of butanone-2 in a photocatalytic reactor. The influence of water vapour (relative humidity) was shown using the Langmuir-Hinshelwood kinetic model. PMID:14979545

  3. Reaction of nitric oxide with heme proteins and model compounds of hemoglobin

    SciTech Connect

    Sharma, V.S.; Traylor, T.G.; Gardiner, R.; Mizukami, H.

    1987-06-30

    Rates for the reaction of nitric oxide with several ferric heme proteins and model compounds have been measured. The NO combination rates are markedly affected by the presence or absence of distal histidine. Elephant myoglobin in which the E7 distal histidine has been replaced by glutamine reacts with NO 500-1000 times faster than do the native hemoglobins or myoglobins. By contrast, there is not difference in the CO combination rate constants of sperm whale and elephant myoglobins. Studies on ferric model compounds for the R and T states of hemoglobin indicate that their NO combination rate constants are similar to those observed for the combination of CO with the corresponding ferro derivatives. The last observation suggests that the presence of an axial water molecule at the ligand binding site of ferric hemoglobin A prevents it from exhibiting significant cooperativity in its reactions with NO.

  4. Sustained nitric oxide (NO)-releasing compound reverses dysregulated NO signal transduction in priapism

    PubMed Central

    Lagoda, Gwen; Sezen, Sena F.; Hurt, K. Joseph; Cabrini, Marcelo R.; Mohanty, Dillip K.; Burnett, Arthur L.

    2014-01-01

    We evaluated the therapeutic potential of a sustained nitric oxide (NO)-releasing compound to correct the molecular hallmarks and pathophysiology of priapism, an important but poorly characterized erectile disorder. 1,5-Bis-(dihexyl-N-nitrosoamino)-2,4-dinitrobenzene (C6′) and an inactive form of the compound [1,5-bis-(dihexylamino)-2,4-dinitrobenzene (C6)] were tested in neuronal cell cultures and penile lysates for NO release (Griess assay) and biological activity (cGMP production). The effect of local depot C6′ or C6 was evaluated in mice with a priapic phenotype due to double neuronal and endothelial NO synthase deletion (dNOS−/−) or human sickle hemoglobin transgenic expression (Sickle). Changes in NO signaling molecules and reactive oxygen species (ROS) surrogates were assessed by Western blot. The physiological response after C6′ treatment was assessed using an established model of electrically stimulated penile erection. C6′ generated NO, increased cGMP, and dose dependently increased NO metabolites. C6′ treatment reversed abnormalities in key penile erection signaling molecules, including phosphodiesterase type 5, phosphorylated endothelial nitric oxide synthase, and phosphorylated vasodilator-stimulated phosphoprotein. In Sickle mice, C6′ also attenuated the increased ROS markers gp91phox, 4-hydroxynonenal, and 3-nitrotyrosine. Finally, C6′ corrected the excessive priapic erection response of dNOS−/− mice. Exogenous sustained NO release from C6′ corrects pathological erectile signaling in mouse models of priapism and suggests novel approaches to human therapy.—Lagoda, G., Sezen, S. F., Hurt, K. J., Cabrini, M. R., Mohanty, D. K., Burnett, A. L. Sustained nitric oxide (NO)-releasing compound reverses dysregulated NO signal transduction in priapism. PMID:24076963

  5. Vapor-phase catalytic oxidesulfurization (ODS) of organosulfur compounds over supported metal oxide catalysts

    NASA Astrophysics Data System (ADS)

    Choi, Sukwon

    Sulfur in transportation fuels remains a leading source of SOx emissions from vehicle engines and is a major source of air pollution. The very low levels of sulfur globally mandated for transportation fuels in the near future cannot be achieved by current practices of hydrodesulfurization (HDS) for sulfur removal, which operate under severe conditions (high T, P) and use valuable H2. Novel vapor-phase catalytic oxidesulfurization (ODS) processes of selectively oxidizing various organosulfur compounds (carbonyl sulfide, carbon disulfide, methanethiol, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), thiophene, 2,5-dimenthylthiophene) typically found in various industrial streams (e.g., petroleum refining, pulp and paper) into valuable chemical intermediates (H 2CO, CO, H2, maleic anhydride and concentrated SO2) has been extensively studied. This research has primarily focused on establishing the fundamental kinetics and mechanisms of these selective oxidation reactions over well-defined supported metal oxide catalysts. The selective oxidation reactions of COS + O2 → CO + SO2; 2CS2 + 5O2 → 2CO + 4SO2; CH3SH + 2O 2 → H2CO + SO2 + H2O; C4 H4S + 3O2 → C4H2O 3 + H2O + SO2; were studied. Raman spectroscopy revealed that the supported metal oxide phases were 100% dispersed on the oxide substrate. All the catalysts were highly active and selective for the oxidesulfurization of carbonyl sulfide, carbon disulfide, methanethiol, and thiophene between 290--330°C, 230--270°C, 350--400°C, and 250--400°C, respectively and did not deactivate. The TOFs (turnover frequency, normalized activity per active catalytic site) for all ODS reactions over supported vanadia catalysts, only containing molecularly dispersed surface vanadia species, varied within one order of magnitude and revealed the V-O-Support bridging bond was involved in the critical rate-determining kinetic steps. The surface reaction mechanism for each reaction was revealed by in situ IR (infrared) and

  6. Electronic Raman scattering in copper-oxide superconductors and related compounds

    SciTech Connect

    Hackl, R.; Krug, G.; Nemetschek, R.; Opel, M.; Stadlober, B.

    1996-12-31

    The authors describe Raman-scattering experiments in copper-oxide superconductors with transition temperatures between 12 and 90 K as a function of temperature and polarization. The broad continuum observed in all compounds in both the normal and the superconducting state is attributed predominantly to electronic excitations and will be interpreted in terms of charge-carrier fluctuations. The effect of impurities is studied systematically. The limitations of the present theoretical approach as well as possible generalizations will be discussed. 60 refs., 11 figs., 1 tab.

  7. Production of the pepper aroma compound, (-)-rotundone, by aerial oxidation of α-guaiene.

    PubMed

    Huang, An-Cheng; Burrett, Stacey; Sefton, Mark A; Taylor, Dennis K

    2014-11-01

    The aroma link between pepper and wine has recently been elucidated to be due to the important aroma compound rotundone. To date, rotundone is the only known impact odorant with a peppery aroma. Although the concentration found in products of natural origin is small, the odor detection threshold is among the lowest of any natural product yet discovered. We report herein the identification of the first known precursor to rotundone, namely, α-guaiene, and that one mechanism of transformation is simple aerial oxidation. PMID:25307830

  8. Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds

    NASA Technical Reports Server (NTRS)

    Alim, M. A.; Penn, B. G.; Currie, J. R., Jr.; Batra, A. K.; Aggarwal, M. D.

    2008-01-01

    Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

  9. Sono-bromination of aromatic compounds based on the ultrasonic advanced oxidation processes.

    PubMed

    Fujita, Mitsue; Lévêque, Jean-Marc; Komatsu, Naoki; Kimura, Takahide

    2015-11-01

    A novel, mild "sono-halogenation" of various aromatic compounds with potassium halide was investigated under ultrasound in a biphasic carbon tetrachloride/water medium. The feasibility study was first undertaken with the potassium bromide and then extended to chloride and iodide analogues. This methodology could be considered as a new expansion of the ultrasonic advanced oxidation processes (UAOPs) into a synthetic aspect as the developed methodology is linked to the sonolytic disappearance of carbon tetrachloride. Advantages of the present method are not only that the manipulation of the bromination is simple and green, but also that the halogenating agents used are readily available, inexpensive, and easy-handling. PMID:26186842

  10. Removal of Indoor Volatile Organic Compounds via Photocatalytic Oxidation: A Short Review and Prospect.

    PubMed

    Huang, Yu; Ho, Steven Sai Hang; Lu, Yanfeng; Niu, Ruiyuan; Xu, Lifeng; Cao, Junji; Lee, Shuncheng

    2016-01-01

    Volatile organic compounds (VOCs) are ubiquitous in indoor environments. Inhalation of VOCs can cause irritation, difficulty breathing, and nausea, and damage the central nervous system as well as other organs. Formaldehyde is a particularly important VOC as it is even a carcinogen. Removal of VOCs is thus critical to control indoor air quality (IAQ). Photocatalytic oxidation has demonstrated feasibility to remove toxic VOCs and formaldehyde from indoor environments. The technique is highly-chemical stable, inexpensive, non-toxic, and capable of removing a wide variety of organics under light irradiation. In this paper, we review and summarize the traditional air cleaning methods and current photocatalytic oxidation approaches in both of VOCs and formaldehyde degradation in indoor environments. Influencing factors such as temperature, relative humidity, deactivation and reactivations of the photocatalyst are discussed. Aspects of the application of the photocatalytic technique to improve the IAQ are suggested. PMID:26742024

  11. Comprehensive NO-dependent study of the products of the oxidation of atmospherically relevant aromatic compounds.

    PubMed

    Birdsall, Adam W; Elrod, Matthew J

    2011-06-01

    A comprehensive product study, performed via the turbulent flow chemical ionization mass spectrometry (TF-CIMS) technique, of the primary OH-initiated oxidation of many of the atmospherically abundant aromatic compounds was performed. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of aromatics, was detected in all cases, as were stable bicyclic species. The NO product yield dependences suggest a potential role for bicyclic peroxy radical + HO(2) reactions at high HO(2)/NO ratios, which are postulated to be a possible source of the inconsistencies between previous environmental chamber results and predictions from the MCM for ozone production and OH reactivity. The TF-CIMS product yield results are also compared to previous environment chamber results and to the latest MCM parametrization. PMID:21553858

  12. Liquid phase oxidation of thiophene compounds by tert-butyl hydroperoxide

    SciTech Connect

    Mushrush, G.W.; Watkins, J.M. Jr.; Hazlett, R.N.; Hardy, D.R.; Eaton, H.G. )

    1987-08-01

    Oxidative instability problems in both shale and petroleum-derived middle distillate fuels are related to the presence of hydroperoxides. Although a good body of knowledge exists concerning the formation of peroxides in the liquid phase, relatively little is known about the reaction/decomposition pathways when other functional groups are present. One of the significant and undesirable problems is the formation of solid deposits which can plug nozzles and filters and coal heat exchanger surfaces. Deposit formation in fuels is triggered by autoxidation reactions and is closely associated with elemental oxygen and/or hydroperoxide concentration. This paper reports on the reaction between a primary autoxidation product, a hydroperoxide, and sulfur compounds of the type present in petroleum-derived middle distillate fuels. Specifically, we examine the t-butyl hydroperoxide oxidation of thiophene, 2, 5-dimethylthiophene, tetrahydrothiophene and benzothiophene in a deaerated model fuel, tetradecane, at 120{degree}C.

  13. Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds.

    PubMed

    Zhang, Lanjun; Li, Zenghua; Li, Jinhu; Zhou, Yinbo; Yang, Yongliang; Tang, Yibo

    2015-01-01

    This paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. The results show that between 30°C to 80°C, the interaction between diphenyl sulfide and oxygen is mainly one of physical adsorption. After 80°C, chemical adsorption and chemical reactions begin. The main reaction mechanism in the low-temp oxidation of the model compound diphenyl sulfide is diphenyl sulfide generates diphenyl sulfoxide, and then this sulfoxide is further oxidized to diphenyl sulphone. A small amount of free radicals is generated in the process. The model compound cysteine behaves differently from diphenyl sulfide. The main reaction low-temp oxidation mechanism involves the thiol being oxidized into a disulphide and finally evolving to sulfonic acid, along with SO₂ being released at 130°C and also a small amount of free radicals. We also conducted an experiment on coal from Xingcheng using X-ray photoelectron spectroscopy (XPS). The results show that the major forms of organic sulfur in the original coal sample are thiophene and sulfone. Therefore, it can be inferred that there is none or little mercaptan and thiophenol in the original coal. After low-temp oxidation, the form of organic sulfur changes. The sulfide sulfur is oxidized to the sulfoxide, and then the sulfoxide is further oxidized to a sulfone, and these steps can be easily carried out under experimental conditions. What's more, the results illustrate that oxidation promotes sulfur element enrichment on the surface of coal. PMID:26690405

  14. Chemical indicators of sulfate sensitivity to nitrogen oxides and volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Stein, Ariel F.; Lamb, Dennis

    2002-10-01

    The formation of aerosol sulfate (SO42-) in eastern North America is chemically linked to the emissions of nitrogen oxides (NOx) and volatile organic compounds (VOC) through oxidation of the gaseous precursor, sulfur dioxide (SO2). The response of sulfate production to controls in NOx and VOC emissions depends, in part, on the resulting changes in oxidant levels and the competition that naturally exists between the gas- and aqueous-phase pathways for SO2 oxidation. We propose the use of a combination of concentrations of nitric acid, particulate nitrate, hydrogen peroxide, and ambient sulfate as a nondimensional indicator of the effectiveness of VOC or NOx controls in decreasing SO42- abundance. The concentrations of these indicator species were calculated from a series of photochemical model simulations with varying rates of NOx and VOC emissions using a three-dimensional Eulerian model (MODELS-3) that covers the northeastern United States. This study shows that ambient sulfate concentrations are likely to decrease more effectively as VOC emissions are reduced, when the nondimensional indicator is less than a certain threshold. However, a higher value of the indicator identifies a regime in which NOx emissions reductions are more effective for reducing sulfate than are VOC emissions. In addition, a description of the sulfate-formation pathways, along with a theoretical analysis of the transition between NOx- and VOC-sensitive regimes, provides a strong rationale for the use of the sulfate sensitivity indicator.

  15. Chloride promoted room temperature preparation of silver nanoparticles on two dimensional tungsten oxide nanoarchitectures for the catalytic oxidation of tertiary N-compounds to N-oxides.

    PubMed

    Ghosh, Shilpi; Acharyya, Shankha S; Kumar, Malika; Bal, Rajaram

    2015-10-01

    A halide ion promoted two dimensional silver tungsten-based nanomaterial was synthesized by a facile one-pot synthesis protocol at room temperature. The 2D morphology features high activity and selectivity for the oxidation of a wide range of tertiary N-compounds to their corresponding N-oxides. The morphology of Ag/WO3 materials can be varied by changing the synthesis parameters. The unique 2D plate like morphology of tungsten oxide increases adsorption sites of the support, leading to less sintering and higher dispersion of silver nanoparticles, resulting in significantly enhanced activity for the reaction. The influence of reaction parameters such as temperature, substrate to oxidant molar ratio, reaction time, etc. was investigated in detail. The catalyst was characterized by XRD, XPS, ICP-AES, TGA, FT-IR, UV-vis, Raman, SEM, TEM and STEM. Raman studies further provide mechanistic insight which proves that the formation of peroxo tungsten species is responsible for the N-oxidation reaction. High stability and recyclability of the 2D Ag/WO3 nanoplates are also observed under the investigated conditions. PMID:26313877

  16. Kinetics of OH-initiated oxidation of some oxygenated organic compounds in the aqueous phase under tropospheric conditions

    NASA Astrophysics Data System (ADS)

    Poulain, L.; Grubert, S.; François, S.; Monod, A.; Wortham, H.

    2003-04-01

    The interest for multiphase interactions of Volatile Organic Compounds (VOCs) in the troposphere has increased for a few years. Inside the clouds water droplets, soluble VOCs can be oxidized by free radicals thus modifying the droplet composition. This reactivity has an impact on the tropospheric oxidizing capacity as well as the aerosols' properties. In the present work, we measured aqueous phase OH-initiated oxidation rate constants of several oxygenated organic compounds relevant to the atmosphere or chosen as test compounds (ethanol, t-butanol, 1-butanol, iso-propanol, 1-propanol, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, phenol, ethyl ter-butyl ether (ETBE), n-propyl acetate, acetone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK), ethyl formate). Experiments took place in an aqueous phase photoreactor. The rate constants were determinated using the relative kinetic method. Different OH-radical sources were tested, as well as different reference compounds in order to detect any artifact. The results have shown validation of the experimental protocol on test compounds. The overall results allowed to propose a structure reactivity method in order to predict OH-oxidation rate constant of new compounds. Finally, tropospheric life times of the studied compounds were compared inside and outside a cloud.

  17. Formation of biomineral iron oxides compounds in a Fe hyperaccumulator plant: Imperata cylindrica (L.) P. Beauv.

    PubMed

    Fuente, V; Rufo, L; Juárez, B H; Menéndez, N; García-Hernández, M; Salas-Colera, E; Espinosa, A

    2016-01-01

    We report a detailed work of composition and location of naturally formed iron biominerals in plant cells tissues grown in iron rich environments as Imperata cylindrica. This perennial grass grows on the Tinto River banks (Iberian Pyritic Belt) in an extreme acidic ecosystem (pH∼2.3) with high concentration of dissolved iron, sulphate and heavy metals. Iron biominerals were found at the cellular level in tissues of root, stem and leaf both in collected and laboratory-cultivated plants. Iron accumulated in this plant as a mix of iron compounds (mainly as jarosite, ferrihydrite, hematite and spinel phases) was characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy (MS), magnetometry (SQUID), electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX; TEM-EDX; HRSTEM). A low fraction of phosphorous was detected in this iron hyperaccumulator plant. Root and rhizomes tissues present a high proportion of ferromagnetic iron oxide compounds. Iron oxides-rich zones are localized in electron dense intra and inter-cellular aggregates that appear as dark deposits covering the inner membrane and organelles of the cell. This study aims to contribute to a better understanding of the mechanisms of accumulation, transport, distribution of iron in Imperata cylindrica. PMID:26592710

  18. Crystal chemical and quantum chemical studies of Ba(Sr)-Nb oxide compounds

    NASA Technical Reports Server (NTRS)

    Zubkov, V. G.; Turzhevsky, S. A.; Pereliaev, V. A.; Liechtenstein, A. I.; Gubanov, V. A.

    1990-01-01

    The information available on the BaO(SrO)-NbO-NbO2 system with the niobium atom in the lower oxidation degree is very limited. Very few compounds have been found previously in this system. They are BaNbO3, SrxNbO3(0,7=x=1), Ba2Nb2O9, SrNb8O14; and some suggestions on the BaNb8O14 existence have been made also. At the same time Nb-based oxide compounds could be quite interesting in the search of new noncopper high T(sub c) superconductors Researchers studied Ba(Sr) NbxO2x-2 and Ba2(Sr2)-NbxO2x-1 compositions in the phase diagram of BaO(SrO)-NbO-NbO2 system. The synthesis of the materials was carried out in vacuum at the temperatures of 1000 to 1500 C. Barium carbonate and niobium pentoxide were used as initial components. X-ray analysis was carried out.

  19. Treatment of halogenated phenolic compounds by sequential tri-metal reduction and laccase-catalytic oxidation.

    PubMed

    Dai, Yunrong; Song, Yonghui; Wang, Siyu; Yuan, Yu

    2015-03-15

    Halogenated phenolic compounds (HPCs) are exerting negative effects on human beings and ecological health. Zero-valence metal reduction can dehalogenate HPCs rapidly but cannot mineralize them. Enzymatic catalysis can oxidize phenolic compounds but fails to dehalogenate efficiently, and sometimes even produces more toxic products. In this study, [Fe|Ni|Cu] tri-metallic reduction (TMR) and laccase-catalytic oxidation (LCO) processes were combined to sequentially remove HPCs, including triclosan, tetrabromobisphenol A, and 2-bromo-4-fluorophenol in water. The kinetics, pH and temperature dependences of TMR and LCO were obtained. The detailed TMR, LCO, and TMR-LCO transformation pathways of three HPCs were well described based on the identification of intermediate products and frontier molecular orbitals (FMOs) theory. The results showed that the two-stage process worked synergically: TMR that reductively dehalogenated HPCs followed by LCO that completely removed dehalogenated products. TMR was proven to not only improve biodegradability of HPCs but also reduce the yield of potential carcinogenic by-products. Furthermore, a TMR-LCO flow reactor was assembled and launched for 256 h, during which >95% HPCs and >75% TOC were removed. Meanwhile, monitored by microorganism indicators, 83.2%-92.7% acute toxicity of HPCs was eliminated, and the genotoxicity, produced by LCO, was also avoided by using TMR as pretreatment process. PMID:25596562

  20. Oxidative properties and chemical stability of fluoronanotubes in matrixes of binary inorganic compounds.

    PubMed

    Peng, Haiqing; Gu, Zhenning; Liu, Yu; Chiang, Ivana W; Smalley, Richard E; Hauge, Robert H; Khabashesku, Valery N; Margrave, John L

    2003-01-01

    The chemical stability of fluoronanotubes in selected solid inorganic matrixes has been studied by initially mixing and mechanically grinding the components and subsequently heating them at temperatures ranging from 35 to 600 degrees C. The inorganic compounds selected for matrixes included halides (KBr, KI, Lil, LiBr, LiCl, NaCl, Znl2), oxides (Li2O, Fe2O3, PbO, MnO), lithium peroxide (Li2O2), potassium superoxide (KO2), sulfides (Li2S and ZnS), zinc selenide (ZnSe), lithium nitride (Li3N), and aluminum phosphide (AIP). Solid products, resulting from the proceeding chemical reactions, were analyzed by X-ray diffraction, Raman spectroscopy, and SEM/EDX elemental analysis. Gaseous and volatile products were identified with the help of the TGA/MS technique. Experimental data presented in this paper provide clear evidence that fluoronanotubes are not chemically inert toward the solid matrixes studied and exhibit significant oxidative properties in the redox reactions occurring under various temperatures, depending on the nature of the inorganic compound. PMID:12908234

  1. Macroscopic and spectroscopic investigations of the adsorption of nitroaromatic compounds on graphene oxide, reduced graphene oxide, and graphene nanosheets.

    PubMed

    Chen, Xiaoxiao; Chen, Baoliang

    2015-05-19

    The surface properties and adsorption mechanisms of graphene materials are important for potential environmental applications. The adsorption of m-dinitrobenzene, nitrobenzene, and p-nitrotoluene onto graphene oxide (GO), reduced graphene oxide (RGO), and graphene (G) nanosheets was investigated using IR spectroscopy to probe the molecular interactions of graphene materials with nitroaromatic compounds (NACs). The hydrophilic GO displayed the weakest adsorption capability. The adsorption of RGO and G was significantly increased due to the recovery of hydrophobic π-conjugation carbon atoms as active sites. RGO nanosheets, which had more defect sites than did GO or G nanosheets, resulted in the highest adsorption of NACs which was 10-50 times greater than the reported adsorption of carbon nanotubes. Superior adsorption was dominated by various interaction modes including π-π electron donor-acceptor interactions between the π-electron-deficient phenyls of the NACs and the π-electron-rich matrix of the graphene nanosheets, and the charge electrostatic and polar interactions between the defect sites of graphene nanosheets and the -NO2 of the NAC. The charge transfer was initially proved by FTIR that a blue shift of asymmetric -NO2 stretching was observed with a concomitant red shift of symmetric -NO2 stretching after m-dinitrobenzene was adsorbed. The multiple interaction mechanisms of the adsorption of NAC molecule onto flat graphene nanosheets favor the adsorption, detection, and transformation of explosives. PMID:25877513

  2. Development of Alkaline Oxidative Dissolution Methods for Chromium (III) Compounds Present in Hanford Site Tank Sludges

    SciTech Connect

    Delegard, Calvin H.; Krot, N N.; Shilov, V P.; Fedoseev, A M.; Budantseva, N A.; Nikonov, M V.; Yusov, A B.; Garnov, A Y.; Charushnikova, I A.; Perminov, V P.; Astafurova, L N.; Lapitskaya, T S.; Makarenkov, V I.

    1999-07-02

    The high-level radioactive waste sludge in the underground storage tanks at the Hanford Site contains various chromium solid phases. Dissolution and removal of chromium from tank waste sludges is desirable prior to high-level waste vitrification because increased volume is required to incorporate the residual chromium. Unfortunately, dissolution of chromium from the sludge to form Cr(OH){sub 4}{sup -} through treatment with heated NaOH solution (also used to dissolve aluminum phases and metathesize phosphates to sodium salts) generally has been unsuccessful in tests with both simulated and genuine Hanford waste sludges. Oxidative dissolution of the Cr(III) compounds to form soluble chromate has been proposed as an alternative chromium solid phase dissolution method and results of limited prior testing have been reported. The present systematic tests investigated oxygen gas, hydrogen peroxide, and sodium persulfate oxidants to dissolve Cr(III) under alkaline conditions to form soluble chromate. Permanganate and ozone also were considered for testing but were thought to be of secondary interest because of the insoluble residue (MnO{sub 2} from permanganate) and complex equipment (necessary to generate ozone) implicit with use of these reagents. The oxygen and hydrogen peroxide reagents leave no condensable residue and sodium persulfate only leaves soluble sodium sulfate. Crystalline Cr(OH){sub 3}, various hydrothermally aged amorphous Cr(III) oxide hydrates, mixed Fe(III)/Cr(III) oxide hydrates, and nickel and iron Cr(III) spinels, all of which have been identified or are likely constituents in Hanford tank wastes, were prepared and characterized for the dissolution tests. The effects of reagent and hydroxide concentrations, reaction temperature, and transition metal catalysts on reaction progress were investigated for each reagent as functions of reaction time. Reaction progress was measured by monitoring chromate concentration. Oxidation of chromium compounds by

  3. Chemical kinetic study of the oxidation of toluene and related cyclic compounds

    SciTech Connect

    Mehl, M; Frassoldati, A; Fietzek, R; Faravelli, T; Pitz, W; Ranzi, E

    2009-10-01

    Chemical kinetic models of hydrocarbons found in transportation fuels are needed to simulate combustion in engines and to improve engine performance. The study of the combustion of practical fuels, however, has to deal with their complex compositions, which generally involve hundreds of compounds. To provide a simplified approach for practical fuels, surrogate fuels including few relevant components are used instead of including all components. Among those components, toluene, the simplest of the alkyl benzenes, is one of the most prevalent aromatic compounds in gasoline in the U.S. (up to 30%) and is a promising candidate for formulating gasoline surrogates. Unfortunately, even though the combustion of aromatics been studied for a long time, the oxidation processes relevant to this class of compounds are still matter of discussion. In this work, the combustion of toluene is systematically approached through the analysis of the kinetics of some important intermediates contained in its kinetic submechanism. After discussing the combustion chemistry of cyclopentadiene, benzene, phenol and, finally, of toluene, the model is validated against literature experimental data over a wide range of operating conditions.

  4. Treatment of biorefractory organic compounds in wool scour effluent by hydroxyl radical oxidation.

    PubMed

    Poole, Andrew J

    2004-01-01

    Wool scouring effluent that had been treated with chemical flocculation and aerobic biological treatment (Sirolan CFB effluent) was tertiary treated by hydroxyl radical oxidation to remove residual organic compounds. These compounds impart a high chemical oxygen demand of 500-3000 mg/L and dark colour. However, a H2O2/UV process was found to effectively treat the majority of residual compounds, with up to 75% COD, 85% total organic carbon, and 100% removal of colour (T(480 nm)) achieved. This was despite the effluent being strongly absorbing in the UV region, with a film thickness of 0.21 mm reducing T(254 nm) by 50%. Treatment was unaffected by pH over the range 3-9. H2O2/UV treatment increased the biodegradability of the effluent (5-day biochemical oxygen demand increased from < 10 to 86 mg/L), but a combined chemical and biological process did not increase maximum COD removal or overall process efficiency. The tertiary treated effluent had a final COD in the range 125-750 mg/L, equating to a total COD removal from raw wool scour effluent of approximately 97.5%. This degree of treatment is sufficient for discharge in many, but not all, circumstances. PMID:15276763

  5. Destruction of polychlorinated aromatic compounds by spinel-type complex oxides.

    PubMed

    Fan, Yun; Lu, Xianbo; Ni, Yuwen; Zhang, Haijun; Zhao, Liang; Chen, Jiping; Sun, Chenglin

    2010-04-15

    Destruction of polychlorinated aromatic compounds was carried out over spinel-type catalysts XY2O4 (where X = Mg, Ca, Cu, Ni, Zn, and Y = Al, Fe). The catalysts were characterized by XRD, nitrogen adsorption-desorption isotherms and FTIR. The performance of these catalysts toward the decomposition of hexachlorobenzene (HCB) and octachlorodibenzo-p-dioxin (OCDD) was evaluated in a closed system. The spinel-type catalyst with mesoporous structure demonstrated high catalytic activity for the hydrodechlorination of polychlorinated aromatic compounds. Among them, the copper-aluminum spinel (CuAl2O4), specifically calcined at 600 degrees C, exhibited the best activity. More than 85% dechlorination efficiency of HCB and 99% decomposition of polychlorinated dibenzodioxin (PCDD) were achieved at 250 degrees C for 30 min over the above catalyst which was more effective than the corresponding metallic copper and copper oxide catalysts during the thermal degradation of polychlorinated aromatic compounds. The correlation of catalytic performance to structural characteristics is discussed based on the detailed characterization. The simple preparation procedure and reasonable cost of the spinel-type catalysts present a good potential for the thermal treatment of polychlorinated aromatic pollutants at lower temperatures. PMID:20334415

  6. Oxides on GaAs and InAs surfaces: An x-ray-photoelectron-spectroscopy study of reference compounds and thin oxide layers

    NASA Astrophysics Data System (ADS)

    Hollinger, G.; Skheyta-Kabbani, R.; Gendry, M.

    1994-04-01

    The chemical composition of thin native oxide layers grown on GaAs and InAs by ultraviolet (UV)/ozone and thermal oxidation is investigated using x-ray-photoelectron spectroscopy. Core-level binding energies, core-level intensities, and valence-band spectra are compared with data for bulk crystalline binary or ternary As, In, and Ga oxides. The chemical compositions, which vary strongly from GaAs to InAs and from thermal to UV oxidation, appear to be controlled by both thermodynamic and kinetic factors. Only for GaAs thermal oxidation are the products predicted at thermodynamic equilibrium obtained. In all cases the native oxides can be described as single phase nonstoichiometric compounds and not as a macroscopic mixture of stoichiometric binary oxides.

  7. Hydrogen Peroxide Production as a Limiting Factor in Xenobiotic Compound Oxidation by Nitrogen-Sufficient Cultures of Bjerkandera sp. Strain BOS55 Overproducing Peroxidases

    PubMed Central

    Kotterman, M.; Wasseveld, R. A.; Field, J. A.

    1996-01-01

    The overproduction of ligninolytic peroxidase by the N-deregulated white rot fungus Bjerkandera sp. strain BOS55 under nitrogen-sufficient conditions had no noteworthy effect on the oxidation of anthracene or the decolorization of the polymeric aromatic dye Poly R-478 in 6-day-old cultures. Only when the endogenous production of H(inf2)O(inf2) was increased by the addition of extra oxygen and glucose could a 2.5-fold increase in the anthracene oxidation rate and a 6-fold increase in the Poly R-478 decolorization rate be observed in high-N cultures with 10- to 35-fold higher peroxidase activities than N-limited cultures. Further increase of the H(inf2)O(inf2) generation rate in high-N cultures with glucose oxidase led to an additional 3.5-fold increase in the anthracene oxidation rate (350 mg liter(sup-1) day(sup-1)) and a 10-fold increase in the Poly R-478 decolorization rate. These results indicate that xenobiotic compound oxidation by white rot fungi cannot be improved by overproducing peroxidases without increasing the endogenous production of H(inf2)O(inf2). The absence of Mn, which decreased the manganese peroxidase titers and increased the lignin peroxidase titers, was associated with up to 95% improvements in the anthracene oxidation rate. The simultaneous presence of Mn and veratryl alcohol was observed to have a synergistic negative effect on the oxidation of anthracene and the decolorization of Poly R-478. PMID:16535276

  8. Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds

    NASA Astrophysics Data System (ADS)

    Tanev, Peter T.; Chibwe, Malama; Pinnavaia, Thomas J.

    1994-03-01

    TITANIUM silicalite is an effective molecular-sieve catalyst for the selective oxidation of alkanes, the hydroxylation of phenol and the epoxidation of alkenes in the presence of H2O2 (refs 1-3). The range of organic compounds that can be oxidized is greatly limited, however, by the relatively small pore size (about 0.6 nm) of the host framework4. Large-pore (mesoporous) silica-based molecular sieves have been prepared recently by Kresge et all5-7 and Kuroda et al 8.; the former used a templating approach in which the formation of an inorganic mesoporous structure is assisted by self-organization of surfactants, and the latter involved topochemical rearrangement of a layered silica precursor. Here we describe the use of the templating approach to synthesize mesoporous silica-based molecular sieves partly substituted with titanium-large-pore analogues of titanium silicalite. We find that these materials show selective catalytic activity towards the oxidation of 2,6-ditert-butyl phenol to the corresponding quinone and the conversion of benzene to phenol.

  9. Preparation of extrusions of bulk mixed oxide compounds with high macroporosity and mechanical strength

    DOEpatents

    Flytzani-Stephanopoulos, Maria; Jothimurugesan, Kandaswami

    1990-01-01

    A simple and effective method for producing bulk single and mixed oxide absorbents and catalysts is disclosed. The method yields bulk single oxide and mixed oxide absorbent and catalyst materials which combine a high macroporosity with relatively high surface area and good mechanical strength. The materials are prepared in a pellet form using as starting compounds, calcined powders of the desired composition and physical properties these powders are crushed to broad particle size distribution, and, optionally may be combined with an inorganic clay binder. The necessary amount of water is added to form a paste which is extruded, dried and heat treated to yield and desired extrudate strength. The physical properties of the extruded materials (density, macroporosity and surface area) are substantially the same as the constituent powder is the temperature of the heat treatment of the extrudates is approximately the same as the calcination temperature of the powder. If the former is substantially higher than the latter, the surface area decreases, but the macroporosity of the extrusions remains essentially constant.

  10. Influence of iron solubility and charged surface-active compounds on lipid oxidation in fatty acid ethyl esters containing association colloids.

    PubMed

    Homma, Rika; Johnson, David R; McClements, D Julian; Decker, Eric A

    2016-05-15

    The impact of iron compounds with different solubilities on lipid oxidation was studied in the presence and absence of association colloids. Iron (III) sulfate only accelerated lipid oxidation in the presence of association colloids while iron (III) oleate accelerated oxidation in the presence and absence of association colloids. Further, iron (III) oxide retarded lipid oxidation both with and without association colloids. The impact of charged association colloids on lipid oxidation in ethyl oleate was also investigated. Association colloids consisting of the anionic surface-active compound dodecyl sulphosuccinate sodium salt (AOT), cationic surface-active compound hexadecyltrimethylammonium bromide (CTAB), and nonionic surface-active compound 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-100) retarded, promoted, and had no effect on lipid oxidation rates, respectively. These results indicate that the polarity of metal compounds and the charge of association colloids play a big role in lipid oxidation. PMID:26776045

  11. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    NASA Astrophysics Data System (ADS)

    Razavi, Behnaz; Song, Weihua; Santoke, Hanoz; Cooper, William J.

    2011-03-01

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( rad OH) and reducing aqueous electron (e -aq), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with rad OH determined, (6.96±0.16)×10 9, (2.92±0.06)×10 9, (4.16±0.13)×10 9, and (3.13±0.15)×10 9 M -1 s -1, and for e -aq (2.31±0.06)×10 9, (0.45±0.01)×10 9, (1.26±0.01)×10 9, and (0.69±0.02)×10 9 M -1 s -1, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  12. Could organic matter have been preserved on Mars for 3.5 billion years?

    NASA Technical Reports Server (NTRS)

    Kanavarioti, Anastassia; Mancinelli, Rocco L.

    1990-01-01

    About 3.5 Gyr ago, when it is thought that Mars and earth had similar climates, biological evolution on earth had made considerable progress, such that life was abundant. It is therefore surmised that prior to this time period, the advent of chemical evolution and subsequent origin of life occurred on earth and may have occurred on Mars. Analysis for organic compounds in the soil buried beneath the Martian surface may yield useful information regarding the occurrence of chemical evolution and possibly biological evolution. Calculations based on the stability of amino acids lead to the conclusion that remnants of these compounds, if they existed on Mars 3.5 Gyr ago, might have been preserved buried beneath the surface oxidizing layer. For example, if phenylalanine, an amino acid of average stability, existed on Mars 3.5 Gyr ago, then 1.6 percent would remain buried today. Martian soil may exist from remnants of meteoritic and cometary bombardment, assuming that 1 percent of the organics survived impact.

  13. 43 CFR 3.5 - Application.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 43 Public Lands: Interior 1 2010-10-01 2010-10-01 false Application. 3.5 Section 3.5 Public Lands: Interior Office of the Secretary of the Interior PRESERVATION OF AMERICAN ANTIQUITIES § 3.5 Application. Each application for a permit should be filed with the Secretary having jurisdiction, and must...

  14. 43 CFR 3.5 - Application.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 43 Public Lands: Interior 1 2013-10-01 2013-10-01 false Application. 3.5 Section 3.5 Public Lands: Interior Office of the Secretary of the Interior PRESERVATION OF AMERICAN ANTIQUITIES § 3.5 Application. Each application for a permit should be filed with the Secretary having jurisdiction, and must...

  15. 43 CFR 3.5 - Application.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 43 Public Lands: Interior 1 2012-10-01 2011-10-01 true Application. 3.5 Section 3.5 Public Lands: Interior Office of the Secretary of the Interior PRESERVATION OF AMERICAN ANTIQUITIES § 3.5 Application. Each application for a permit should be filed with the Secretary having jurisdiction, and must...

  16. 43 CFR 3.5 - Application.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 43 Public Lands: Interior 1 2011-10-01 2011-10-01 false Application. 3.5 Section 3.5 Public Lands: Interior Office of the Secretary of the Interior PRESERVATION OF AMERICAN ANTIQUITIES § 3.5 Application. Each application for a permit should be filed with the Secretary having jurisdiction, and must...

  17. 43 CFR 3.5 - Application.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 43 Public Lands: Interior 1 2014-10-01 2014-10-01 false Application. 3.5 Section 3.5 Public Lands: Interior Office of the Secretary of the Interior PRESERVATION OF AMERICAN ANTIQUITIES § 3.5 Application. Each application for a permit should be filed with the Secretary having jurisdiction, and must...

  18. Removal of perfluorinated compounds in wastewater treatment plant effluents by electrochemical oxidation.

    PubMed

    Zhang, Chunhui; Wang, Liangliang; Li, Juan; Su, Peidong; Peng, Chen

    2015-01-01

    The presence of perfluorinated compounds (PFCs) in the effluents of a wastewater treatment plant (WWTP) in Beijing was investigated in the current study. Perfluorooctanoate acid and perfluorooctane sulfonate were the predominant PFCs in wastewater, accounting for 19-27% and 18-31%, respectively. The concentrations of PFCs with long chains were much lower than those PFCs with short chains (≤C8). An electrochemical oxidation reactor was employed for advanced treatment of PFCs in WWTP effluents using stainless steel plates as anode and cathode electrodes. It was concluded that the removal efficiency of PFCs was improved accordingly with the increasing applied current density. The removal efficiencies of target PFCs ranged from 23.53 to 51.79% with a reaction time of 30 minutes, current density of 20 mA/cm(2), electrode plate distance of 1.0 cm and electrode plate amounts of five pairs. PMID:26067497

  19. Development of Alkaline Oxidative Dissolution Methods for Chromium (III) Compounds Present in Hanford Site Tank Sludges

    SciTech Connect

    NN Krot; VP Shilov; AM Fedoseev; NA Budantseva; MV Nikonov; AB Yusov; AYu Garnov; IA Charushnikova; VP Perminov; LN Astafurova; TS Lapitskaya; VI Makarenkov

    1999-07-02

    The high-level radioactive waste sludge in the underground storage tanks at the Hanford Site contains various chromium(III)solid phases. Dissolution and removal of chromium from tank waste sludges is desirable prior to high-level waste vitrification because increased volume is required to incorporate the residual chromium. Unfortunately, dissolution of chromium from the sludge to form Cr(OH){sub 4}{sup {minus}} through treatment with heated NaOH solution (also used to dissolve aluminum phases and metathesize phosphates to sodium salts) generally has been unsuccessful in tests with both simulated and genuine Hanford waste sludges. Oxidative dissolution of the Cr(III) compounds to form soluble chromate has been proposed as an alternative chromium solid phase dissolution method and results of limited prior testing have been reported.

  20. Emissions of Biogenic Volatile Organic Compounds and Observations of VOC Oxidation at Harvard Forest

    NASA Astrophysics Data System (ADS)

    McKinney, K. A.; Pho, T.; Vasta, A.; Lee, B. H.

    2009-12-01

    The contribution of biogenic volatile organic compounds (BVOCs) to oxidant concentrations and secondary organic aerosol (SOA) production in forested environments depends on the emission rates of these compounds. Recent findings have suggested that the emission rates of BVOCs and the range of species emitted could be larger than previously thought. In this study, Proton Transfer Reaction Mass Spectrometry (PTR-MS) was used to obtain fast (<1 Hz) measurements of the predominant BVOC species, including isoprene, monoterpenes, and oxygenated BVOCs, above the canopy at Harvard Forest (Petersham, MA) during the summers of 2005, 2007, and 2008. Together with vertical wind data, these measurements are used to determine fluxes of BVOCs out of the forest using the virtual disjunct eddy covariance method. Concentrations of additional VOCs, including methyl vinyl ketone + methacrolein and terpene oxidation products were also measured. Isoprene is the dominant emitted species, with peak emission rates and midday mixing ratios of ca. 4 mg isoprene m-2 h-1 and ca. 5 ppbv, respectively. Isoprene emission rates are expected to vary with temperature and radiation (PAR) levels, and are compared to standard emission algorithms based on these parameters. Interannual variability in isoprene emission rates is also observed, and contributing factors are explored. In contrast to isoprene, maximum monoterpene concentrations typically were less than 1 ppbv and occurred in the early evening, with a local minimum at midday. Monoterpene fluxes are about an order of magnitude smaller than those of isoprene. The amplitude of the flux diurnal cycle suggests monoterpene emissions at Harvard Forest may exhibit light dependence as well as temperature dependence. Fluxes of oxygenated VOCs, including methanol, acetone, methyl ethyl ketone, and oxygenated terpenes that have rarely been observed previously, are also reported, and the dependence of their emission rates on factors such as time of year

  1. Air/water oxidative desulfurization of coal and sulfur-containing compounds

    NASA Astrophysics Data System (ADS)

    Warzinski, R. P.; Freidman, S.; LaCount, R. B.

    1981-02-01

    Air/water Oxydesulfurization has been demonstrated in autoclave experiments at the Pittsburgh Energy Technology Center for various coals representative of the major U. S. coal basins. The applicability at present of this treatment for producing an environmentally acceptable coal has been restricted by recently proposed SO2 emission standards for utility boilers. The product would, however, be attractive to the many smaller industrial coal users who cannot afford to operate and maintain flue gas desulfurization systems. It is also possible that the utility industry could realize a benefit by using chemically cleaned coal with partial flue gas scrubbing. The higher cost of the cleaned coal would be offset by the reduction in capital and operating costs resulting from decreased FGD requirements. The susceptibility of sulfur in coal to oxidative removal varies with the nature of the sulfur-containing species. The inorganic sulfur compounds, primarily pyrite, marcasite, and iron sulfate, are more amenable to treatment than the organically bound sulfur which exhibits varying degrees of resistance depending on its chemical environment. Air/water Oxydesulfurization consistently removes in excess of 90 percent of the pyritic sulfur; the extent and efficiency of organic sulfur removal however, depends on the type of coal and severity of treatment used. In general, the organic sulfur of the higher rank coals exhibits more resistance to treatment than that of the lower rank coals; however, the accompanying heating value is greater for the latter. Similar treatment of sulfur-containing model compounds further illustrates the relative susceptibilities of different chemical species to oxidation. Application of these data to the understanding of the complex chemistry involved in the treatment of coal is a preliminary step toward improving the efficiency of Oxydesulfurization.

  2. Extraction/oxidation kinetics of low molecular weight compounds in wine brandy resulting from different ageing technologies.

    PubMed

    Canas, Sara; Caldeira, Ilda; Belchior, A Pedro

    2013-06-15

    This study provides innovative information on the influence of new technologies of ageing (stainless steel tanks with wood staves or wood tablets of chestnut or Limousin oak), in comparison with traditional technology (oak wooden barrels), on the extraction/oxidation kinetics of low molecular weight compounds of wine brandy. The brandy was sampled and analysed by HPLC during the first year of ageing. The results show that most of the compounds tend to increase over the time, but their extraction/oxidation kinetics depend on the ageing technology. The wooden barrels promote greater enrichment in the majority of the compounds. However, gallic acid, ellagic acid and syringaldehyde, and vanillin and 5-methylfurfural, which are strong antioxidants and key-odourant compounds, respectively, present higher contents in the brandy aged with the alternative technologies. Chestnut proves to be a suitable alternative to Limousin oak for the ageing of brandy in all the studied technologies, inducing faster evolution and high quality. PMID:23497909

  3. UV spectra and OH-oxidation kinetics of gaseous phase morpholinic compounds

    NASA Astrophysics Data System (ADS)

    Al Rashidi, M.; El Masri, A.; Roth, E.; Chakir, A.

    2014-05-01

    This paper presents an experimental study of the UV spectra as well as the kinetics of gaseous phase OH-oxidation of morpholine, N-formylmorpholine (NFM) and N-acetlymorpholine (NAM). The spectra recorded using a UV spectrometer in the spectral range 200-280 nm show that the analytes mainly absorb at wavelengths less than 280 nm. This indicates that their photolysis potential in the troposphere is insignificant. Meanwhile, the OH-reactivity of these analytes was studied using a triple-jacket 2 m long reactor equipped with a multi-reflection system and coupled to an FTIR spectrometer. The experiments were carried out at 295 and 313 K for the amine and amides, respectively. The study was conducted in the relative mode using isoprene and benzaldehyde as reference compounds. The rate constants obtained are 14.0 ± 1.9, 4.0 ± 1.1 and 3.8 ± 1.0 (in units of 10-11 cm3 molecule-1 s-1) for morpholine, NFM and NAM respectively. These results are discussed in terms of reactivity and compared to those obtained for other oxy-nitrogenated species. In addition, the determined rate constants are used to estimate effective atmospheric lifetimes of the investigated morpholinic compounds with respect to reaction with OH radicals.

  4. Enhancing graphene oxide reinforcing potential in composites by combined latex compounding and spray drying

    NASA Astrophysics Data System (ADS)

    Mao, Yingyan; Zhang, Shubai; Zhang, Dandan; Chan, Tung W.; Liu, Li

    2014-04-01

    A new strategy was developed to prepare graphene oxide/styrene-butadiene rubber (GO/SBR) composites with highly exfoliated GO sheets and strong interfaces. In particular, GO/SBR microparticles, in which exfoliated GO sheets (with a thickness of ˜1 nm and diameter of tens of nanometers) are trapped in a well-dispersed state throughout the SBR matrix, were made by a combined latex-compounding and spray-drying method. Subsequently, a chemical bridge between GO and rubber matrix through KH550 and Si69 was built during vulcanization, and the interfacial strength of the cured GO/SBR composite was remarkably improved. Due to the highly exfoliated structure and the strong interface, the GO/SBR composite exhibited 7.8 times higher modulus at 300% strain and 6.4 times higher tensile strength compared with cured pure SBR. The combined latex-compounding and spray-drying method presented here is feasible and water-mediated and has great potential for industrial applications.

  5. Compound specific radiocarbon content of lignin oxidation products from the Altamaha river and Coastal Georgia

    NASA Astrophysics Data System (ADS)

    Culp, Randy

    2013-01-01

    Compound-specific isotope analysis (CSIA) is a powerful tool in organic geochemistry by providing detailed information about an individual organic compound’s history with regard to its source and process of formation. Most CSIA involves measurement of the stable isotope ratio of carbon (13C/12C) and hydrogen (D/H) following separation by gas or liquid chromatography. New applications are being developed using compound-specific radiocarbon (14C) content for delineating age of materials, rates of decomposition and residence time in various environments. This paper details the isotopic work on specific lignin monomers derived from terrestrial plants transported and deposited within the Altamaha River, estuary and off-shore Georgia in the Atlantic Ocean. By using gas chromatographic separation and identification of selected lignin oxidation products (LOP), the harvesting of these compounds using preparative fraction collection, and measurement of their 14C content using accelerator mass spectrometry, details of the age and presence of specific biomarkers unique to a given terrestrial source are revealed. Radiocarbon ages determined from water-column particulate organic carbon and sediment LOPs indicate a range of ages from modern to well over 5,000 years for the former and latter respectively. Transport mechanisms and particle size associations on mineral grains may play a significant role in 14C distribution in estuary and near-shore coastal environments. This data indicates higher than modern 14C activities in large particle-size sediment fractions in contrast to older LOP 14C ages found associated with the same coarse grain sediments. Individual LOP ages substantiate older terrestrial materials persist in the off-shore environment even though in the presence of modern marine 14C sources.

  6. Degradation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Stenotrophomonas maltophilia PB1.

    PubMed Central

    Binks, P R; Nicklin, S; Bruce, N C

    1995-01-01

    A mixed microbial culture capable of metabolizing the explosive RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) was obtained from soil enrichments under aerobic and nitrogen-limiting conditions. A bacterium, Stenotrophomonas maltophilia PB1, isolated from the culture used RDX as a sole source of nitrogen for growth. Three moles of nitrogen was used per mole of RDX, yielding a metabolite identified by mass spectroscopy and 1H nuclear magnetic resonance analysis as methylene-N-(hydroxymethyl)-hydroxylamine-N'-(hydroxymethyl)nitroamin e. The bacterium also used s-triazine as a sole source of nitrogen but not the structurally similar compounds octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, cyanuric acid, and melamine. An inducible RDX-degrading activity was present in crude cell extracts. PMID:7747953

  7. Experimental study of the supercritical water oxidation of recalcitrant compounds under hydrothermal flames using tubular reactors.

    PubMed

    Cabeza, Pablo; Bermejo, M Dolores; Jiménez, Cristina; Cocero, M José

    2011-04-01

    The hydrothermal flame is a new method of combustion that takes place in supercritical water oxidation reactions when the temperature is higher than the autoignition temperature. In these conditions, waste can be completely mineralized in residence times of milliseconds without the formation of by-products typical of conventional combustion. The object of this work is to study the hydrothermal flame formation in aqueous streams with high concentrations of recalcitrant compounds: an industrial waste with a high concentration of acetic acid and various concentrated solutions of ammonia. A tubular reactor with a residence time of 0.7 s was used. Oxygen was used as the oxidant and isopropyl alcohol (IPA) as co-fuel to reach the operation temperature required. The increase of IPA concentrations in the feeds resulted in a better TOC removal. For mixtures containing acetic acid, 99% elimination of TOC was achieved at temperatures higher than 750 °C. In the case of mixtures containing ammonia, TOC removals reached 99% while maximum total nitrogen removals were never higher than 94%, even for reaction temperatures higher than 710 °C. Ignition was observed at concentrations as high as 6% wt NH(3) with 2% wt IPA while at IPA concentrations below 2% wt IPA, the ammonia did not ignite. PMID:21420141

  8. Understanding the Oxidative Addition of σ-Bonds to Group 13 Compounds.

    PubMed

    García-Rodeja, Yago; Bickelhaupt, F Matthias; Fernández, Israel

    2016-09-12

    The oxidative addition reaction of X-H σ-bonds to Group 13 (E=Al, Ga, In) containing compounds has been computationally explored within the density functional theory framework. These reactions, which proceed concertedly involving the E(I) →E(III) oxidation, are exothermic and associated with relatively low activation barriers. In addition, the following trends in reactivity are found: (i) the activation barriers are lower for the X-H bonds involving the heavier element in the same group (ΔE(≠) : C>Si; N>P; O>S), (ii) the process becomes kinetically more favorable in going from left to right in the same period (ΔE(≠) : C>N>O; Si≈P>S), and (iii) the activation barrier systematically increases when heavier Group 13 elements are involved in the transformation (ΔE(≠) : Al

  9. RNA transcript sequencing reveals inorganic sulfur compound oxidation pathways in the acidophile Acidithiobacillus ferrivorans.

    PubMed

    Christel, Stephan; Fridlund, Jimmy; Buetti-Dinh, Antoine; Buck, Moritz; Watkin, Elizabeth L; Dopson, Mark

    2016-04-01

    Acidithiobacillus ferrivorans is an acidophile implicated in low-temperature biomining for the recovery of metals from sulfide minerals. Acidithiobacillus ferrivorans obtains its energy from the oxidation of inorganic sulfur compounds, and genes encoding several alternative pathways have been identified. Next-generation sequencing of At. ferrivorans RNA transcripts identified the genes coding for metabolic and electron transport proteins for energy conservation from tetrathionate as electron donor. RNA transcripts suggested that tetrathionate was hydrolyzed by the tetH1 gene product to form thiosulfate, elemental sulfur and sulfate. Despite two of the genes being truncated, RNA transcripts for the SoxXYZAB complex had higher levels than for thiosulfate quinone oxidoreductase (doxDAgenes). However, a lack of heme-binding sites in soxX suggested that DoxDA was responsible for thiosulfate metabolism. Higher RNA transcript counts also suggested that elemental sulfur was metabolized by heterodisulfide reductase (hdrgenes) rather than sulfur oxygenase reductase (sor). The sulfite produced as a product of heterodisulfide reductase was suggested to be oxidized by a pathway involving the sat gene product or abiotically react with elemental sulfur to form thiosulfate. Finally, several electron transport complexes were involved in energy conservation. This study has elucidated the previously unknown At. ferrivorans tetrathionate metabolic pathway that is important in biomining. PMID:26956550

  10. Performance of the wet oxidation unit of the HPLC isotope ratio mass spectrometry system for halogenated compounds.

    PubMed

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans Hermann

    2014-08-01

    The performance of liquid chromatography-isotope ratio mass spectrometry (LC-IRMS) for polar halogenated compounds was evaluated. Oxidation capacity of the system was tested with halogenated acetic acids and halogenated aromatic compounds. Acetic acid (AA) was selected as a reference compound for complete oxidation and compared on the molar basis to the oxidation of other analytes. The isotope values were proofed with calibrated δ(13)C values obtained with an elemental analyzer (EA). Correct isotope values were obtained for mono- and dichlorinated, fluorinated, and tribrominated acetic acids and also for aniline, phenol, benzene, bromobenzene, chlorobenzene, 1,2-dichlorobenzene, 2,4,6-trichlorophenol, pentafluorophenol, and nitrobenzene. Incomplete oxidation of trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) resulted in lower recovery compared to AA (37% and 24%, respectively) and in isotopic shift compared to values obtained with EA (TCA Δδ(13)C(EA/LC-IRMS) = 8.8‰, TFA Δδ(13)C(EA/LC-IRMS) = 6.0‰). Improvement of oxidation by longer reaction time in the reactor and increase in the concentration of sulfate radicals did not lead to complete combustion of TCA and TFA needed for δ(13)C analysis. To the best of our knowledge, this is the first time such highly chlorinated compounds were studied with the LC-IRMS system. This work provides information for method development of LC-IRMS methods for halogenated contaminants that are known as potential threats to public health and the environment. PMID:24975492