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Sample records for vicinal tert-butyl substituent

  1. Organic Semiconductors and Conductors with tert-Butyl Substituents

    Directory of Open Access Journals (Sweden)

    Toshiki Higashino

    2012-08-01

    Full Text Available Tetrathiafulvalene (TTF, pentacene, and quarterthiophene with tert-butyl substituents are synthesized, and the crystal structures and the transistor properties are investigated. The tetracyanoquinodimethane (TCNQ complex of tert-butyl TTF constructs highly one-dimensional segregated columns with tetragonal crystal symmetry.

  2. An efficient and highly selective ortho-tert-butylation of p-cresol with methyl tert-butyl ether catalyzed by sulfonated ionic liquids

    Directory of Open Access Journals (Sweden)

    Alamdari Reza Fareghi

    2014-01-01

    Full Text Available A novel series of sulfonic acid-functionalized ionic liquids (SFILs was found to act as efficient catalysts for ortho-tert-butylation of p-cresol with methyl tert-butyl ether (MTBE as the tert-butylating agent without an added solvent. The mono o-tert-butylated product was obtained in up to 80.4% isolated yield and 95.2% selectivity under such green conditions. No O-tert-butylated byproducts were formed.

  3. Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA).

    Science.gov (United States)

    Finneran, K T; Lovley, D R

    2001-05-01

    The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.

  4. 27 CFR 21.101 - tert-Butyl alcohol.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false tert-Butyl alcohol. 21.101 Section 21.101 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS FORMULAS FOR DENATURED ALCOHOL AND RUM Specifications for Denaturants § 21...

  5. N-tert-Butyl-3-hydroxy-5-androstene-17-carboxamide monohydrate

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    Jiang-Sheng Li

    2009-07-01

    Full Text Available In the title compound, C24H39NO2·H2O, the A and C rings of the pregnolene derivative sterol adopt chair conformations, with the B ring in a flattened chair conformation and the five-membered ring in an envelope conformation twisted about the C/D ring junction. The N-tert-butylcarboxamide substituent is equatorial. The 3β-hydroxy H atom and one H atom of the water molecule are disordered over two positions with equal occupancies. In the crystal structure, O—H...O hydrogen bonds between the 3β-hydroxy groups of neighbouring molecules form dimers in the bc plane and these dimers are stacked along the a axis by additional O—H...O hydrogen bonds involving the water molecules. The steric effect of the bulky tert-butyl substituent in the carboxamide chain precludes hydrogen-bond formation by the N—H group.

  6. Thermodynamic properties of 4-tert-butyl-diphenyl oxide

    International Nuclear Information System (INIS)

    Druzhinina, A.I.; Pimenova, S.M.; Tarazanov, S.V.; Nesterova, T.N.; Varushchenko, R.M.

    2015-01-01

    Highlights: • The sample of the 4-tert-butyl-diphenyl oxide was synthesized and purified. • Heat capacities, energy of combustion, saturation vapor pressures were measured. • The temperature, the enthalpy and the entropy of fusion were determined. • The enthalpy of sublimation at T = 298.15 K was derived. • The main thermodynamic functions and functions of formation were computed. - Abstract: The main thermodynamic functions (changes of the entropy, enthalpy, and Gibbs free energy) and functions of formation at T = 298.15 K of 4-tert-butyl-diphenyl oxide in condensed and ideal gas states were computed on the basis of experimental results obtained. The heat capacities of 4-tert-butyl-diphenyl oxide was measured by vacuum adiabatic calorimetry over the temperature range (8 to 371) K. The temperature, the enthalpy and the entropy of fusion were determined. The energy of combustion of the sample was determined by static-bomb combustion calorimetry. The saturation vapor pressures of the substance were measured by dynamic transpiration method over the temperature and pressure intervals (298 to 325) K and (0.05 to 1.2) Pa. The enthalpy of sublimation at T = 298.15 K was derived. The contribution of O-(2C b ) group (where C b is the carbon atom in a benzene ring) into the absolute entropies of diphenyl oxide derivatives was assessed

  7. Synthesis of 4-tert-butyl-1,1-dimethylindan and 7-tert-Butyl-3,3-dimethyl-1-indanone and a comparison of isomers

    International Nuclear Information System (INIS)

    Eisenbraun, E.J.; Harms, W.M.; Paraniswamy, V.A.; Chen, H.H.; Porcaro, P.J.; Wood, T.F.; Chien, M.

    1982-01-01

    4-tert-Butyl-1,1-dimethylindan was synthesized to help establish the identity of products (5- and 6-tert-butyl-1,1-dimethylindan as minor and major products, respectively) from the sulfuric acid catalyzed condensation of tert-butylbenzene and isoprene. NMR ( 1 H and 13 C) studies of these hydrocarbons and their corresponding indanones, obtained through chromic acid oxidation, provided structural proof. Gated decoupling experiments were crucial to complete assignment

  8. Synthesis of Highly Porous Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) Asymmetric Membranes

    KAUST Repository

    Xie, Yihui; Moreno Chaparro, Nicolas; Calo, Victor M.; Cheng, Hong; Hong, Pei-Ying; Sougrat, Rachid; Behzad, Ali Reza; Tayouo Djinsu, Russell; Nunes, Suzana Pereira

    2016-01-01

    For the first time, self-assembly and non-solvent induced phase separation was applied to polysulfone-based linear block copolymers, reaching mechanical stability much higher than other block copolymers membranes used in this method, which were mainly based on polystyrene blocks. Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) (PtBA30k-b-PSU14k-b-PtBA30k) with a low polydispersity of 1.4 was synthesized by combining step-growth condensation and RAFT polymerization. Various advanced electron microscopies revealed that PtBA30k-b-PSU14k-b-PtBA30k assembles into worm-like cylindrical micelles in DMAc and adopts a “flower-like” arrangement with the PSU central block forming the shell. Computational modeling described the mechanism of micelle formation and morphological transition. Asymmetric nanostructured membranes were obtained with a highly porous interconnected skin layer and a sublayer with finger-like macrovoids. Ultrafiltration tests confirmed a water permeance of 555 L m-2 h-1 bar-1 with molecular weight cut-off of 28 kg/mol. PtBA segments on the membrane surface were then hydrolyzed and complexed with metals, leading to cross-linking and enhancement of antibacterial capability.

  9. Synthesis of Highly Porous Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) Asymmetric Membranes

    KAUST Repository

    Xie, Yihui

    2016-03-24

    For the first time, self-assembly and non-solvent induced phase separation was applied to polysulfone-based linear block copolymers, reaching mechanical stability much higher than other block copolymers membranes used in this method, which were mainly based on polystyrene blocks. Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) (PtBA30k-b-PSU14k-b-PtBA30k) with a low polydispersity of 1.4 was synthesized by combining step-growth condensation and RAFT polymerization. Various advanced electron microscopies revealed that PtBA30k-b-PSU14k-b-PtBA30k assembles into worm-like cylindrical micelles in DMAc and adopts a “flower-like” arrangement with the PSU central block forming the shell. Computational modeling described the mechanism of micelle formation and morphological transition. Asymmetric nanostructured membranes were obtained with a highly porous interconnected skin layer and a sublayer with finger-like macrovoids. Ultrafiltration tests confirmed a water permeance of 555 L m-2 h-1 bar-1 with molecular weight cut-off of 28 kg/mol. PtBA segments on the membrane surface were then hydrolyzed and complexed with metals, leading to cross-linking and enhancement of antibacterial capability.

  10. Sorption of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) to synthetic resins.

    Science.gov (United States)

    Bi, Erping; Haderlein, Stefan B; Schmidt, Torsten C

    2005-10-01

    Methyl tert-butyl ether (MTBE) is a widely used gasoline oxygenate. Contamination of MTBE and its major degradation product tert-butyl alcohol (TBA) in groundwater and surface water has received great attention. However, sorption affinity and sorption mechanisms of MTBE and TBA to synthetic resins, which can be potentially used in removal of these contaminants from water, in passive sampling, or in enrichment of bacteria, have not been studied systemically. In this study, kinetic and equilibrium sorption experiments (single solute and binary mixtures) on four synthetic resins were conducted. The sorption affinity of the investigated sorbents for MTBE and TBA decreases in the order Ambersorb 563>Optipore L493>Amberlite XAD4>Amberlite XAD7, and all show higher sorption affinity for MTBE than for TBA. Binary experiments with o-xylene, a major compound of gasoline as co-contaminant, imply that all resins preferentially sorb o-xylene over MTBE or TBA, i.e., there is sorption competition. In the equilibrium aqueous concentration (Ceq) range (0.1-139.0 mg/L for MTBE, and 0.01-48.4 mg/L for TBA), experimental and modeling results as well as sorbent characteristics indicate that micropore filling and/or some other type of adsorption process (e.g., adsorption to specific sites of high sorption potential at low concentrations) rather than partitioning were the dominant sorption mechanisms. Optipore L493 has favourable sorption and desorption characteristics, and is a suitable sorbent, e.g., in bacteria enrichment or passive sampling for moderately polar compounds. However, for highly polar compounds such as TBA, Ambersorb 563 might be a better choice, especially in water treatment.

  11. APPLICATION OF PHOTOCATALYTIC PROCESS FOR REMOVAL OF METHYL TERT-BUTYL ETHER FROM HIGHLYCONTAMINATED WATER

    Directory of Open Access Journals (Sweden)

    A. Mesdaghinia

    2007-09-01

    Full Text Available The oxygenate methyl tert-butyl ether is added to gasoline to increase the octane level and to reduce carbon monoxide and hydrocarbon emissions by vehicles. The high mobility, water solubility, and resistance to natural attenuation associated with methyl tert-butyl ether may result in contamination of ground and surface waters. In this research the degradation of aqueous methyl tert-butyl ether at relatively high concentrations was investigated by UV-vis/TiO2/H2O2 photocatalytic process. The effect of important operational parameters such as pH, amount of H2O2, catalyst loading, and irradiation time were also studied. Concentrations of methyl tert-butyl ether and intermediates such as tert-butyl formate and tert-butyl alcohol were measured over a 180 min period using a gas chromatograph equipped with flame ionization detector and combined with headspace sampler. Results showed that the time required for complete degradation increased from 30 to 180min, when the initial concentration was increased from 10 to 500mg/L. The first order rate constant for degradation of methyl tert-butyl ether from the hydroxyl radical was estimated to be 0.177 to 0.022 1/min as the concentration increased from 10 to 500mg/L. Study on the overall mineralization monitored by total organic carbon (TOC analysis showed that in the initial concentration of 100mg/L methyl tert-butyl ether, complete mineralization was obtained after 110min under UV-vis/TiO2/H2O2 photocatalytic process.

  12. Biodegradation of methyl tert-butyl ether by Kocuria sp.

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    Kiković Dragan D.

    2012-01-01

    Full Text Available Methyl tert-butyl ether (MTBE has been used to replace the toxic compounds from gasoline and to reduce emission of air pollutants. Due to its intensive use, MTBE has become one of the most important environment pollutants. The aim of this paper is isolation and identification of the bacteria from wastewater sample of “HIP Petrohemija” Pančevo (Serbia, capable of MTBE biodegradation. The results of the investigation showed that only the bacterial isolate 27/1 was capable of growth on MTBE. The result of sequence analyzes of 16S rDNA showed that this bacterial isolate belongs to the Kocuria sp. After the incubation period of 86 days, the degradation rates of initial MTBE concentration of 25 and 125 μg/ml were 55 and 36%, respectively. These results indicated that bacteria Kocuria sp. is successfully adapted on MTBE and can be potentially used in bioremediation of soils and waters contaminated with MTBE.

  13. Electrochemical and Spin-Trapping Properties of para-substituted α-Phenyl-N-tert-butyl Nitrones

    International Nuclear Information System (INIS)

    Rosselin, Marie; Tuccio, Béatrice; Pério, Pierre; Villamena, Frederick A.; Fabre, Paul-Louis; Durand, Grégory

    2016-01-01

    Nitrones are known both as therapeutic antioxidants and efficient spin-traps. In this work, the redox behavior of various para-substituted α-phenyl-N-tert-butyl nitrones (PBN) was studied by cyclic voltammetry. The polar effect of the substituents was found to correlate with the electrochemical properties of the nitronyl function. Compounds bearing an electron-withdrawing group were more easily reduced than those having an electron-donating group and an opposite trend was observed for the oxidation. Ease of oxidation was also computationally rationalized using DFT approach showing increased ease of oxidation with electron donating functionalities. Since electrochemical properties of nitrones are known to correlate with biological properties, this work provides insights in the design of potent nitrone antioxidants. Using cyclic voltammetry the relative rate of superoxide trapping by nitrones was investigated and compared to the classical antioxidant BHT. The determination of the relative rate of phenyl radical trapping was also carried out but showed no clear correlation with the nature of the substituents. This indicates the absence of a polar effect in agreement with previous data and further supports the intermediate nature, that is, non- or weakly nucleophile, of phenyl radical. On the contrary kinetics of hydroxymethyl radical trapping was found to correlate with the nature of the substituents, demonstrating the nucleophilic nature of its addition onto nitrones.

  14. Reaction of biscyclopentadienyl molybdendihalides with tert.-butyl hydroperoxide and its using for cyclohexene epoxidation

    International Nuclear Information System (INIS)

    Aleksandrov, Yu.A.; Fomin, V.M.; Kolmakov, A.O.

    1983-01-01

    As a result of reactions of biscyclopentadienyl molybden-dihalides (Cp 2 MoX 2 , X=Cl, Br or I) with tert.-butyl hydroperoxide, tert.-butylperoxides of biscyclopentadienyl molybdendichloride and-dibromide are synthesized for the first time, which are characterized by physico-chemical properties. Cyclohexene in the reaction mixture of Cp 2 MoX 2 with tert -butyl hydroperoxide is oxidated to form cyclohexene oxide, the reaction proceeding at a high rate and with a quantitative yield. Tert.-butylperoxide of biscyclopentadienyl molybdendihalide is responsible for the cyclohexene epoxidation reaction. The schemes for the mechanism of Cp 2 MoX 2 reactions with tert.-butyl hydroperoxide in the absence and presence of olefine are suggested

  15. EFFECTS OF STIMULATOR SUBSTANCES ON AEROBIC METHYL TERT-BUTYL ETHER BIODEGRADATION BY MICROBIAL CONSORTIUM

    Directory of Open Access Journals (Sweden)

    M. Farrokhi ، S. Ahmadizad

    2009-04-01

    Full Text Available In this study dissolved humic substances and yeast extract were tested in different concentrations for enhancing methyl tert-butyl ether mineralization by isolated microorganisms from a variety of sources. All experiments were conducted at a constant temperature of 25ºC. Vials of 50 mL and 125 mL volume sealed with Teflon-lined Mini-Nert caps was used for microcosm experiments. In all experiments 1% sodium azide were used as control. Samples of bacterial cultures that metabolize methyl tert-butyl ether have been analysed by direct GC analysis using flame ionization detector. Cultures able to metabolize have been found in activated sludge and soils. These microorganisms weregram-positive bacterium. An aerobic microbial consortium was enriched in laboratory for four months. Methyl tert-butyl ether has been shown to biodegrade under aerobic and co-metabolic conditions. A microbial consortium isolated from activated sludges was identified as Cocobacillus. The concentration of the initial attached biomass was about 0.11 g/L of dry weight. The maximum mineralization rate and beneficial effects of stimulator substances on aerobic biodegradation of methyl tert-butyl ether occurred with the culture by combined concentrations of 500 mg/L of yeast extract and 20 mg/L of peat humic growth support of microbial consortium within 216 h and in presence of high oxygen levels and well mixing conditions. It was shown that adding, peat humic and yeast extract together, had better stimulatory effect on methyl tert-butyl ether biodegradation. Results clearly showed a stimulatory effect on methyl tert-butyl ether consumption higher than 20%. Consortium was capable of degrading concentrations of ≤1000 mg/L, whereas concentrations of >1000 mg/L, were not degraded.

  16. Method for determination of methyl tert-butyl ether and its degradation products in water

    Science.gov (United States)

    Church, C.D.; Isabelle, L.M.; Pankow, J.F.; Rose, D.L.; Tratnyek, P.G.

    1997-01-01

    An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method

  17. Temperature influence on mixing properties of {ethyl tert-butyl ether (ETBE) + gasoline additives}

    International Nuclear Information System (INIS)

    Gonzalez-Olmos, R.; Iglesias, M.

    2007-01-01

    The densities and ultrasonic velocity of {ethyl tert-butyl ether (ETBE) + (benzene, toluene, ethylbenzene, isooctane, tert-butyl alcohol, and ethanol)} over the temperature range (288.15 to 323.15) K and atmospheric pressure, have been measured over the whole concentration range. The experimental excess volumes and deviation of isentropic compressibilities data have been analysed in terms of different theoretical models. The gathered data improve open literature related to gasoline additives, and help to understand the ETBE volumetric and acoustic trend into different chemical environment

  18. Continuous synthesis of tert.-butyl peroxypivalate using a single channel micro reactor equipped with orifices as emulsification units

    NARCIS (Netherlands)

    Illg, T.; Hessel, V.; Löb, P.; Schouten, J.C.

    2011-01-01

    The two-step synthesis of tert-butyl peroxypivalate is performed in a single-channel microreactor. The first step, the deprotonation of tert-butyl hydroperoxide, is done in a simple mixer tube setup. The residence time section for the second reaction step is equipped with orifices for interfacial

  19. Atomic Force Microscopy Based Thermal Lithography of Poly(tert-butyl acrylate) Block Copolymer Films for Bioconjugation

    NARCIS (Netherlands)

    Duvigneau, Joost; Schönherr, Holger; Vancso, Gyula J.

    2008-01-01

    In this paper, we report on the local thermal activation of thin polymer films for area-selective surface chemical modification on micrometer and nanometer length scales. The thermally induced activation of tert-butyl ester moieties in polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) block

  20. Temperature effect on tert-butyl alcohol (TBA) biodegradation kinetics in hyporheic zone soils.

    Science.gov (United States)

    Greenwood, Mark H; Sims, Ronald C; McLean, Joan E; Doucette, William J

    2007-09-19

    Remediation of tert-butyl alcohol (TBA) in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-butyl formate (TBF). The effect of temperature on TBA biodegradation has not been not been published in the literature. Biodegradation of [U 14C] TBA was determined using hyporheic zone soil microcosms. First order mineralization rate constants of TBA at 5 degrees C, 15 degrees C and 25 degrees C were 7.84 +/- 0.14 x 10-3, 9.07 +/- 0.09 x 10-3, and 15.3 +/- 0.3 x 10-3 days-1, respectively (or 2.86 +/- 0.05, 3.31 +/- 0.03, 5.60 +/- 0.14 years-1, respectively). Temperature had a statistically significant effect on the mineralization rates and was modelled using the Arrhenius equation with frequency factor (A) and activation energy (Ea) of 154 day-1 and 23,006 mol/J, respectively. Results of this study are the first to determine mineralization rates of TBA for different temperatures. The kinetic rates determined in this study can be used in groundwater fate and transport modelling of TBA at the Ronan, MT site and provide an estimate for TBA removal at other similar shallow aquifer sites and hyporheic zones as a function of seasonal change in temperature.

  1. (R-N-{2-tert-Butyl-2-[(R-tert-butylsulfonamido]ethylidene}-tert-butanesulfonamide

    Directory of Open Access Journals (Sweden)

    Cong-Bin Fan

    2008-10-01

    Full Text Available The title compound, C14H30N2O2S2, is the product of the monoaddition reaction of tert-butyl magnesium chloride with bis-[(R-N-tert-butanesulfinyl]ethanediimine. There are two almost identical molecules in the asymmetric unit, the molecular conformation of which is stabilized by an intramolecular N—H...N hydrogen bond.

  2. A new efficient synthesis of isothiocyanates from amines using di-tert-butyl dicarbonate

    DEFF Research Database (Denmark)

    Munch, Henrik; Hansen, Jon S.; Pittelkow, Michael

    2008-01-01

    Alkyl and aryl amines are converted smoothly to the corresponding isothiocyanates via the dithiocarbamates in good to excellent yields using di-tert-butyl dicarbonate (Boc(2)O) and 1-3 mol% of DMAP or DABCO as catalyst. As most of the byproducts are volatile, the work-up involves simple evaporation...

  3. INHALATION EXPOSURE TO METHYL TERT-BUTYL ETHER (MTBE) AND DIBROMOCHLOROMETHANE (DBCM) USING CONTINUOUS BREATH ANALYSIS

    Science.gov (United States)

    The oxygenate methyl tert-butyl ether (MTBE) has been added to gasoline to help meet national ambient air quality standards in those parts of the U.S. that are non-compliant for carbon monoxide. Although MTBE has provided important health benefits in terms of reduced haza...

  4. and triorganotin(IV) complexes of 2-tert-butyl-4-methyl phenol

    Indian Academy of Sciences (India)

    TECS

    -2-Me-4) have been synthesized by the reactions of di-n-butyl and dimethyltin dichlorides and tri-n-butyltin(IV) chloride with 2-tert-butyl-4-methylphenol and triethylamine in tetrahydrofuran. The reaction of triphenyltin chloride with trimethylsilyl-2-t-butyl-4- methylphenoxide in the same solvent however, gives a complex of ...

  5. 2-tert-Butyl-5,6,7,8,9,10-hexahydrocyclohepta[b]indole

    Directory of Open Access Journals (Sweden)

    Janina Wobbe

    2011-09-01

    Full Text Available 2-tert-Butyl-5,6,7,8,9,10-hexahydrocyclohepta[b]indole was synthesized by reaction of cycloheptanone and (4-tert-butylphenylhydrazine hydrochloride in the presence of sodium acetate and sulfuric acid in glacial acetic acid via Fischer indole synthesis.

  6. IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) (External Review Draft)

    Science.gov (United States)

    The IRIS Toxicological Review of tert-Butyl Alcohol (tert-Butanol) was released for external peer review in June 2017. EPA’s Science Advisory Board’s (SAB) Chemical Assessment Advisory Committee (CAAC) will conduct a peer review of the scientific basis supporting ...

  7. IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) (Public Comment Draft)

    Science.gov (United States)

    EPA is developing an Integrated Risk Information System (IRIS) assessment of tert-butyl Alcohol (tert-butanol) and has released the public comment draft assessment for public comment and external peer review. When final, the assessment will appear on the IRIS databa...

  8. Estimation of the fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample

    DEFF Research Database (Denmark)

    Waul, Christopher Kevin; Arvin, Erik; Schmidt, Jens Ejbye

    2008-01-01

    The fraction of biologically active methyl tert-butyl ether degraders in reactors is just as important for prediction of removal rates as knowledge of the kinetic parameters. The fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample, taken from a packed...... bed reactor, was determined using a batch kinetic based approach. The procedure involved modeling of methyl tert-butyl ether removal rates from batch experiments followed by parameter estimations. It was estimated to be 5-14% (w/w) of the measured volatile suspended solids concentration in the reactor....

  9. Synthesis, characterization and gas separation properties of novel polyimides containing cardo and tert-butyl-m-terphenyl moieties

    Directory of Open Access Journals (Sweden)

    L. A. Bermejo

    2018-05-01

    Full Text Available A series of aromatic polyimides has been obtained by the reaction of two dianhydrides, the commercial 2,2′-bis(3,4-dicarboxyphenylhexafluoropropane dianhydride (6FDA and another having a 5′-tert-butyl-m-terphenyl moiety (BTPDA, with several diamines, including two that have a cardo structure (derived from 9H-fluorene, one of them bearing methyl groups ortho to the amino functionalities (TMeCardo. The solubility, and also the thermal, mechanical, and gas separation properties of the corresponding polyimide membranes were evaluated and compared in order to explore the effect of the different groups in the polyimide backbone. The novel polyimides, which were derived from BTPDA and the cardo diamines, showed high thermal stability, excellent solubility in organic solvents and good gas separation properties, especially the polyimide that bore the ortho methyl substituents. The behavior was especially good for the pair O2/N2, where the TMeCardo polymer overpassed the Robeson upper bound.

  10. Polyvinylpolypyrrolidone-Supported Boron Trifluoride; Highly Efficient Catalyst for the Synthesis of N-tert-Butyl Amides

    Directory of Open Access Journals (Sweden)

    Masoud Mokhtary

    2012-01-01

    Full Text Available Highly efficient method for the preparation of N-tert-butyl amides by reaction of nitriles with tert-butyl acetate is described using polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3 at 70°C in good to excellent yields. Selective amidation of benzonitrile in the presence of acetonitrile was also achieved. polyvinylpolypyrrolidone-boron trifluoride complex shows non-corrosive and stable solid catalyst elevated Lewis acid property.

  11. Temperature effect on tert-butyl alcohol (TBA biodegradation kinetics in hyporheic zone soils

    Directory of Open Access Journals (Sweden)

    Sims Ronald C

    2007-09-01

    Full Text Available Abstract Background Remediation of tert-butyl alcohol (TBA in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE, ethyl tert-butyl ether (ETBE, and tert-butyl formate (TBF. The effect of temperature on TBA biodegradation has not been not been published in the literature. Methods Biodegradation of [U 14C] TBA was determined using hyporheic zone soil microcosms. Results First order mineralization rate constants of TBA at 5°C, 15°C and 25°C were 7.84 ± 0.14 × 10-3, 9.07 ± 0.09 × 10-3, and 15.3 ± 0.3 × 10-3 days-1, respectively (or 2.86 ± 0.05, 3.31 ± 0.03, 5.60 ± 0.14 years-1, respectively. Temperature had a statistically significant effect on the mineralization rates and was modelled using the Arrhenius equation with frequency factor (A and activation energy (Ea of 154 day-1 and 23,006 mol/J, respectively. Conclusion Results of this study are the first to determine mineralization rates of TBA for different temperatures. The kinetic rates determined in this study can be used in groundwater fate and transport modelling of TBA at the Ronan, MT site and provide an estimate for TBA removal at other similar shallow aquifer sites and hyporheic zones as a function of seasonal change in temperature.

  12. {2,6-Bis[(di-tert-butyl-phosphino)-methyl]-phenyl}chloridonickel(II).

    Science.gov (United States)

    Boro, Brian J; Dickie, Diane A; Goldberg, Karen I; Kemp, Richard A

    2008-09-20

    In the title compound, [Ni(C(24)H(43)P(2))Cl], the Ni atom adopts a distorted square-planar geometry, with the P atoms of the 2,6-bis-[(di-tert-butyl-phosphino)meth-yl]phenyl ligand trans to one another. The P-Ni-P plane is twisted out of the plane of the aromatic ring by 21.97 (6)°.

  13. 1-[(E-2-(5-tert-Butyl-2-hydroxyphenyldiazen-1-yl]naphthalen-2-ol

    Directory of Open Access Journals (Sweden)

    Hassiba Bougueria

    2014-02-01

    Full Text Available The non-H atoms of the title compound, C20H20N2O2, is located on a mirror plane except two methyl groups of the tert-butyl group. Intramolecular N—H...O hydrogen bonds exist between the hydroxy and diazenyl groups. In the crystal, molecules are linked by weak C—H...O hydrogen bonds into supramolecular chains running along the a-axis direction.

  14. n-Alkane assimilation and tert-butyl alcohol (TBA) oxidation capacity in Mycobacterium austroafricanum strains.

    Science.gov (United States)

    Lopes Ferreira, Nicolas; Mathis, Hugues; Labbé, Diane; Monot, Frédéric; Greer, Charles W; Fayolle-Guichard, Françoise

    2007-06-01

    Mycobacterium austroafricanum IFP 2012, which grows on methyl tert-butyl ether (MTBE) and on tert-butyl alcohol (TBA), the main intermediate of MTBE degradation, also grows on a broad range of n-alkanes (C2 to C16). A single alkB gene copy, encoding a non-heme alkane monooxygenase, was partially amplified from the genome of this bacterium. Its expression was induced after growth on n-propane, n-hexane, n-hexadecane and on TBA but not after growth on LB. The capacity of other fast-growing mycobacteria to grow on n-alkanes (C1 to C16) and to degrade TBA after growth on n-alkanes was compared to that of M. austroafricanum IFP 2012. We studied M. austroafricanum IFP 2012 and IFP 2015 able to grow on MTBE, M. austroafricanum IFP 2173 able to grow on isooctane, Mycobacterium sp. IFP 2009 able to grow on ethyl tert-butyl ether (ETBE), M. vaccae JOB5 (M. austroaafricanum ATCC 29678) able to degrade MTBE and TBA and M. smegmatis mc2 155 with no known degradation capacity towards fuel oxygenates. The M. austroafricanum strains grew on a broad range of n-alkanes and three were able to degrade TBA after growth on propane, hexane and hexadecane. An alkB gene was partially amplified from the genome of all mycobacteria and a sequence comparison demonstrated a close relationship among the M. austroafricanum strains. This is the first report suggesting the involvement of an alkane hydroxylase in TBA oxidation, a key step during MTBE metabolism.

  15. Degradation of a recalcitrant xenobiotic compound: methyl tert-butyl ether (MTBE) metabolism by mycobacterium austroafricanum; Degradation d'un compose xenobiotique recalcitrant: metabolisme du methyl tert-butyl ether (MTBE) par mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Francois, A

    2002-11-01

    Methyl tert-butyl ether (MTBE) is introduced up to 15% (vol/vol) in gasoline in order to obtain a good octane number and to prevent carbon monoxide emissions. However, as a consequence of storage tanks leakage, MTBE became one of the major pollutants of aquifers because of its very low biodegradability. The present study aimed at investigating the biodegradation of MTBE by Mycobacterium austroafricanum IFP 2012. The MTBE metabolic pathway was partially elucidated owing to the identification of some intermediates (tert-butyl formate (TBF), tert-butyl alcohol (TBA), a-hydroxy-isobutyric acid and acetone) and some enzymatic activities (MTBE/TBA monooxygenase (non hemic and inducible), TBF esterase, 2-propanol: NDMA oxidoreductase and another monooxygenase involved in acetone degradation). The involvement of TBF and the requirement of cobalt could be explanations for the low natural attenuation of MTBE; whereas the methoxy group does not seem to be implicated. (author)

  16. Degradation of a recalcitrant xenobiotic compound: methyl tert-butyl ether (MTBE) metabolism by mycobacterium austroafricanum; Degradation d'un compose xenobiotique recalcitrant: metabolisme du methyl tert-butyl ether (MTBE) par mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Francois, A.

    2002-11-01

    Methyl tert-butyl ether (MTBE) is introduced up to 15% (vol/vol) in gasoline in order to obtain a good octane number and to prevent carbon monoxide emissions. However, as a consequence of storage tanks leakage, MTBE became one of the major pollutants of aquifers because of its very low biodegradability. The present study aimed at investigating the biodegradation of MTBE by Mycobacterium austroafricanum IFP 2012. The MTBE metabolic pathway was partially elucidated owing to the identification of some intermediates (tert-butyl formate (TBF), tert-butyl alcohol (TBA), a-hydroxy-isobutyric acid and acetone) and some enzymatic activities (MTBE/TBA monooxygenase (non hemic and inducible), TBF esterase, 2-propanol: NDMA oxidoreductase and another monooxygenase involved in acetone degradation). The involvement of TBF and the requirement of cobalt could be explanations for the low natural attenuation of MTBE; whereas the methoxy group does not seem to be implicated. (author)

  17. Synchrotron Photoionization Investigation of the Oxidation of Ethyl tert-Butyl Ether.

    Science.gov (United States)

    Winfough, Matthew; Yao, Rong; Ng, Martin; Catani, Katherine; Meloni, Giovanni

    2017-02-23

    The oxidation of ethyl tert-butyl ether (ETBE), a widely used fuel oxygenated additive, is investigated using Cl atoms as initiators in the presence of oxygen. The reaction is carried out at 293, 550, and 700 K. Reaction products are probed by a multiplexed chemical kinetics photoionization mass spectrometer coupled with the synchrotron radiation produced at the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory. Products are identified on the basis of mass-to-charge ratio, ionization energies, and shape of photoionization spectra. Reaction pathways are proposed together with detected primary products.

  18. Overview of technologies for removal of methyl tert-butyl ether (MTBE) from water.

    Science.gov (United States)

    Levchuk, Irina; Bhatnagar, Amit; Sillanpää, Mika

    2014-04-01

    Wide use of methyl tert-butyl ether (MTBE) as fuel oxygenates leads to worldwide environment contamination with this compound basically due to fuel leaks from storage or pipelines. Presence of MTBE in drinking water is of high environmental and social concern. Existing methods for MTBE removal from water have a number of limitations which can be possibly overcome in the future with use of emerging technologies. This work aims to provide an updated overview of recent developments in technologies for MTBE removal from water. Copyright © 2014. Published by Elsevier B.V.

  19. (N-Benzyl-N-ethyl­dithio­carbamato)di-tert-butyl­chloridotin(IV)

    OpenAIRE

    Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R. T.

    2011-01-01

    The SnIV atom in the title diorganotin dithio­carbamate, [Sn(C4H9)2Cl(C10H12NS2)], is penta­coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C—H⋯π contacts link centrosymmetrically related mol­ecules into dimeric aggregates...

  20. Di-tert-butyl­chlorido(N,N-dibenzyl­dithio­carbamato)tin(IV)

    Science.gov (United States)

    Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R. T.

    2011-01-01

    The SnIV atom in the title diorganotin dithio­carbamate, [Sn(C4H9)2(C15H14NS2)Cl], is penta­coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl atom and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. PMID:21522304

  1. Di-tert-butyl-chlorido(N,N-dibenzyl-dithio-carbamato)tin(IV).

    Science.gov (United States)

    Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R T

    2011-02-26

    The Sn(IV) atom in the title diorganotin dithio-carbamate, [Sn(C(4)H(9))(2)(C(15)H(14)NS(2))Cl], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl atom and two C atoms of the Sn-bound tert-butyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former.

  2. (N-Benzyl-N-ethyl­dithio­carbamato)di-tert-butyl­chloridotin(IV)

    Science.gov (United States)

    Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R. T.

    2011-01-01

    The SnIV atom in the title diorganotin dithio­carbamate, [Sn(C4H9)2Cl(C10H12NS2)], is penta­coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C—H⋯π contacts link centrosymmetrically related mol­ecules into dimeric aggregates. PMID:21522295

  3. (N-Benzyl-N-ethyl-dithio-carbamato)di-tert-butyl-chloridotin(IV).

    Science.gov (United States)

    Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R T

    2011-02-26

    The Sn(IV) atom in the title diorganotin dithio-carbamate, [Sn(C(4)H(9))(2)Cl(C(10)H(12)NS(2))], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C-H⋯π contacts link centrosymmetrically related mol-ecules into dimeric aggregates.

  4. Enhancement of methyl tert-butyl ether degradation by the addition of readily metabolizable organic substrates

    International Nuclear Information System (INIS)

    Chen Dongzhi; Chen Jianmeng; Zhong Weihong

    2009-01-01

    Supplements with readily metabolizable organic substrates were investigated to increase the biomass and enhance degradation of methyl tert-butyl ether (MTBE) due to the low biomass yield of MTBE which has been one of the factors for low-rate MTBE degradation. The influence of various organic substrates on the rate of aerobic degradation of methyl tert-butyl ether (MTBE) by Methylibium petroleiphilum PM1 was investigated, and only yeast extract (YE), beef extract and tryptone exhibited stimulatory effect. With the concentration of each substrate being 100 mg/L, the average MTBE removal rate could increase to 1.29, 1.20 and 1.04 mg/(L h), respectively, in comparison with 0.71 mg/(L h) when carried out in medium without addition. The stimulatory effects of YE addition, as well as induction period required by MTBE degradation, varied dramatically with the storage conditions, pre-culture medium and concentrations of the inoculums. The extent of stimulatory effects of YE might be closely related to the proportion of induction period in the total time of MTBE-degradation. The removal efficiency increased from about 50% to 90.5% with the addition of YE in a packed-bed reactor loaded with calcium alginate immobilized cells.

  5. Biodegradation of Methyl tert-Butyl Ether by Co-Metabolism with a Pseudomonas sp. Strain

    Directory of Open Access Journals (Sweden)

    Shanshan Li

    2016-09-01

    Full Text Available Co-metabolic bioremediation is supposed to be an impressive and promising approach in the elimination technology of methyl tert-butyl ether (MTBE, which was found to be a common pollutant worldwide in the ground or underground water in recent years. In this paper, bacterial strain DZ13 (which can co-metabolically degrade MTBE was isolated and named as Pseudomonas sp. DZ13 based on the result of 16S rRNA gene sequencing analysis. Strain DZ13 could grow on n-alkanes (C5-C8, accompanied with the co-metabolic degradation of MTBE. Diverse n-alkanes with different carbon number showed a significant influence on the degradation rate of MTBE and accumulation of tert-butyl alcohol (TBA. When Pseudomonas sp. DZ13 co-metabolically degraded MTBE with n-pentane as the growth substrate, a higher MTBE-degrading rate (Vmax = 38.1 nmol/min/mgprotein, Ks = 6.8 mmol/L and lower TBA-accumulation was observed. In the continuous degradation experiment, the removal efficiency of MTBE by Pseudomonas sp. Strain DZ13 did not show an obvious decrease after five times of continuous addition.

  6. INTERACTION OF METHYL-TERT BUTYL ETHER AND WATER STRESS ON SEED GERMINATION AND SEEDLING GROWTH IN SOIL MICROCOSMS

    Science.gov (United States)

    Methyl tert-butyl ether (MTBE) is a widespread contaminant in surface and ground water in the United States. Frequently irrigation is used to water fields to germinate planted seeds and sustain plant growth. A likely possibility exists that water used may have some MTBE. Our s...

  7. Reactive Imprint Lithography: Combined Topographical Patterning and Chemical Surface Functionalization of Polystyrene-block-poly(tert-butyl acrylate) Films

    NARCIS (Netherlands)

    Duvigneau, Joost; Cornelissen, Stijn; Bardajı´Valls, Nuria; Schönherr, Holger; Vancso, Gyula J.

    2009-01-01

    Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) are imprinted with PDMS master stamps at

  8. Voltammetric Determination of Nitro Derivative of Synthetic Antioxidant 2,6-di-tert-butyl-4-methyl-phenol

    Czech Academy of Sciences Publication Activity Database

    Chýlková, J.; Machalický, O.; Tomášková, M.; Šelešovská, R.; Navrátil, Tomáš

    2016-01-01

    Roč. 49, č. 1 (2016), s. 92-106 ISSN 0003-2719 R&D Projects: GA ČR(CZ) GAP208/12/1645 Institutional support: RVO:61388955 Keywords : 2,6-di-tert-butyl-4-methyl-phenol * handing drop mercury electrode * nitration Subject RIV: CG - Electrochemistry Impact factor: 1.150, year: 2016

  9. Substituted 2,2'-bipyridines by nickel-catalysis: 4,4'-di-tert-butyl-2,2'-bipyridine.

    Science.gov (United States)

    Buonomo, Joseph A; Everson, Daniel A; Weix, Daniel J

    2013-11-01

    A simple, ligand-free synthesis of the important bipyridyl ligand 4,4'-di- tert -butyl-2,2'-bipyridine is presented. 5,5'-bis(trifluoromethyl)-2,2'-bipyridine is also synthesized by the same protocol. The syntheses efficiently couple the parent 2-chlorpyridies by a nickel-catalyzed dimerization with manganese powder as the terminal reductant.

  10. SYNTHESIS OF METHYL TERT-BUTYL ETHER CATALYZED BY ACIDIC ION-EXCHANGE RESINS - INFLUENCE OF THE PROTON ACTIVITY

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1995-01-01

    The catalytic activity of various strong acid ion-exchange resins on the synthesis of methyl tert-butyl ether (MtBE) from methanol and isobutene has been investigated. Relative to Amberlyst 15, Kastel CS 381 and Amberlyst CSP have similar rate constants, whereas Duolite ES 276 and Amberlyst XE 307

  11. Novel process window for the safe and continuous synthesis of tert.-butyl peroxy pivalate in a micro reactor

    NARCIS (Netherlands)

    Illg, T.; Hessel, V.; Löb, P.; Schouten, J.C.

    2011-01-01

    In this paper, the two step synthesis of tert.-butyl peroxy pivalate using two different flow regimes is introduced, in particular the use of "segmented flow" and the concept of "dispersed flow". The use of the segmented flow process, in this case, is challenging due to the very low interfacial

  12. Crystal structure of 2-tert-butyl-1,3-thiazolo[4,5-b]pyridine

    Directory of Open Access Journals (Sweden)

    Gamal A. El-Hiti

    2014-09-01

    Full Text Available The title compound, C10H12N2S, does not contain any strong hydrogen-bond donors but two long C—H...N contacts are observed in the crystal structure, with the most linear interaction linking molecules along [010]. The ellipsoids of the tert-butyl group indicate large librational motion.

  13. Quercetin protects human hepatoma HepG2 against oxidative stress induced by tert-butyl hydroperoxide

    International Nuclear Information System (INIS)

    Alia, Mario; Ramos, Sonia; Mateos, Raquel; Granado-Serrano, Ana Belen; Bravo, Laura; Goya, Luis

    2006-01-01

    Flavonols such as quercetin, have been reported to exhibit a wide range of biological activities related to their antioxidant capacity. The objective of the present study was to investigate the protective effect of quercetin on cell viability and redox status of cultured HepG2 cells submitted to oxidative stress induced by tert-butyl hydroperoxide. Concentrations of reduced glutathione and malondialdehyde, generation of reactive oxygen species and activity and gene expression of antioxidant enzymes were used as markers of cellular oxidative status. Pretreatment of HepG2 with 10 μM quercetin completely prevented lactate dehydrogenase leakage from the cells. Pretreatment for 2 or 20 h with all doses of quercetin (0.1-10 μM) prevented the decrease of reduced glutathione and the increase of malondialdehyde evoked by tert-butyl hydroperoxide in HepG2 cells. Reactive oxygen species generation induced by tert-butyl hydroperoxide was significantly reduced when cells were pretreated for 2 or 20 h with 10 μM and for 20 h with 5 μM quercetin. Finally, some of the quercetin treatments prevented the significant increase of glutathione peroxidase, superoxide dismutase, glutathione reductase and catalase activities induced by tert-butyl hydroperoxide. Gene expression of antioxidant enzymes was also affected by the treatment with the polyphenol. The results of the biomarkers analyzed clearly show that treatment of HepG2 cells in culture with the natural dietary antioxidant quercetin strongly protects the cells against an oxidative insult

  14. Design and Control of Glycerol-tert-Butyl Alcohol Etherification Process

    Directory of Open Access Journals (Sweden)

    Elena Vlad

    2012-01-01

    Full Text Available Design, economics, and plantwide control of a glycerol-tert-butyl alcohol (TBA etherification plant are presented. The reaction takes place in liquid phase, in a plug flow reactor, using Amberlyst 15 as a catalyst. The products' separation is achieved by two distillation columns where high-purity ethers are obtained and a section involving extractive distillation with 1,4-butanediol as solvent, which separates TBA from the TBA/water azeotrope. Details of design performed in AspenPlus and an economic evaluation of the process are given. Three plantwide control structures are examined using a mass balance model of the plant. The preferred control structure fixes the fresh glycerol flow rate and the ratio glycerol + monoether : TBA at reactor-inlet. The stability and robustness in the operation are checked by rigorous dynamic simulation in AspenDynamics.

  15. Photoelectric conversion and electrochromic properties of lutetium tetrakis(tert-butyl)bisphthalocyaninate

    International Nuclear Information System (INIS)

    Hu, Andrew Teh; Hu Tenyi; Liu Lungchang

    2003-01-01

    Both photoelectric and electrochromic effects on lutetium tetrakis(tert-butyl)bisphthalocyaninate (Lu(TBPc) 2 ) have been carried out in this study. Lu(TBPc) 2 is known for its electrochromic performance, but its photoelectric effect has not mentioned in the literature. The electrochromic properties of Lu(TBPc) 2 have been measured by cyclic voltammetry (CV) and UV-Vis spectrometer at the same time. It takes less than 1.5 s for the color to change from red to green under 0.9 V. Its cycle life is at least over 500 times. Furthermore, we also investigate its photoelectric conversion properties. Its photoelectric cell exhibits a positive photo-electricity conversion effect with a short-circuit photocurrent (46.4 μA/cm 2 ) under illumination of white light (1.201 mW/cm 2 )

  16. Influence of mass transport towards deactivation in tert-butyl-source driven isobutane/2-butene alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Aschauer, S.J.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2011-07-01

    The deactivation of i-butane/trans-2-butene alkylation using tert-butyl-halide promoted ionic liquid catalysts is studied.Here, the mass transport was modified by varying the feed rate and the type of promoter addition. The experimental data show that the deactivation increases with increasing feed rate. Moreover, a biliquid foam is formed when feed rates above 1 g/min are adjusted. As the results indicate a strong influence of the biliquid foam and its formation on deactivation, both aspects are also discussed.When the promoter is added to the feed mixture an increase of conversion with time on stream is observed. A deactivation in continuous promoter addition mode could not be noted in the investigated time-on-stream range. (orig.)

  17. Di-tert-butyl 2,2′-(biphenyl-2,2′-diyldioxydiacetate

    Directory of Open Access Journals (Sweden)

    Qamar Ali

    2008-08-01

    Full Text Available The title compound, C24H30O6, does not exhibit π–π interactions due to the steric effect of the bulky tert-butyl groups present in the molecule. The presence of these groups at the 2 and 2′ positions hinders the free motion of the benzene rings relative to each other, causing them to adopt an antiperiplanar arrangement. The benzene rings are twisted by just under 50.96 (17° with respect to each other. The carbonyl groups within the molecule are directed in different directions, one towards the biphenyl group and the other away from it. The molecules are linked together by C=O...H—C hydrogen bonds.

  18. Actinide-carbon bonds: insertion reactions of carbon monoxide, tert-butyl isocyanide, and tert-butyl cyanide into [(Me3Si)2N]2MCH2Si(Me)2NSiMe3

    International Nuclear Information System (INIS)

    Simpson, S.J.; Andersen, R.A.

    1981-01-01

    The thorium or uranium metallacycles [(Me 2 Si) 2 N] 2 MCH 2 Si(Me) 2 NSiMe 3 (I) react with tert-butyl cyanide to give the six-membered ring compounds [(Me 3 Si) 2 N] 2 MN = C(t-Bu)CH 2 Si(Me) 2 NSiMe 3 . The metallacycles (I) also react with the isoelectronic molecules tert-butyl isocyanide and carbon monoxide to give the unique five-membered ring compounds with exocyclic carbon-carbon double bonds, [(Me 3 Si) 2 N] 2 MXC(=CH 2 )Si(Me) 2 NSiMe 3 , where X is t-BuN or oxygen. The four-membered ring metallacycles (I) give simple coordination complexes of the type [(Me 3 Si) 2 N] 2 MCH 2 Si-(Me) 2 NSiMe 3 (N 3 SiMe 3 ) with trimethylsilyl azide

  19. Standard thermochemical characteristics of combustion and formation of 3,5-di-tert-butyl-o-benzoquinone and 3,6-di-tert-butyl-o-benzoquinone at T = 298.15 K

    International Nuclear Information System (INIS)

    Pashanova, Kira I.; Abakumov, Gleb A.; Markin, Alexey V.; Piskunov, Alexander V.; Smirnova, Natalia N.

    2016-01-01

    Highlights: • We report the results of thermochemical study for benzoquinone derivatives. • Optimal conditions for determination of combustion energy for benzoquinone were done. • The formation enthalpies for crystalline benzoquinone have been detected at T = 298.15 K. • The formation enthalpy of isomeric quinones were compared. - Abstract: Optimal conditions for investigations of thermodynamic properties have been determined experimentally by the method of combustion calorimetry for compounds of the o-benzoquinone series. In the present work, the energies of combustion in oxygen were measured at T = 298.15 K by static bomb combustion calorimetry for 3,5-di-tert-butyl-o-benzoquinone and 3,6-di-tert-butyl-o-benzoquinone. The experimental values have been used to calculate the standard (p° = 0.1 MPa) molar enthalpy of combustion Δ_cH"o_m and formation Δ_fH"o_m for the examined compounds in the crystalline phase.

  20. Substituent effects in heterogeneous catalysis--5. The steric hindrance of bulky alkyl substituents in cyclohexanone hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Chihara, T; Tanaka, K

    1979-02-01

    The steric hindrance of bulky alkyl substituents in cyclohexanone hydrogenation was demonstrated by the reactivities of 2-isopropyl and 2-tert.-butyl cyclohexanone relative to cyclohexanone in individual and competitive hydrogenation at 30/sup 0/C over alumina-supported ruthenium, rhodium, and platinum catalysts. The results indicate that the ketone adsorption onto the catalyst is sterically hindered by the alkyl substitution significantly more than the surface reaction which follows the adsorption.

  1. Effect of tert-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Pápai, Mátyás Imre; Penfold, Thomas J.; Møller, Klaus Braagaard

    2016-01-01

    -vibronic quantum dynamics simulations on the Fe-N-heterocyclic carbene complex, [Fe(btbip)2]2+ (btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine). The results demonstrate that a relatively minor structural change compared to its parent complex, [Fe(bmip)2]2+ (bmip = 2,6-bis(3-methyl-imidazole-1-ylidene....... This occurs because the tert-butyl functionalization stabilizes the 1MC states, enabling the 1,3MLCT → 1MC population transfer to occur close to the Franck-Condon geometry, making the conversion very efficient. Subsequently, a spin cascade occurs within the MC manifold, leading to the population of triplet...

  2. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.

    1995-01-01

    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

  3. Di-tert-butyl 2,2′-[(biphenyl-4,4′-diyldioxy]diacetate

    Directory of Open Access Journals (Sweden)

    Qamar Ali

    2010-07-01

    Full Text Available The complete molecule of the title compound, C24H30O6, is generated by a crystallographic inversion centre. In the unique part of the molecule, the four-atom –O–CH2–C(= O–O– chain between the benzene ring and the tert-butyl group assumes a zigzag conformation [O—C—C—O torsion angle = −162.3 (1°].

  4. Degradation of methyl tert-butyl ether by gel immobilized Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Chen, Dongzhi; Chen, Jianmeng; Zhong, Weihong; Cheng, Zhuowei

    2008-07-01

    Cells of Methylibium petroleiphilum PM1 were immobilized in gel beads to degrade methyl tert-butyl ether (MTBE). Calcium alginate, agar, polyacrylamide and polyvinvyl alcohol were screened as suitable immobilization matrices, with calcium alginate demonstrating the fastest MTBE-degradation rate. The rate was accelerated by 1.8-fold when the beads had been treated in physiological saline for 24h at 28 degrees C. MTBE degradation in mineral salts medium (MSM) was accompanied by the increase of biomass. The half-life of MTBE-degradation activity for the encapsulated cells stored at 28 degrees C was about 120 h, which was obviously longer than that of free cells (approximately 36 h). Efficient reusability of the beads up to 30 batches was achieved in poor nutrition solution as compared to only 6 batches in MSM. The immobilized cells could be operated in a packed-bed reactor for degradation of 10 mg L(-1) MTBE in groundwater with more than 99% removal efficiency at hydraulic retention time of 20 min. These results suggested that immobilized cells of PM1 in bioreactor might be applicable to a groundwater treatment system for the removal of MTBE.

  5. Entanglement Dynamics in Miscible Polyisoprene / Poly(p-tert-butyl styrene) Blends

    Science.gov (United States)

    Watanabe, Hiroshi

    2011-03-01

    Viscoelastic and dielectric behavior was examined for well entangled, miscible blends of high- M cis-polyisoprene (PI) and poly(p-tert-butyl styrene) (PtBS). The dielectric data of the blends, reflecting the global motion of the PI chains having the type-A dipoles, indicated that PI and PtBS were the fast and slow components therein. At high temperatures T , the blends exhibited two-step entanglement plateau. The high frequency (ω) plateau height was well described by a simple mixing rule of the entanglement length based on the number fraction of the Kuhn segments. At low T , the blend exhibited the Rouse-like power-law behavior of storage and loss moduli, G ' = G ~ω0.5 , in the range of ω where the high- ω plateau was supposed to emerge. This lack of the high- ω plateau was attributed to retardation of the Rouse equilibration of the PI chain over the entanglement length due to the hindrance from the slow PtBS chains: The PI and PtBS chains were equilibrated cooperatively, and the retardation due to PtBS shortened the plateau for PI to a width not resolved experimentally. A simple model for this cooperative equilibration formulated on the basis of the dielectric data described the viscoelastic data surprisingly well.

  6. Facile reactions of gold(i) complexes with tri(tert-butyl)azadiboriridine.

    Science.gov (United States)

    Shang, Rong; Saito, Souta; Jimenez-Halla, J Oscar C; Yamamoto, Yohsuke

    2018-04-17

    Direct structural evidence for group 11 metal-mediated B-B bond activation was obtained from reactions of tri(tert-butyl)azadiboriridine (1) with AuCl(L) complexes. The AuCl(SMe2) reaction afforded [η2-B,B-B(tBu)N(tBu)B(tBu)]AuCl (2) by ligand displacement. More donating phosphines as co-ligands led to B-B bond cleavage accompanied by either halide or L migration to form boron-gold complexes 3 (L = PPh3) and 4 (L = PMe3). A similar product 5, which is isostructural to 4, was obtained by the addition of dimethylaminopyridine (DMAP) to 2-4. Complexes 2-5 constitute rare examples of metal complexes bearing two Lewis acidic centres. The effect of the boryl ligand was demonstrated in the formation of a gold(i) complex 6 bearing a 5-membered heterocycle from 3 and tert-butylisonitrile. Plausible reaction mechanisms that led to these complexes and their bonding situation were explored computationally at the DFT level.

  7. Protective effects of hesperidin against oxidative stress of tert-butyl hydroperoxide in human hepatocytes.

    Science.gov (United States)

    Chen, Mingcang; Gu, Honggang; Ye, Yiyi; Lin, Bing; Sun, Lijuan; Deng, Weiping; Zhang, Jingzhe; Liu, Jianwen

    2010-10-01

    Increasing evidence regarding free radical generating agents and the inflammatory process suggest that accumulation of reactive oxygen species (ROS) could involve hepatotoxicity. Hesperidin, a naturally occurring flavonoid presents in fruits and vegetables, has been reported to exert a wide range of pharmacological effects that include antioxidant, anti-inflammatory, antihypercholesterolemic, and anticarcinogenic actions. However, the cytoprotection and mechanism of hesperidin to neutralize oxidative stress in human hepatic L02 cells remain unclear. In this work, we assessed the capability of hesperidin to prevent tert-butyl hydroperoxide (t-BuOOH)-induced cell damage by augmenting cellular antioxidant defense. Hesperidin significantly protected hepatocytes against t-BuOOH-induced cell cytotoxicity, such as mitochondrial membrane potential (MMP) deplete and lactate dehydrogenase (LDH) release. Hesperidin also remarkably prevented indicators of oxidative stress, such as the ROS and lipid peroxidation level in a dose-dependent manner. Western blot showed that hesperidin facilitated ERK/MAPK phosphorylation which appeared to be responsible for nuclear translocation of Nrf2, thereby inducing cytoprotective heme oxygenase-1 (HO-1) expression. Based on the results described above, it suggested that hesperidin has potential as a therapeutic agent in the treatment of oxidative stress-related hepatocytes injury and liver dysfunctions. Copyright © 2010 Elsevier Ltd. All rights reserved.

  8. Two DSC Glass Transitions in Miscible Blends of Polyisoprene / Poly(4-tert-butyl styrene)

    Science.gov (United States)

    Zhao, Junshu; Sun, Ye; Yu, Lian; Ediger, Mark

    2009-03-01

    Conventional and temperature modulated differential scanning calorimetry experiments have been carried out on miscible blends of polyisoprene (PI) and poly(4-tert-butyl styrene) (P4tBS) over a broad composition range. This system is characterized by an extraordinarily large component Tg difference (˜215 K) between the two homopolymers. Two distinct calorimetric Tgs were observed in blends with an intermediate composition range (25%˜50% PI) by both conventional and temperature modulated DSC. Good agreement was found between the Tg values measured by the two methods. Fitting of the measured Tgs to the Lodge-McLeish model gives a φself of 0.62˜0.64 for PI in this blend and 0.02˜0.05 for P4tBS. The extracted φself for PIis comparable to reported values for PEO in blends with PMMA and is significantly larger than those reported for other PI blends with smaller component Tg differences. This observation suggests the presence of a confinement effect in PI/P4tBS blends, which results in enhanced fast component dynamics below the effective Tg of the slow component.

  9. Artificial Neural Network Approach to Predict Biodiesel Production in Supercritical tert-Butyl Methyl Ether

    Directory of Open Access Journals (Sweden)

    Obie Farobie

    2016-05-01

    Full Text Available In this study, for the first time artificial neural network was used to predict biodiesel yield in supercritical tert-butyl methyl ether (MTBE. The experimental data of biodiesel yield conducted by varying four input factors (i.e. temperature, pressure, oil-to-MTBE molar ratio, and reaction time were used to elucidate artificial neural network model in order to predict biodiesel yield. The main goal of this study was to assess how accurately this artificial neural network model to predict biodiesel yield conducted under supercritical MTBE condition. The result shows that artificial neural network is a powerful tool for modeling and predicting biodiesel yield conducted under supercritical MTBE condition that was proven by a high value of coefficient of determination (R of 0.9969, 0.9899, and 0.9658 for training, validation, and testing, respectively. Using this approach, the highest biodiesel yield was determined of 0.93 mol/mol (corresponding to the actual biodiesel yield of 0.94 mol/mol that was achieved at 400 °C, under the reactor pressure of 10 MPa, oil-to-MTBE molar ratio of 1:40 within 15 min of reaction time.

  10. Methyl tert-butyl ether biodegradation by indigenous aquifer microorganisms under natural and artificial oxic conditions

    Science.gov (United States)

    Landmeyer, J.E.; Chapelle, F.H.; Herlong, H.H.; Bradley, P.M.

    2001-01-01

    Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert-butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were > 1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/L to a depth of 1.5 m, and MTBE concentrations decreased to CO2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.

  11. Redox Regulation of the Tumor Suppressor PTEN by Hydrogen Peroxide and Tert-Butyl Hydroperoxide

    Directory of Open Access Journals (Sweden)

    Ying Zhang

    2017-05-01

    Full Text Available Organic peroxides and hydroperoxides are skin tumor promoters. Free radical derivatives from these compounds are presumed to be the prominent mediators of tumor promotion. However, the molecular targets of these species are unknown. Phosphatase and tensin homologs deleted on chromosome 10 (PTEN are tumor suppressors that play important roles in cell growth, proliferation, and cell survival by negative regulation of phosphoinositol-3-kinase/protein kinase B signaling. PTEN is reversibly oxidized in various cells by exogenous and endogenous hydrogen peroxide. Oxidized PTEN is converted back to the reduced form by cellular reducing agents, predominantly by the thioredoxin (Trx system. Here, the role of tert-butyl hydroperoxide (t-BHP in redox regulation of PTEN was analyzed by using cell-based and in vitro assays. Exposure to t-BHP led to oxidation of recombinant PTEN. In contrast to H2O2, PTEN oxidation by t-BHP was irreversible in HeLa cells. However, oxidized PTEN was reduced by exogenous Trx system. Taken together, these results indicate that t-BHP induces PTEN oxidation and inhibits Trx system, which results in irreversible PTEN oxidation in HeLa cells. Collectively, these results suggest a novel mechanism of t-BHP in the promotion of tumorigenesis.

  12. Steric/π-electronic insulation of the carbo-benzene ring: dramatic effects of tert-butyl vs phenyl crowns on geometric, chromophoric, redox and magnetic properties.

    Science.gov (United States)

    Listunov, Dymytrii; Duhayon, Carine; Poater, Albert; Mazères, Serge; Saquet, Alix; Maraval, Valérie; Chauvin, Remi

    2018-04-13

    Hexa-tert-butyl-carbo-benzene C18tBu6 and three phenylated counterparts C18tBumPh6-m (m = 4, 2) have been synthesized. The peralkylated version (m = 6) provides experimental access to intrinsic features of the insulated C18 core independently from the influence of π-conjugated substituent. Over the series, structural, spectroscopical and electrochemical properties are compared with those of the hexaphenylated reference (m = 0). Anchoring tBu substituents at the C18 macrocycle is shown to enhance stability and solubility, and to dramatically modify UV-vis absorption and redox properties. Whereas all the carbo-benzenes reported hitherto were obtained as dark-reddish/greenish solids, crystals and solutions of C18tBu6 happen to be yellow (max = 379 nm vs 472 nm for C18Ph6). By comparison to C18Ph6, reduction of C18tBu6 remains reversible but occurs at a twice higher absolute potential (E1/2 = -1.36 V vs -0.72 V). Systematic X-ray diffraction analyses and DFT calculations show that the C18 ring symmetry is the nearest to D6h for m = 6, indicating a maximum geometrical aromaticity. According to calculated nucleus independent chemical shifts, the macrocyclic magnetic aromaticity is also found to be maximum for C18tBu6: NICS(0)=-17.2 ppm, vs -18.0±0.1 ppm for the theoretical references C18H6 and C18F6, and -13.5 ppm for C18Ph6. Accurate correlations of NICS(0) with experimental or calculated maximum UV-vis absorption wavelength max and chemical hardness =ELUMO-EHOMO are evidenced. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Enhancement of the Biodegradability of Methyl tert- Butyl Ether (MTBE by Advanced Oxidation

    Directory of Open Access Journals (Sweden)

    Mehraban Sadeghi

    2006-06-01

    Full Text Available The effectiveness of ozone treatment for improving the biodegradability of recalcitrant pollutants has been proved by investigating the ozonation reaction of Methyl tert-Butyl Ether (MTBE as a bioresistant gasoline oxygenate. Laboratory scale experiments have been carried out at room temperature by bubbling for 120 minutes ozonated air (3.4 ppm/min into 3 liter of an alkaline (pH=11.5 aqueous solution (100 mg/L of MTBE. The experimental results indicated that during the ozonation, complete MTBE degradation occurs in 100 minutes and after this time, ozone consumption goes on very slowly. At the end of the ozonation, after 100 minutes, the initial value of COD (256 mg O2/L is 98 and corresponds to a relative removal of about 62%. As for MTBE solution biodegradability expressed as (BOD5 / (COD ratio, during the first 90 minutes, its value regularly increases from lowest 0.01 up to a maximum of 0.68 that corresponds to an ozone consumption of 1.25 mg per each mg of COD initially present in the solution. The research showed that partial degradation of MTBE in the advanced oxidation processes results an increase in its biological degradation. But more oxidation results lower  (BOD5 / (COD ratio. Also the research showed that for idealization of the chemical oxidation conditions of MTBE, it needs to decrease COD to 46-68% before the biological degradation. The experimental results for determining the rate of MTBE removal due to stripping showed that about 14% of MTBE strips out after an hour of sparging with oxygen gas. The fraction of MTBE oxidized and/or striped increases to about 28% (in pH=7 and 70% (in pH=11.5 with ozonation over the same time period.

  14. Development of natural rubber membranes for separation of methyl tert-butyl ether and methanol

    International Nuclear Information System (INIS)

    Nur Azrini Ramlee; Ghazali Mohd Nawawi; Khairul Zaman Dahlan

    2010-01-01

    As a new commercial process, membrane separation raises significant expectations in the process plant of the future and therefore this research was being initiated to develop and characterize pervaporation membrane based on natural rubber (NR). Natural Rubber SMR-L grade which was supplied by Malaysia Rubber Research Institute (MRRI) was used for the development of the membranes via interpenetrating polymer network (IPN) techniques. Polystyrene (PS) was used to modify the natural rubber to further improve their mechanical and chemical properties. The membranes were prepared with various blend ratios of natural rubber, polystyrene and divinyl benzene as cross linker with constant 1 % of dicumyl peroxide as the initiator. The developed membranes were then characterized to study the functional group presence, membranes morphology, crosslink density, tear strength, adsorption of the membranes and pervaporation separation of Methyl-Tert-Butyl-Ether (MTBE) and Methanol. Pervaporation process was conducted by using varies of MTBE concentration 10, 30, 50 and 70 wt % and at differ operation temperature, 25 degree Celsius and 55 degree Celsius. Separation performance of IPN NR/ PS membranes were based on the presented permeation flux and separation factor. Examination through Fourier Transform Infrared Spectroscopy (FTIR), determined crosslink density and tear strength, 6 series of IPN NR/ PS membranes were successfully developed using natural rubber. Observation from Scanning Electron Microscopy (SEM) showed that the membranes were dense and appropriated for the pervaporation process application. From the pervaporation of MTBE and Methanol, IPN NR/ PS membranes of series D4N30 shown low permeation flux of MTBE but high separation factor while D2N70 membranes was vice versa for both temperature of 25 degree Celsius and 55 degree Celsius. (author)

  15. Dynamics in miscible blends of polyisoprene and poly(p-tert-butyl styrene): thermo–rheological behavior of components

    OpenAIRE

    Chen, Quan; Matsumiya, Yumi; Watanabe, Hiroshi

    2011-01-01

    For miscible blends of moderately entangled cis-polyisoprene (PI) and poly(p-tert-butyl styrene) (PtBS), viscoelastic and dielectric properties were examined over a wide range of temperature (T) to discuss the thermo–rheological behavior of respective components. Because PI has the type-A dipole, whereas PtBS does not, the slow dielectric response of the blends was exclusively attributed to the global motion of the PI chains therein. In most of the blends examined, the viscoelastic relaxation...

  16. Use of experimental design for the purge-and-trap-gas chromatography-mass spectrometry determination of methyl tert.-butyl ether, tert.-butyl alcohol and BTEX in groundwater at trace level.

    Science.gov (United States)

    Bianchi, F; Careri, M; Marengo, E; Musci, M

    2002-10-25

    An efficient method for the simultaneous determination of methyl tert.-butyl ether, tert.-butyl alcohol, benzene, toluene, ethylbenzene and xylene isomers in groundwater by purge-and-trap-gas chromatography-mass spectrometry was developed and validated. Experimental design was used to investigate the effects of temperature of extraction, time of extraction and percentage of salt added to the water samples. Regression models and desirability functions were applied to find the experimental conditions providing the highest global extraction yield. Validation was carried out in terms of limits of detection (LOD), limits of quantitation (LOQ), linearity and precision. LOD values ranging from 2.6 to 23 ng l(-1) were achieved, whereas linearity was statistically verified over two orders of magnitude for each compound. Precision was evaluated testing two concentration levels. Good results were obtained both in terms of intra-day repeatability and intermediate precision: RSD% lower than 4.5% at the highest concentration and lower than 13% at the lowest one were calculated for intra-day repeatability. A groundwater sample suspected of contamination by leaking underground petroleum storage tanks was analysed and some of the analytes were detected and quantitated.

  17. Biofiltration and inhibitory interactions of gaseous benzene, toluene, xylene, and methyl tert-butyl ether.

    Science.gov (United States)

    Shim, Eun-Hwa; Kim, Jaisoo; Cho, Kyung-Suk; Ryu, Hee Wook

    2006-05-01

    This study evaluated the individual and combined removal capacities of benzene, toluene, and xylene (B, T, and X) in the presence and absence of methyl tert-butyl ether (MTBE) in a polyurethane biofilter inoculated with a BTX-degrading microbial consortium, and further examined their interactive effects in various mixtures. In addition, Polymerase chain reaction-denaturing gradient gel electrophoresis and phylogenetic analysis of 16S rRNA gene sequences were used to compare the microbial community structures found in biofilters exposed to the various gases and gas mixtures. The maximum individual elimination capacities (MECs) of B, T, and X were 200, 238, and 400 g m(-3) h(-1), respectively. There was no significant elimination of MTBE alone. Addition of MTBE decreased the MECs of B,T, and X to 75, 100, and 300 g m(-3) h(-1), respectively, indicating that benzene was most strongly inhibited by MTBE. When the three gases were mixed (B + T + X), the removal capacities of individual B, T, and X were 50, 90, and 200 g m(-3) h(-1), respectively. These capacities decreased to 40, 50, and 100 g m(-3) h(-1) when MTBE was added to the mix. The MEC of the three-gas mixture (B + T + X) was 340 g m(-3) h(-1), and that of the four-gas mixture was 200 g m(-3) h(-1). Although MTBE alone was not degraded by the biofilter, it could be co-metabolically degraded in the presence of toluene, benzene, or xylene with the MECs of 34, 23, and 14 g m(-3) h(-1), respectively. The microbial community structure analysis revealed that two large groups could be distinguished based on the presence or absence of MTBE, and many of the dominant bacteria in the consortia were closely related to bacteria isolated from aromatic hydrocarbon-contaminated sites and/ or oil wastewaters. These findings provide important new insights into biofiltration and may be used to improve the rational design of biofilters for remediation of petroleum gas-contaminated airstreams according to composition types of mixed

  18. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrapropynyloxy-2,8,14,20-tetrathiacalix[4]arene

    Directory of Open Access Journals (Sweden)

    Xiang-Gao Meng

    2009-12-01

    Full Text Available The title compound [systematic name: 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrapropynyloxy-2,8,14,20-tetrathiacalix[4]arene], C52H56O4S4, is an alkylated product bearing four propyne groups at the lower rim of a 5,11,17,23-tetra-tert-butyl-tetrathiacalix[4]arene. The molecule is located on a crystallographic twofold rotation axis, running through two S atoms and perpendicular to the long axis of the molecule. The four propyne groups, located in an alternate fashion above and below the mean plane of the four S atoms, are almost parallel to the calixarene long axis. The dihedral angle between the two crystallographically independent benzene rings is 86.77 (14°. Two tert-butyl groups are disordered over two positions with site occupancies of 0.59 (2 and 0.41 (2.

  19. Involvement of a novel enzyme, MdpA, in methyl tert-butyl ether degradation in Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R

    2008-11-01

    Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr(59) distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum.

  20. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111

    Directory of Open Access Journals (Sweden)

    A. Schuler

    2017-01-01

    Full Text Available Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111 in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

  1. Microbial community composition during anaerobic mineralization of tert-butyl alcohol (TBA) in fuel-contaminated aquifer material.

    Science.gov (United States)

    Wei, Na; Finneran, Kevin T

    2011-04-01

    Anaerobic mineralization of tert-butyl alcohol (TBA) and methyl tert-butyl ether (MTBE) were studied in sediment incubations prepared with fuel-contaminated aquifer material. Microbial community compositions in all incubations were characterized by amplified ribosomal DNA restriction analysis (ARDRA). The aquifer material mineralized 42.3±9.9% of [U-(14)C]-TBA to 14CO2 without electron acceptor amendment. Fe(III), sulfate, and Fe(III) plus anthraquinone-2,6-disulfonate addition also promoted U-[14C]-TBA mineralization at levels similar to those of the unamended controls. Nitrate actually inhibited TBA mineralization relative to unamended controls. In contrast to TBA, [U-(14)C]-MTBE was not significantly mineralized in 400 days regardless of electron acceptor amendment. Microbial community analysis indicated that the abundance of one dominant clone group correlated closely with anaerobic TBA mineralization. The clone was phylogenetically distinct from known aerobic TBA-degrading microorganisms, Fe(III)- or sulfate-reducing bacteria. It was most closely associated with organisms belonging to the alphaproteobacteria. Microbial communities were different in MTBE and TBA amended incubations. Shannon indices and Simpson indices (statistical community comparison tools) both demonstrated that microbial community diversity decreased in incubations actively mineralizing TBA, with distinct "dominant" clones developing. These data contribute to our understanding of anaerobic microbial transformation of fuel oxygenates in contaminated aquifer material and the organisms that may catalyze the reactions.

  2. Assessment of genotoxicity of methyl-tert-butyl ether, benzene, toluene, ethylbenzene, and xylene to human lymphocytes using comet assay

    International Nuclear Information System (INIS)

    Chen, Colin S.; Hseu, You C.; Liang, Shih H.; Kuo, J.-Y.; Chen, Ssu. C.

    2008-01-01

    Methyl-tert-butyl ether (MTBE) is a gasoline oxygenate and antiknock additive substituting for lead alkyls currently in use worldwide. Benzene, toluene, ethylbenzene, and xylene (BTEX) are volatile monoaromatic hydrocarbons which are commonly found together in crude petroleum and petroleum products such as gasoline. The aim of this study is to evaluate the genotoxic effects of these tested chemicals in human lymphocytes. Using the alkaline comet assay, we showed that all of the tested chemicals induce DNA damage in isolated human lymphocytes. This effect could follow from the induction of DNA strands breaks. The neutral version of the test revealed that MTBE, benzene, and xylenes induce DNA double-strand breaks at 200 μM. Apart from MTBE, the spin traps, 5,5-dimethyl-pyrroline-N-oxide (DMPO) and N-tert-butyl-α-phenylnitrone (PBN) can decrease the level of DNA damage in BTEX at 200 μM. This indicated that DNA damage could result from the participation of free radicals in DNA-damaging effect, which was further supported by the fact that post-treatment of formamidopyrimidine-DNA glycosylase (Fpg), enzyme recognizing oxidized DNA purines, gave rise to a significant increase in the extent of DNA damage in cells treated with benzene, and xylene at 200 μM. The results obtained suggested that MTBE and BTEX could induce a variety type of DNA damage such as single-strand breaks (SSBs), double-strand breaks (DSBs), and oxidative base modification

  3. Formation of Germa-ketenimine on the Ge(100) Surface by Adsorption of tert-Butyl Isocyanide.

    Science.gov (United States)

    Shong, Bonggeun; Yoo, Jong Suk; Sandoval, Tania E; Bent, Stacey F

    2017-06-28

    Reactions of the (100) surfaces of Ge and Si with organic molecules have been generally understood within the concept of "dimers" formed by the 2 × 1 surface reconstruction. In this work, the adsorption of tert-butyl isocyanide on the Ge(100)-2 × 1 surface at large exposures is investigated under ultrahigh vacuum conditions. A combination of infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption experiments along with dispersion-corrected density functional theory calculations is used to determine the surface products. Upon adsorption of a dense monolayer of tert-butyl isocyanide, a product whose structure resembles a germa-ketenimine (N=C=Ge) with σ donation toward and π back-donation from the Ge(100) surface appears. Formation of this structure involves divalent-type surface Ge atoms that arise from cleavage of the Ge(100)-2 × 1 surface dimers. Our results reveal an unprecedented class of reactions of organic molecules at the Ge(100) surface.

  4. Tailored Interfaces for Biosensors and Cell-Surface Interaction Studies via Activation and Derivatization of Polystyrene-block-poly(tert-butyl acrylate) Thin Films

    NARCIS (Netherlands)

    Feng, C.L.; Embrechts, A.; Bredebusch, Ilona; Bouma, Anita; Schnekenburger, Jürgen; Garcia Parajo, M.F.; Domschke, Wolfram; Vancso, Gyula J.; Schönherr, Holger

    2007-01-01

    Thin spin-coated films of polystyrene-block-poly(tert-butyl acrylate) (PS690-b-PtBA1210) on various substrates are introduced as versatile, robust reactive platform for the immobilization of (bio)molecules for the fabrication of tailored biointerfaces. The films are characterized by high stability

  5. Hydrophobic hydration and anomalous excess partial molar volume of tert-butyl alcohol-water mixture studied by quasielastic neutron scattering

    International Nuclear Information System (INIS)

    Nakada, Masaru; Maruyama, Kenji; Misawa, Masakatsu; Yamamuro, Osamu

    2007-01-01

    Quasielastic neutron scattering has been used to investigate the hydration of alcohol clusters in tert-butyl alcohol-water mixture. The measurements were made in a range of alcohol concentration, x TBA , from 0.0 to 0.17 in mole fraction at 25degC. Fraction, α, of water molecules hydrated to fractal-surface of alcohol clusters in tert-butyl alcohol-water mixture was obtained as a function of alcohol concentration. Average hydration number N WS of tert-butyl alcohol molecule was derived from the value of α as a function of alcohol concentration. The value of N WS for an isolated alcohol molecule in water was 19-21. The anomalous excess partial molar volume of tert-butyl alcohol-water mixture was interpreted successfully by applying the same model with the same values of volume parameter as used for 1-propanol-water mixture, δ 1 (=-0.36 cm 3 ·mol -1 ) and δ 2 (=0.60 cm 3 ·mol -1 ). (author)

  6. Bromine catalyzed conversion of S-tert-butyl groups into versatile and, for self-assembly processes accessible, acetyl-protected thiols.

    Science.gov (United States)

    Blaszczyk, Alfred; Elbing, Mark; Mayor, Marcel

    2004-10-07

    The facile and efficient conversion of a tert-butyl protecting group to an acetyl protecting group for thiols by catalytic amounts of bromine in acetyl chloride and the presence of acetic acid has been developed. The fairly mild reaction conditions are of particular interest for new protecting group strategies for sulfur functionalised target structures. Copyright 2004 The Royal Society of Chemistry

  7. Effect of benzene, toluene, ethylbenzene, and p-xylene (BTEX) mixture on biodegradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) by pure culture UC1.

    Science.gov (United States)

    Pruden, Amy; Suidan, Makram

    2004-08-01

    The effect of a BTEX mixture on the biodegradation of methyl tert-butyl ether (MTBE) and its degradation intermediate, tert-butyl alcohol (TBA) was investigated in the pure bacterial culture UC1, which has been identified to be a strain of the known MTBE-degrader PM1 based on greater than 99% 16S rDNA similarity. Several degradation studies were carried out on UC1 at three initial concentration levels of MTBE or TBA: 6-7; 15-17; and 40-45 mg/l, both with and without BTEX present cumulatively at about half of the MTBE or TBA molar mass in the system. The BTEX mixture was observed not to affect either the rate or the degradation lag period of MTBE or TBA degradation, except that the TBA degradation rate actually increased when BTEX was present initially in the highest concentration studies. When serving as the sole substrate, the MTBE degradation rate ranged from 48 +/- 1.2 to 200 +/- 7.0 mg(MTBE)/g(dw) h, and the TBA degradation rate from 140 +/- 18 to 530 +/- 70 mg(TBA)/g(dw) h. When present with BTEX, MTBE and TBA rates ranged from 46 +/- 2.2 to 210 +/- 14 and 170 +/- 28 to 780 +/- 43 mg(TBA)/g(dw) h, respectively. In studies where varying concentrations of TBA were present with 5 mg/l MTBE, both compounds were degraded simultaneously with no obvious preference for either substrate. In the highest concentration study of TBA with 5 mg/l MTBE, BTEX was also observed to increase the ultimate rate of TBA degradation. In addition to exploring the affect of BTEX, this study also provides general insight into the metabolism of MTBE and TBA by pure culture UC1.

  8. 3,3′-Di-tert-butyl-1,1′-[1,3-phenylenebis(methylene]diurea

    Directory of Open Access Journals (Sweden)

    Md. Alamgir Hossain

    2010-03-01

    Full Text Available The title compound, C18H30N4O2, contains two tert-butyl urea groups, each connected to a benzene ring though a methylene group. One of the groups occupies a position almost normal to the aromatic plane with a C—N—C—C torsion angle of −94.4 (4°, while the other is considerably twisted from the ring with a C—N—C—C torsion angle of −136.1 (4°. In the crystal, pairs of molecules are connected to each other, forming centrosymmetric dimers in which two NH groups of one molecule act as hydrogen-bond donors to one carbonyl O atom of the other molecule. The dimers are linked into sheets parallel to (100 by N—H...O hydrogen bonds involving the remaining N—H and C=O groups.

  9. (1S,3S,4S-tert-Butyl N-[1-benzyl-3-hydroxy-5-phenyl-4-(picolinamidopentyl]carbamate

    Directory of Open Access Journals (Sweden)

    Jian-Feng Zheng

    2008-07-01

    Full Text Available The title compound, C29H35N3O4, was obtained by the reaction of (2S,4S,5S-tert-butyl N-(4-amino-1-benzyl-3-hydroxy-5-phenylpentylcarbamate and picolinic acid using oxalyl chloride as a chlorinating reagent to activate the carboxyl group. In the crystal structure there are two molecules in the asymmetric unit, which are aligned edge-to-face. In one molecule, the pyridyl ring forms a dihedral angle of 22.0 (1° with the phenyl ring of the terminal benzyl group and 14.3 (1° with the other phenyl ring; in the other molecule, the corresponding angles are 12.1 (1 and 10.6 (1°, respectively. The packing is stabilized by intermolecular hydrogen bonds and C—H...π interactions.

  10. Calculation of carbon-14, chlorine-37, and deuterium kinetic isotope effects in the solvolysis of tert-butyl chloride

    International Nuclear Information System (INIS)

    Burton, G.W.; Sims, L.B.; Wilson, J.C.; Fry, A.

    1977-01-01

    In the solvolysis of tert-butyl chloride, satisfactory α-carbon-14, β-deuterium, and chlorine kinetic isotope effects (KIE) may be calculated for a productlike transition state characterized by bond orders n/sub C Cl/ = 0.2, n/sub C C/ = 1.18, and n/sub C H/ = 0.94, employing a diagonal valence force field, provided that allowance is made for hydrogen-bonded solvation of the developing chloride ion with n/sub Cl H/ approx. 0.05 (approx. 7 kcal/mole hydrogen bonds). The effect of the three solvating molecules appears to be to increase the ''effective'' mass of the incipient chloride ion and to decrease the loss of zero-point energy in going to the transition state. Reaction coordinates more complicated than a simple heterolysis of the carbon-chlorine bond appear to be unnecessary and there is no advantage in employing force fields more complex than a simple valence force field containing only diagonal elements for both the reactant and the transition state model. The structural and bonding features of the proposed transition state are in accord with earlier more qualitative conclusions concerning the polar nature and productlike character of the transition state, and provide a reasonable explanation of the kinetic and equilibrium isotope effects (EIE) for the reaction. An alternative transition state model involving weak solvent nucleophilic assistance provides reasonable calculated values for the KIE, but the EIE strongly suggest the importance of solvation of the leaving group which, together with the hyperconjugation of the β hydrogens, provides a preferred explanation of the tert-butyl solvolysis results

  11. U.S. Geological Survey laboratory method for methyl tert-Butyl ether and other fuel oxygenates

    Science.gov (United States)

    Raese, Jon W.; Rose, Donna L.; Sandstrom, Mark W.

    1995-01-01

    Methyl tert-butyl ether (MTBE) was found in shallow ground-water samples in a study of 8 urban and 20 agricultural areas throughout the United States in 1993 and 1994 (Squillace and others, 1995, p. 1). The compound is added to gasoline either seasonally or year round in many parts of the United States to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL), near Denver, uses state-of-the-art technology to analyze samples for MTBE as part of the USGS water-quality studies. In addition, the NWQL offers custom analyses to determine two other fuel oxygenates--ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME). The NWQL was not able to obtain a reference standard for tert-amyl ethyl ether (TAEE), another possible fuel oxygenate (Shelley and Fouhy, 1994, p. 63). The shallow ground-water samples were collected as part of the USGS National Water-Quality Assessment Program. These samples were collected from 211 urban wells or springs and 562 agricultural wells sampled by the USGS in 1993 and 1994. The wells were keyed to specific land-use areas to assess the effects of different uses on ground-water quality (Squillace and others, 1995, p. 2). Ground-water samples were preserved on site to pH less than or equal to 2 with a solution of 1:1 hydrochloric acid. All samples were analyzed at the NWQL within 2 weeks after collection. The purpose of this fact sheet is to explain briefly the analytical method implemented by the USGS for determining MTBE and other fuel oxygenates. The scope is necessarily limited to an overview of the analytical method (instrumentation, sample preparation, calibration and quantitation, identification, and preservation of samples) and method performance (reagent blanks, accuracy, and precision).

  12. Determination of Methyl tert-Butyl Ether and tert-Butyl Alcohol in Water by Solid-Phase Microextraction/Head Space Analysis in Comparison to EPA Method 5030/8260B

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Keun-Chan; Stringfellow, William T.

    2003-10-02

    Methyl tert-butyl ether (MTBE) is now one of the most common groundwater contaminants in the United States. Groundwater contaminated with MTBE is also likely to be contaminated with tert-butyl alcohol (TBA), because TBA is a component of commercial grade MTBE, TBA can also be used as a fuel oxygenate, and TBA is a biodegradation product of MTBE. In California, MTBE is subject to reporting at concentrations greater than 3 {micro}g/L. TBA is classified as a ''contaminant of current interest'' and has a drinking water action level of 12 {micro}g/L. In this paper, we describe the development and optimization of a simple, automated solid phase microextraction (SPME) method for the analysis of MTBE and TBA in water and demonstrate the applicability of this method for monitoring MTBE and TBA contamination in groundwater, drinking water, and surface water. In this method, the headspace (HS) of a water sample is extracted with a carboxen/polydimethylsiloxane SPME fiber, the MTBE and TBA are desorbed into a gas chromatograph (GC), and detected using mass spectrometry (MS). The method is optimized for the routine analysis of MTBE and TBA with a level of quantitation of 0.3 {micro}g/L and 4 {micro}g/L, respectively, in water. MTBE quantitation was linear for over two orders of concentration (0.3 {micro}g/L -80 {micro}g/L). TBA was found to be linear within the range of 4 {micro}g/L-7,900 {micro}g/L. The lower level of detection for MTBE is 0.03 {micro}g/L using this method. This SPME method using headspace extraction was found to be advantageous over SPME methods requiring immersion of the fiber into the water samples, because it prolonged the life of the fiber by up to 400 sample analyses. This is the first time headspace extraction SPME has been shown to be applicable to the measurement of both MTBE and TBA at concentrations below regulatory action levels. This method was compared with the certified EPA Method 5030/8260B (purge-and-trap/GC/MS) using split

  13. Study of an aquifer contaminated by ethyl tert-butyl ether (ETBE): Site characterization and on-site bioremediation

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, Francoise, E-mail: francoise.fayolle@ifpen.fr [IFP Energies nouvelles, 1 et 4 avenue de Bois-Preau, 92852 Rueil-Malmaison (France); Durand, Jonathan [Institut EGID Bordeaux 3, 1 Allee Daguin 33607 Pessac Cedex (France); SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Cheucle, Mathilde [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Rosell, Monica [Department of Isotope Biogeochemistry, Helmholtz Centre for Environmental Research - UFZ, Permoserstrasse 15, 04318 Leipzig (Germany); Michelland, Rory Julien [Universite de Lyon, F-69622 Lyon (France); Universite Lyon 1, Villeurbanne (France); CNRS, UMR5557, Ecologie Microbienne (France); Tracol, Jean-Philippe [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Le Roux, Francoise [IFP Energies nouvelles, 1 et 4 avenue de Bois-Preau, 92852 Rueil-Malmaison (France); Grundman, Genevieve [Universite de Lyon, F-69622 Lyon (France); Universite Lyon 1, Villeurbanne (France); CNRS, UMR5557, Ecologie Microbienne (France); Atteia, Olivier [Institut EGID Bordeaux 3, 1 Allee Daguin 33607 Pessac Cedex (France); Richnow, Hans H. [Department of Isotope Biogeochemistry, Helmholtz Centre for Environmental Research - UFZ, Permoserstrasse 15, 04318 Leipzig (Germany); Dumestre, Alain [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); and others

    2012-01-30

    Highlights: Black-Right-Pointing-Pointer Ethyl tert-butyl ether (ETBE) (>300 mg L{sup -1}) found in a groundwater (gas-station). Black-Right-Pointing-Pointer No significant carbon or hydrogen isotopic fractionation of ETBE along the plume. Black-Right-Pointing-Pointer MC-IFP culture degraded ETBE (0.91 mg L{sup -1} h{sup -1}) and BTEX (0.64 mg L{sup -1} h{sup -1}). Black-Right-Pointing-Pointer A pilot plant (2 m{sup 3}) inoculated with MC-IFP degraded ETBE in groundwater (15 Degree-Sign C). Black-Right-Pointing-Pointer ethB gene (ETBE biodegradation) amplified during bioaugmentation (5 Multiplication-Sign 10{sup 6}ethB gene copies L{sup -1}). - Abstract: Ethyl tert-butyl ether (ETBE) was detected at high concentration (300 mg L{sup -1}) in the groundwater below a gas-station. No significant carbon neither hydrogen isotopic fractionation of ETBE was detected along the plume. ETBE and BTEX biodegradation capacities of the indigenous microflora Pz1-ETBE and of a culture (MC-IFP) composed of Rhodococcus wratislaviensis IFP 2016, Rhodococcus aetherivorans IFP 2017 and Aquincola tertiaricarbonis IFP 2003 showed that ETBE and BTEX degradation rates were in the same range (ETBE: 0.91 and 0.83 mg L{sup -1} h{sup -1} and BTEX: 0.64 and 0.82 mg L{sup -1} h{sup -1}, respectively) but tert-butanol (TBA) accumulated transiently at a high level using Pz1-ETBE (74 mg L{sup -1}). An on-site pilot plant (2 m{sup 3}) filled with polluted groundwater and inoculated by MC-IFP, successfully degraded four successive additions of ETBE and gasoline. However, an insignificant ETBE isotopic fractionation was also accompanying this decrease which suggested the involvement of low fractionating-strains using EthB enzymes, but required of additional proofs. The ethB gene encoding a cytochrome P450 involved in ETBE biodegradation (present in R. aetherivorans IFP 2017) was monitored by quantitative real-time polymerase chain reaction (q-PCR) on DNA extracted from water sampled in the pilot plant

  14. Study of an aquifer contaminated by ethyl tert-butyl ether (ETBE): Site characterization and on-site bioremediation

    International Nuclear Information System (INIS)

    Fayolle-Guichard, Françoise; Durand, Jonathan; Cheucle, Mathilde; Rosell, Mònica; Michelland, Rory Julien; Tracol, Jean-Philippe; Le Roux, Françoise; Grundman, Geneviève; Atteia, Olivier; Richnow, Hans H.; Dumestre, Alain

    2012-01-01

    Highlights: ► Ethyl tert-butyl ether (ETBE) (>300 mg L −1 ) found in a groundwater (gas-station). ► No significant carbon or hydrogen isotopic fractionation of ETBE along the plume. ► MC-IFP culture degraded ETBE (0.91 mg L −1 h −1 ) and BTEX (0.64 mg L −1 h −1 ). ► A pilot plant (2 m 3 ) inoculated with MC-IFP degraded ETBE in groundwater (15 °C). ► ethB gene (ETBE biodegradation) amplified during bioaugmentation (5 × 10 6 ethB gene copies L −1 ). - Abstract: Ethyl tert-butyl ether (ETBE) was detected at high concentration (300 mg L −1 ) in the groundwater below a gas-station. No significant carbon neither hydrogen isotopic fractionation of ETBE was detected along the plume. ETBE and BTEX biodegradation capacities of the indigenous microflora Pz1-ETBE and of a culture (MC-IFP) composed of Rhodococcus wratislaviensis IFP 2016, Rhodococcus aetherivorans IFP 2017 and Aquincola tertiaricarbonis IFP 2003 showed that ETBE and BTEX degradation rates were in the same range (ETBE: 0.91 and 0.83 mg L −1 h −1 and BTEX: 0.64 and 0.82 mg L −1 h −1 , respectively) but tert-butanol (TBA) accumulated transiently at a high level using Pz1-ETBE (74 mg L −1 ). An on-site pilot plant (2 m 3 ) filled with polluted groundwater and inoculated by MC-IFP, successfully degraded four successive additions of ETBE and gasoline. However, an insignificant ETBE isotopic fractionation was also accompanying this decrease which suggested the involvement of low fractionating-strains using EthB enzymes, but required of additional proofs. The ethB gene encoding a cytochrome P450 involved in ETBE biodegradation (present in R. aetherivorans IFP 2017) was monitored by quantitative real-time polymerase chain reaction (q-PCR) on DNA extracted from water sampled in the pilot plant which yield up to 5 × 10 6 copies of ethB gene per L −1 .

  15. Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Ellermann, T.

    1995-01-01

    UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm, sigma(R) = (2.6 +/- 0.4) X...... and the alkylperoxy radicals with NO and NO2 are (9.1 +/- 1.5) X 10(-13), (4.3 +/- 1.6) X 10(-12) and (1.2 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1), respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule....

  16. Structure of methylene chloride addition product to zirconium tetrachloride complex with 1-tert.-butyl-2,4,4-trimethyl-2-thio-trimethylsilyl-1,3,2,4-diazaphosphasilatedine

    International Nuclear Information System (INIS)

    Brusilovets, A.I.; Rusanov, Eh.B.; Chernega, A.N.

    1995-01-01

    Complex of zirconium tetrachloride with 1-tert.-butyl-2,4,4-trimethyl--2-thio-3-trimethyl-silyl-1,3,2,4-diazaphosphasilatedine interacts with methylene chloride with formation of bis[3-tert.-butyl-2,4,4-trimethyl-1--trimethylsilyl-2-chloremethylthio-1,3,2,4-diazaphosphasilatedinium] decachlorodizirconate. Specific features of crystal and molecular structure of the compound prepared have been studied by X-ray diffraction method. 21 refs.; 2 figs.; 2 tabs

  17. Detection and Quantification of Methyl tert-Butyl Ether-Degrading Strain PM1 by Real-Time TaqMan PCR

    OpenAIRE

    Hristova, Krassimira R.; Lutenegger, Christian M.; Scow, Kate M.

    2001-01-01

    The fuel oxygenate methyl tert-butyl ether (MTBE), a widely distributed groundwater contaminant, shows potential for treatment by in situ bioremediation. The bacterial strain PM1 rapidly mineralizes and grows on MTBE in laboratory cultures and can degrade the contaminant when inoculated into groundwater or soil microcosms. We applied the TaqMan quantitative PCR method to detect and quantify strain PM1 in laboratory and field samples. Specific primers and probes were designed for the 16S ribos...

  18. Substituted 2,2′-bipyridines by nickel-catalysis: 4,4′-di-tert-butyl-2,2′-bipyridine

    OpenAIRE

    Buonomo, Joseph A.; Everson, Daniel A.; Weix, Daniel J.

    2013-01-01

    A simple, ligand-free synthesis of the important bipyridyl ligand 4,4′-di-tert-butyl-2,2′-bipyridine is presented. 5,5′-bis(trifluoromethyl)-2,2′-bipyridine is also synthesized by the same protocol. The syntheses efficiently couple the parent 2-chlorpyridies by a nickel-catalyzed dimerization with manganese powder as the terminal reductant.

  19. Substituted 2,2′-bipyridines by nickel-catalysis: 4,4′-di-tert-butyl-2,2′-bipyridine

    Science.gov (United States)

    Buonomo, Joseph A.; Everson, Daniel A.; Weix, Daniel J.

    2014-01-01

    A simple, ligand-free synthesis of the important bipyridyl ligand 4,4′-di-tert-butyl-2,2′-bipyridine is presented. 5,5′-bis(trifluoromethyl)-2,2′-bipyridine is also synthesized by the same protocol. The syntheses efficiently couple the parent 2-chlorpyridies by a nickel-catalyzed dimerization with manganese powder as the terminal reductant. PMID:25221358

  20. Gene mdpC plays a regulatory role in the methyl-tert-butyl ether degradation pathway of Methylibium petroleiphilum strain PM1.

    Science.gov (United States)

    Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

    2015-04-01

    Among the few bacteria known to utilize methyl tert-butyl ether (MTBE) as a sole carbon source, Methylibium petroleiphilum PM1 is a well-characterized organism with a sequenced genome; however, knowledge of the genetic regulation of its MTBE degradation pathway is limited. We investigated the role of a putative transcriptional activator gene, mdpC, in the induction of MTBE-degradation genes mdpA (encoding MTBE monooxygenase) and mdpJ (encoding tert-butyl alcohol hydroxylase) of strain PM1 in a gene-knockout mutant mdpC(-). We also utilized quantitative reverse transcriptase PCR assays targeting genes mdpA, mdpJ and mdpC to determine the effects of the mutation on transcription of these genes. Our results indicate that gene mdpC is involved in the induction of both mdpA and mdpJ in response to MTBE and tert-butyl alcohol (TBA) exposure in PM1. An additional independent mechanism may be involved in the induction of mdpJ in the presence of TBA. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  1. Thermochemical studies on two alkyl-bulky substituted xanthene derivatives: 9,9-dimethylxanthene and 2,7-di-tert-butyl-9,9-dimethylxanthene

    International Nuclear Information System (INIS)

    Freitas, Vera L.S.; Gomes, José R.B.; Ribeiro da Silva, Maria D.M.C.

    2017-01-01

    Highlights: • Energetic characterization of two alkyl-bulky substituted xanthene derivatives. • Massic energies of combustion of xanthene derivatives. • Enthalpies of sublimation determined by vacuum drop microcalorimetry technique. • Temperature-vapour pressure dependence by mass-loss Knudsen effusion method. • Gas-phase enthalpies of formation of alkyl xanthene derivatives. - Abstract: Thermodynamic properties of 9,9-dimethylxanthene and 2,7-di-tert-butyl-9,9-dimethylxanthene for the condensed and gas states were derived from experimental and computational studies. Static-bomb combustion calorimetry, vacuum drop microcalorimetry and the Knudsen effusion techniques were used. Computational calculations of the enthalpies of hypothetical reactions in the gaseous phase, using the G3(MP2)//B3LYP composite method, were performed for the two xanthene derivatives. Natural bond orbital (NBO) calculations were also performed to ascertain the structure and reactivity of these compounds. The energetic effects caused by replacing hydrogen atoms in the xanthene moiety by methyl and tert-butyl groups yielding 9,9-dimethylxanthene and 2,7-di-tert-butyl-9,9-dimethylxanthene species were determined from direct comparison of their standard (p o = 0.1 MPa) molar enthalpies of formation in the gaseous phase, at T = 298.15 K.

  2. [Biodegradation of methyl tert-butyl ether by stabilized immobilized Methylibium petroleiphilum PM1 cells and its biodegradation kinetics analysis].

    Science.gov (United States)

    Cheng, Zhuo-wei; Fu, Ling-xiao; Jiang, Yi-feng; Chen, Jian-meng; Zhang, Rong

    2011-05-01

    Methylibium petroleiphilum PM1, which is capable of degrading methyl tert-butyl ether (MTBE) , was immobilized in calcium alginate gel beads. Several methods were explored to increase the strength of these gel beads. The central composite design analysis indicated that the introduction of 0.2 mol x L(-1) Ca2+ into the crosslinking solution, 1.38 mmol x L(-1) Ca2+ into the growth medium and 0.1% polyethyleneimine (PEI) as the chemical crosslinking agent could increase the stability of the Ca-alginate gel beads with no loss of biodegradation activity. The stabilized immobilized cells could be used 400 h continuously with no breakage and no bioactivity loss. Examination of scanning electron microscope demonstrated that a membrane surrounding the gel beads was formed and the cells could grow and breed well in the stabilized calcium alginate gel beads. Kinetic analysis of the gel bead-degradation indicated that the rate-limiting step was biochemical process instead of intraparticle diffusion process. The diameter of 3 mm affected the biodegradability less while high concentration of PEI induced much more serious mass transfer restraint.

  3. Interactions of poly(tert-butyl acrylate)-poly(styrene) diblock copolymers with lipids at the air-water interface.

    Science.gov (United States)

    Mudgil, Poonam; Dennis, Gary R; Millar, Thomas J

    2006-08-29

    Diblock copolymers with hydrophilic poly(tert-butyl acrylate) (PtBA) and hydrophobic poly(styrene) (PS) blocks were synthesized with a view to use them as a surfactant in tear film for increasing the ocular comfort in dry eye syndrome. Interactions of six PtBA-PS copolymers with four important lipids found in the tear film, namely cholesterol, cholesteryl palmitate, dipalmitoyl phosphatidylcholine, and phosphatidylinositol, were studied at the air-water interface using a Langmuir trough. Thermodynamics of mixing of the copolymers and the lipids in the mixed monolayers was determined by calculating excess free energy of mixing. The diblock copolymers showed repulsive interactions with cholesteol and cholesteryl palmitate, near neutral interactions with dipalmitoyl phosphatidylcholine, and attractive interactions with phosphatidylinositol. The lipids interacted with the PS component of the copolymer. The results indicate that a copolymer with a small hydrophilic group and a big hydrophobic group can be a likely candidate for forming stable interactions with the lipids present in the tear film and hence increase the ocular comfort.

  4. Characterization and photoconductivity study of well-defined C60 terminated poly(tert-butyl acrylate-b-styrene)

    International Nuclear Information System (INIS)

    Yang Dong; Li Lang; Wang Changchun

    2004-01-01

    Atom transfer radical polymerization (ATRP) catalyzed by N,N',N',N'',N''-pentamethyldiethylenetriamine (PMDETA)/CuBr was performed to synthesize poly (tert-butyl acrylate) (PtBA-Br) with predesigned molecular weight and narrow polydispersity. Using the PtBA-Br as macroinitiator, the PtBA-block-PS copolymer was prepared through ATRP. After terminated bromine atom was converted to end-functional azide group (P(tBA-b-St)-N 3 ), C 60 end-capped PtBA-PS block copolymers (P(tBA-b-St)-C 60 ) were synthesized by reacting C 60 with P(tBA-b-St)-N 3 . GPC characterizations showed that C 60 was chemically bonded to the end of P(tBA-b-St) chain and the products were mono-substituted. FT-IR, UV-Vis measurements confirmed that hydrolysis of P(tBA-b-St)-C 60 resulted in amphiphilic C 60 end-capped PAA-PS block copolymers. In additional, the photoconductivity of P(tBA-b-St)-C 60 was measured

  5. Synthesis, Crystal Growth, Spectroscopic and Electrical Properties of 5-tert-Butyl-1,2,3-trinitrobenzene

    Directory of Open Access Journals (Sweden)

    S. Sahaya Jude Dhas

    2013-01-01

    Full Text Available 5-tert-Butyl-1,2,3-trinitrobenzene (TBTB was synthesized and characterized by NMR so as to confirm the structure. Single crystals were obtained from methanol by solvent evaporation technique at room temperature. Optically transparent single crystals with dimension up to 17×4×3 mm3 have been grown by submerged seed solution method within a period of 30 days. The modes of vibration of different molecular groups present in the title compound were identified by FTIR and FT-Raman spectral analyses, and it was found with the tabulation that both of the spectral vibrations are very close to each other confirming the existence of specific functional groups in the crystal. Optical behaviour of the crystal was analyzed by UV-Vis absorption studies, and the value of the optical band gap energy (Eg of the crystal has been determined using the optical absorption spectrum. The dielectric behaviour and AC conductivity of the grown crystals were also analyzed, and it is shown that both properties vary with respect to frequency and do not vary in accordance with temperature.

  6. Method detection limit determination and application of a convenient headspace analysis method for methyl tert-butyl ether in water.

    Science.gov (United States)

    O'Neill, Dennis T; Rochette, Elizabeth A; Ramsey, Philip J

    2002-11-15

    Methyl tert-butyl ether (MTBE) is a common groundwater contaminant, introduced to the environment by leaking petroleum storage tanks, urban runoff, and motorized watercraft. In this study. a simplified (static) headspace analysis method was adapted for determination of MTBE in water samples and soil water extracts. The MDL of the headspace method was calculated to be 2.0 microg L(-1) by the EPA single-concentration design method(1) and 1.2 microg L(-1) by a calibration method developed by Hubaux and Vos (Hubaux, A.; Vos, G. Anal. Chem. 1970,42, 849-855). The MDL calculated with the Hubaux and Vos method was favored because it considers both a true positive and a false positive. The static headspace method was applied to analysis of a tap water sample and a monitoring well sample from a gasoline service station, a river sample, and aqueous extracts from soil excavated during removal of a leaking underground storage tank (LUST). The water samples examined in this study had MTTBE concentrations ranging from 6 to 19 microg L(-1). Aqueous extracts of a soil sample taken from the LUST site had 8 microg L(-1) MTBE.

  7. Bis(formylphenolatocobalt(II-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate

    Directory of Open Access Journals (Sweden)

    Sanjib Banerjee

    2017-12-01

    Full Text Available The organometallic-mediated radical polymerization (OMRP of vinyl acetate (VAc and its OMR copolymerization (OMRcoP with tert-butyl 2-trifluoromethylacrylate (MAF-TBE mediated by Co(SAL2 (SAL = 2-formylphenolato or deprotonated salicylaldehyde produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE copolymers at moderate temperature (<40 °C in bulk. The resulting alternating copolymer was characterized by 1H-, 13C- and 19F-nuclear magnetic resonance (NMR spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (Đ~1.55 of the resulting copolymers suggest that this cobalt complex provides some degree of control over the copolymerization of VAc and MAF-TBE. Compared to the previously investigated cobalt complex OMRP mediators having a fully oxygen-based first coordination sphere, this study emphasizes a few peculiarities of Co(SAL2: a lower ability to trap radical chains as compared to Co(acac2 and the absence of catalytic chain transfer reactions, which dominates polymerizations carried in the presence of 9-oxyphenalenone cobalt derivative.

  8. Assessing soil ecotoxicity of methyl tert-butyl ether using earthworm bioassay; closed soil microcosm test for volatile organic compounds

    International Nuclear Information System (INIS)

    An, Youn-Joo

    2005-01-01

    An earthworm bioassay was conducted to assess ecotoxicity in methyl tert-butyl ether (MTBE)-amended soils. Ecotoxicity of MTBE to earthworms was evaluated by a paper contact method, natural field soil test, and an OECD artificial soil test. All tests were conducted in closed systems to prevent volatilization of MTBE out of test units. Test earthworm species were Perionyx excavatus and Eisenia andrei. Mortality and abnormal morphology of earthworms exposed to different concentrations of MTBE were examined. MTBE was toxic to both earthworm species and the severity of response increased with increasing MTBE concentrations. Perionyx excavatus was more sensitive to MTBE than Eisenia andrei in filter papers and two different types of soils. MTBE toxicity was more severe in OECD artificial soils than in field soils, possibly due to the burrowing behavior of earthworms into artificial soils. The present study demonstrated that ecotoxicity of volatile organic compounds such as MTBE can be assessed using an earthworm bioassay in closed soil microcosm with short-term exposure duration. - Earthworm bioassay can be a good protocol to assess soil ecotoxicity of volatile organic compounds such as MTBE

  9. Protective Effects of Alkaloid Compounds from Nelumbinis Plumula on tert-Butyl Hydroperoxide-Induced Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Ze-Bin Guo

    2013-08-01

    Full Text Available This study was conducted to investigate the effect of Nelumbinis Plumula total alkaloid (NPA and its main alkaloid components on oxidative stress induced by tert-butyl hydroperoxide (t-BHP in the human hepatocellular HepG2 cell line. According to HPLC analysis, several major alkaloid compounds such as liensinine, isoliensinine and neferine were present in NPA. The cytotoxic effects in 0.55 mM t-BHP-induced HepG2 cells were significantly inhibited by NPA and the major compound in NPA, neferine, showed the strongest activities. The protective effect of neferine against oxidative stress induced by t-BHP may be associated with decreased ROS formation, TBARS generation, LDH release and increased GSH levels, suggesting their involvement of the cytoprotective on oxidative stress. The effects were comparable with quercetin, which was used as positive control. Overall, total alkaloid and alkaloid compounds from Nelumbinis Plumula displayed a significant cytoprotective effect against oxidative stress. Further study is needed to elucidate the relationship between the chemical structures of the components in NPA and their protective effect on oxidative stress.

  10. Crystal structure of trans-N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyloxamide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Miguel-Ángel Velázquez-Carmona

    2016-07-01

    Full Text Available The here crystallized oxamide was previously characterized as an unsolvated species [Jímenez-Pérez et al. (2000. J. Organomet. Chem. 614–615, 283–293], and is now reported with methanol as a solvent of crystallization, C30H44N2O4·CH3OH, in a different space group. The introduction of the solvent influences neither the molecular symmetry of the oxamide, which remains centrosymmetric, nor the molecular conformation. However, the unsolvated molecule crystallized as an ordered system, while many parts of the solvated crystal are disordered. The hydroxy group in the oxamide is disordered over two chemically equivalent positions, with occupancies 0.696 (4:0.304 (4; one tert-butyl group is disordered by rotation about the C—C bond, and was modelled with three sites for each methyl group, each one with occupancy 1/3. Finally, the methanol solvent, which lies on a twofold axis, is disordered by symmetry. The disorder affecting hydroxy groups and the solvent of crystallization allows the formation of numerous supramolecular motifs using four hydrogen bonds, with N—H and O—H groups as donors and the oxamide and methanol molecule as acceptors.

  11. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Tingshun, E-mail: tshjiang@mail.ujs.edu.cn; Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-10-15

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.

  12. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    International Nuclear Information System (INIS)

    Jiang, Tingshun; Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-01-01

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO 4 2− /Zr-MCM-48 and SO 4 2− /Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH 3 -TPD and N 2 physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO 4 2− /Zr-MCM-48 and SO 4 2− /Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO 4 2− /Zr-MCM-48 and SO 4 2− /Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO 4 2− /Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h −1 and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO 4 2− /Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO 4 2− /Zr-MCM-48-25

  13. Whole-genome analysis of the methyl tert-butyl ether-degrading beta-proteobacterium Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Kane, Staci R; Chakicherla, Anu Y; Chain, Patrick S G; Schmidt, Radomir; Shin, Maria W; Legler, Tina C; Scow, Kate M; Larimer, Frank W; Lucas, Susan M; Richardson, Paul M; Hristova, Krassimira R

    2007-03-01

    Methylibium petroleiphilum PM1 is a methylotroph distinguished by its ability to completely metabolize the fuel oxygenate methyl tert-butyl ether (MTBE). Strain PM1 also degrades aromatic (benzene, toluene, and xylene) and straight-chain (C(5) to C(12)) hydrocarbons present in petroleum products. Whole-genome analysis of PM1 revealed an approximately 4-Mb circular chromosome and an approximately 600-kb megaplasmid, containing 3,831 and 646 genes, respectively. Aromatic hydrocarbon and alkane degradation, metal resistance, and methylotrophy are encoded on the chromosome. The megaplasmid contains an unusual t-RNA island, numerous insertion sequences, and large repeated elements, including a 40-kb region also present on the chromosome and a 29-kb tandem repeat encoding phosphonate transport and cobalamin biosynthesis. The megaplasmid also codes for alkane degradation and was shown to play an essential role in MTBE degradation through plasmid-curing experiments. Discrepancies between the insertion sequence element distribution patterns, the distributions of best BLASTP hits among major phylogenetic groups, and the G+C contents of the chromosome (69.2%) and plasmid (66%), together with comparative genome hybridization experiments, suggest that the plasmid was recently acquired and apparently carries the genetic information responsible for PM1's ability to degrade MTBE. Comparative genomic hybridization analysis with two PM1-like MTBE-degrading environmental isolates (approximately 99% identical 16S rRNA gene sequences) showed that the plasmid was highly conserved (ca. 99% identical), whereas the chromosomes were too diverse to conduct resequencing analysis. PM1's genome sequence provides a foundation for investigating MTBE biodegradation and exploring the genetic regulation of multiple biodegradation pathways in M. petroleiphilum and other MTBE-degrading beta-proteobacteria.

  14. Fatty acid methyl esters synthesis from non-edible vegetable oils using supercritical methanol and methyl tert-butyl ether

    International Nuclear Information System (INIS)

    Lamba, Neha; Modak, Jayant M.; Madras, Giridhar

    2017-01-01

    Highlights: • FAMEs were synthesized from non-edible oils using supercritical MeOH and MTBE. • Effect of time, temperature, pressure and molar ratio on conversions was studied. • Rate constants of reaction with methanol and MTBE differ by an order of magnitude. • Non-catalytic supercritical reactions are one order faster than acid catalyzed synthesis. - Abstract: Fatty acid methyl esters (FAMEs) are useful as biodiesel and have environmental benefits compared to conventional diesel. In this study, these esters were synthesized non-catalytically from non-edible vegetable oils: neem oil and mahua oil with two different methylating agents: methanol and methyl tert-butyl ether (MTBE). The effects of temperature, pressure, time and molar ratio on the conversion of triglycerides were studied. The temperature was varied in the range of 523–723 K with molar ratios upto 50:1 and a reaction time of upto 150 min. Conversion of neem and mahua oil to FAMEs with supercritical methanol was found to be 83% in 15 min and 99% in 10 min, respectively at 698 K. Further, a conversion of 46% of mahua oil and 59% of neem oil was obtained in 15 min at 723 K using supercritical MTBE. The rate constants evaluated using pseudo first order reaction kinetics were in the range of 4.7 × 10"−"6 to 1.0 × 10"−"3 s"−"1 for the investigated range of temperatures. The activation energies obtained were in the range of 62–113 kJ/mol for the reaction systems investigated. The supercritical synthesis was found to be superior to the catalytic synthesis of the corresponding FAMEs.

  15. Salvianic acid A sodium protects HUVEC cells against tert-butyl hydroperoxide induced oxidative injury via mitochondria-dependent pathway.

    Science.gov (United States)

    Jia, Dan; Li, Tian; Chen, Xiaofei; Ding, Xuan; Chai, Yifeng; Chen, Alex F; Zhu, Zhenyu; Zhang, Chuan

    2018-01-05

    Salvianic acid A (Danshensu) is a major water-soluble component extracted from Salvia miltiorrhiza (Danshen), which has been widely used in clinic in China for treatment of cardiovascular diseases (CVDs). This study aimed to investigate the protective effects of salvianic acid A sodium (SAAS) against tert-butyl hydroperoxide (t-BHP) induced human umbilical vein endothelial cell (HUVEC) oxidative injury and the underlying molecular mechanisms. In the antioxidant activity-assessing model, SAAS pretreatment significantly ameliorated the cell growth inhibition and apoptosis induced by t-BHP. An ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) based-metabolic profiling was developed to investigate the metabolic changes of HUVEC cells in response to t-BHP and SAAS. The results revealed that t-BHP injury upregulated 13 metabolites mainly involved in tryptophan metabolism and phenylalanine metabolism which were highly correlated with mitochondrial function and oxidative stress, and 50 μM SAAS pretreatment effectively reversed these metabolic changes. Further biomedical research indicated that SAAS pretreatment reduced the t-BHP induced increase of lactate dehydrogenase (LDH), intracellular reactive oxygen species (ROS), malondialdehyde (MDA) and mitochondrial membrane potential (MMP), and the decrease of key antioxidant enzymes through mitochondria antioxidative pathways via JAK2/STAT3 and PI3K/Akt/GSK-3β signalings. Taken together, our results suggested that SAAS may protect HUVEC cells against t-BHP induced oxidative injury via mitochondrial antioxidative defense system. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Exposure to methyl tert-butyl ether, benzene, and total hydrocarbons at the Singapore-Malaysia causeway immigration checkpoint

    Energy Technology Data Exchange (ETDEWEB)

    Tan, C.; Ong, H.Y.; Kok, P.W. [and others

    1996-12-31

    The primary aim of this study was to determine the extent and levels of exposure to volatile organic compounds (VOCs) from automobile emissions in a group of immigration officers at a busy cross-border checkpoint. A majority (80%) of the workers monitored were exposed to benzene at levels between 0.01 and 0.5 ppm, with only 1.2% exceeding the current Occupational Safety and Health Administration occupational exposure limit of 1 ppm. The geometric mean (GM) concentrations of 8-hr time-weighted average exposure were 0.03 ppm, 0.9 ppm, and 2.46 ppm for methyl-tert-butyl ether (MTBE), benzene, and total hydrocarbons (THC), respectively. The highest time-weighted average concentrations measured were 1.05 ppm for MTBE, 2.01 ppm for benzene, and 34 ppm for THC. It was found that motorbikes emitted a more significant amount of pollutants compared with motor cars. On average, officers at the motorcycle booths were exposed to four to five times higher levels of VOCs (GMs of 0.07 ppm, 0.23 ppm, and 4.7 ppm for MTBE, benzene, and THC) than their counterparts at the motor car booths (GMs of 0.01 ppm, 0.05 ppm, and 1.5 ppm). The airborne concentrations of all three pollutants correlated with the flow of vehicle traffic. Close correlations were also noted for the concentrations in ambient air for the three pollutants measured. Benzene and MTBE had a correlation coefficient of 0.97. The overall findings showed that the concentrations of various VOCs were closely related to the traffic density, suggesting that they were from a common source, such as exhaust emissions from the vehicles. The results also indicated that although benzene, MTBE, and THC are known to be volatile, a significant amount could still be detected in the ambient environment, thus contributing to our exposure to these compounds. 4 refs., 6 figs.

  17. Volumetric Behaviour of the Ternary System (Methyl Tert-butyl ether + Methylbenzene + Butan-1-ol) and Its Binary sub-System (Methyl Tert-Butyl Ether + Butan-1-ol) within the Temperature Range (298.15–328.15) K

    Czech Academy of Sciences Publication Activity Database

    Morávková, Lenka; Troncoso, J.; Škvorová, M.; Havlica, Jaromír; Petrus, P.; Sedláková, Zuzana

    2015-01-01

    Roč. 90, NOV 2015 (2015), s. 59-70 ISSN 0021-9614 R&D Projects: GA ČR(CZ) GAP105/12/0664; GA MŠk(CZ) LD14094 Grant - others:GNIL(IT) 408 REGALIs (CN2012/120) Institutional support: RVO:67985858 Keywords : methylbenzene * density * methyl-tert-butyl ether Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.196, year: 2015

  18. Complexation study of a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand with uranium(VI) in non-aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Anne; Schmeide, Katja [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The actinide uranium, well known from nuclear power cycle, plays also a role in rare earth production as it is an undesired constituent of the respective ores. To facilitate the production of rare earth elements, uranium has to be removed. Due to their modifiable selectivity and solubility calix[n]arenes are interesting compounds for the extraction of actinides and lanthanides. The mechanism of uranium(VI) interaction with a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand (L1) was studied by TRLFS, UV-vis spectroscopy and isothermal calorimetry.

  19. Isolate PM1 populations are dominant and novel methyl tert-butyl ether-degrading bacterial in compost biofilter enrichments.

    Science.gov (United States)

    Bruns, M A; Hanson, J R; Mefford, J; Scow, K M

    2001-03-01

    The gasoline additive MTBE, methyl tert-butyl ether, is a widespread and persistent groundwater contaminant. MTBE undergoes rapid mineralization as the sole carbon and energy source of bacterial strain PM1, isolated from an enrichment culture of compost biofilter material. In this report, we describe the results of microbial community DNA profiling to assess the relative dominance of isolate PM1 and other bacterial strains cultured from the compost enrichment. Three polymerase chain reaction (PCR)-based profiling approaches were evaluated: denaturing gradient gel electrophoresis (DGGE) analysis of 230 bp 16S rDNA fragments; thermal gradient gel electrophoresis (TGGE) analysis of 575 bp 16S rDNA fragments; and non-denaturing polyacrylamide gel electrophoresis of 300-1,500 bp fragments containing 16S/23S ribosomal intergenic transcribed spacer (ITS) regions. Whereas all three DNA profiling approaches indicated that PM1-like bands predominated in mixtures from MTBE-grown enrichments, ITS profiling provided the most abundant and specific sequence data to confirm strain PM1's presence in the enrichment. Moreover, ITS profiling did not produce non-specific PCR products that were observed with T/DGGE. A further advantage of ITS community profiling over other methods requiring restriction digestion (e.g. terminal restriction fragment length polymorphisms) was that it did not require an additional digestion step or the use of automated sequencing equipment. ITS bands, excised from similar locations in profiles of the enrichment and PM1 pure culture, were 99.9% identical across 750 16S rDNA positions and 100% identical across 691 spacer positions. BLAST comparisons of nearly full-length 16S rDNA sequences showed 96% similarity between isolate PM1 and representatives of at least four different genera in the Leptothrix subgroup of the beta-Proteobacteria (Aquabacterium, Leptothrix, Rubrivivax and Ideonella). Maximum likelihood and parsimony analyses of 1,249 nucleotide

  20. Heterogeneous catalytic epoxidation of C/sub 8/-C/sub 1/4 olefins by tert. -butyl hydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Dahlmann, J; Hoeft, E; Boeden, H F; Dilcher, H

    1979-09-01

    Heterogeneous catalytic epoxidation of C/sub 8/-C/sub 14/ olefins by tert.-butyl hydroperoxide (TBHP) avoids large product losses to side reactions, associated with the use of homogeneous catalysts, such as Mo(CO)/sub 6/. With an unsupported MoO/sub 3/ catalyst, 48% TBHP conversion was achieved after one hour (vs. 24% after two hours for Mo(CO)/sub 6/) in 1-octene epoxidation at 90/sup 0/C and 2:1:3 octene/TBHP/toluene (solvent) molar ratio. The use of silica-supported catalysts, such as Bi/sub 9/PMo/sub 12/O/sub 52//30% SiO/sub 2/ (ACN, an industrial catalyst for acrylonitrile), MoO/sub 3//30% SiO/sub 2/ (D-1), 3MoO/sub 3/-Sb/sub 2/O/sub 5//50% SiO/sub 2/ (D-2), or 2MoO/sub 3/-As/sub 2/O/sub 3//50% SiO/sub 2/ (D-3) increased the conversion to 68, 67, 70, and 73%, respectively, with up to 95-99% selectivities for the epoxide. Under optimum conditions of 3:1 olefin/TBHP, 110/sup 0/C, and 2-4 g/l. catalyst, TBHP conversions in epoxidation of 1-tetradecene in a batch reactor over ACN, D-2, and D-3 after two hours were 94, 88, and 91%, respectively, but they decreased to 52, 78, and 79%, respectively, after five two-hour operating cycles. In epoxidation of 1-decene or a mixture of decene isomers (a model for the industrial olefin mixtures obtained by paraffin dehydrogenation via the Parex process) carried out in a continuous flow reactor over the D-3 catalyst at 90/sup 0/-110/sup 0/C, stable catalytic activities with TBHP conversions of approx. 90% and 90-96% selectivities for epoxides were observed for about 900 hr.

  1. Formation of zinc-peptide spherical microparticles during lyophilization from tert-butyl alcohol/water co-solvent system.

    Science.gov (United States)

    Qian, Feng; Ni, Nina; Chen, Jia-Wen; Desikan, Sridhar; Naringrekar, Vijay; Hussain, Munir A; Barbour, Nancy P; Smith, Ronald L

    2008-12-01

    To understand the mechanism of spherical microparticle formation during lyophilizing a tert-Butyl alcohol (TBA)/water solution of a zinc peptide adduct. A small peptide, PC-1, as well as zinc PC-1 at (3:2) and (3:1) ratios, were dissolved in 44% (wt.%) of TBA/water, gradually frozen to -50 degrees C over 2 h ("typical freezing step"), annealed at -20 degrees C for 6 h ("annealing step"), and subsequently lyophilized with primary and secondary drying. Zinc peptide (3:1) lyophile was also prepared with quench cooling instead of the typical freezing step, or without the annealing step. Other TBA concentrations, i.e., 25%, 35%, 54% and 65%, were used to make the zinc peptide (3:1) adduct lyophile with the typical freezing and annealing steps. The obtained lyophile was analyzed by Scanning Electron Microscopy (SEM). The zinc peptide solutions in TBA/water were analyzed by Differential Scanning Calorimeter (DSC). The surface tension of the TBA/water co-solvent system was measured by a pendant drop shape method. With typical freezing and annealing steps, the free peptide lyophile showed porous network-like structure that is commonly seen in lyophilized products. However, with increasing the zinc to peptide ratio, uniform particles were gradually evolved. Zinc peptide (3:1) adduct lyophiles obtained from 25%, 35% and 44% TBA exhibit a distinctive morphology of uniform and spherical microparticles with diameters of approximately 3-4 microm, and the spherical zinc peptide particles are more predominant when the TBA level approaches 20%. Adopting quench cooling in the lyophilization cycle leads to irregular shape fine powders, and eliminating the annealing step causes rough particles surface. When TBA concentration increases above 54%, the lyophiles demonstrate primarily irregular shape particles. A proposed mechanism of spherical particle formation of the 3:1 zinc peptide encompasses the freezing of a TBA/water solution (20-70% TBA) causing the formation of a TBA hydrate

  2. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene

    International Nuclear Information System (INIS)

    Souane, R.

    2005-03-01

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO 2 2+ form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO 2 ) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO 2 L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid (ΔlogΒ110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO 2 2+ . This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23. (author)

  3. Involvement of a Novel Enzyme, MdpA, in Methyl tert-Butyl Ether Degradation in Methylibium petroleiphilum PM1 ▿

    Science.gov (United States)

    Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R.

    2008-01-01

    Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr59 distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum. PMID:18791002

  4. Effect of benzene and ethylbenzene on the transcription of methyl-tert-butyl ether degradation genes of Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

    2016-09-01

    Methyl-tert-butyl ether (MTBE) and its degradation by-product, tert-butyl alcohol (TBA), are widespread contaminants detected frequently in groundwater in California. Since MTBE was used as a fuel oxygenate for almost two decades, leaking underground fuel storage tanks are an important source of contamination. Gasoline components such as BTEX (benzene, toluene, ethylbenzene and xylenes) are often present in mixtures with MTBE and TBA. Investigations of interactions between BTEX and MTBE degradation have not yielded consistent trends, and the molecular mechanisms of BTEX compounds' impact on MTBE degradation are not well understood. We investigated trends in transcription of biodegradation genes in the MTBE-degrading bacterium, Methylibium petroleiphilum PM1 upon exposure to MTBE, TBA, ethylbenzene and benzene as individual compounds or in mixtures. We designed real-time quantitative PCR assays to target functional genes of strain PM1 and provide evidence for induction of genes mdpA (MTBE monooxygenase), mdpJ (TBA hydroxylase) and bmoA (benzene monooxygenase) in response to MTBE, TBA and benzene, respectively. Delayed induction of mdpA and mdpJ transcription occurred with mixtures of benzene and MTBE or TBA, respectively. bmoA transcription was similar in the presence of MTBE or TBA with benzene as in their absence. Our results also indicate that ethylbenzene, previously proposed as an inhibitor of MTBE degradation in some bacteria, inhibits transcription of mdpA, mdpJ and bmoAgenes in strain PM1.

  5. Aerobic biodegradation of tert-butyl alcohol (TBA) by psychro- and thermo-tolerant cultures derived from granular activated carbon (GAC).

    Science.gov (United States)

    Reinauer, Kimberly M; Zhang, Yang; Yang, Xiaomin; Finneran, Kevin T

    2008-04-01

    Tert-butyl alcohol (TBA) is a metabolite of methyl tert-butyl ether and is itself possibly a fuel oxygenate. The goals of this study were to enrich and characterize TBA-degrading micro-organism(s) from a granular activated carbon (GAC) unit currently treating TBA. The results reported herein describe the first aerobic, TBA-degrading cultures derived from GAC. Strains KR1 and YZ1 were enriched from a GAC sample in a bicarbonate-buffered freshwater medium. TBA was degraded to 10% of the initial concentration (2-5 mM) within 5 days after initial inoculation and was continuously degraded within 1 day of each re-amendment. Resting cell suspensions mineralized 70 and 60% of the TBA within 24 h for KR1 and YZ1, respectively. Performance optimization with resting cells was conducted to investigate kinetics and the extent of TBA degradation as influenced by oxygen, pH and temperature. The most favorable temperature was 37 degrees C; however, TBA was degraded from 4 to 60 degrees C, indicating that the culture will sufficiently treat groundwater without heating. This is also the first report of psychrotolerant or thermotolerant TBA biodegradation. The pH range for TBA degradation ran from 5.0 to 9.0. Phylogenetic data using a partial 16S rRNA gene sequence (570 bases) suggest that the primary members of KR1 and YZ1 include uncharacterized organisms within the genera Hydrogenophaga, Caulobacter, and Pannonibacter.

  6. Azobenzene versus 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) at Au(111): characterizing the role of spacer groups.

    Science.gov (United States)

    McNellis, Erik R; Bronner, Christopher; Meyer, Jörg; Weinelt, Martin; Tegeder, Petra; Reuter, Karsten

    2010-06-28

    We present large-scale density-functional theory (DFT) calculations and temperature programmed desorption measurements to characterize the structural, energetic and vibrational properties of the functionalized molecular switch 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) adsorbed at Au(111). Particular emphasis is placed on exploring the accuracy of the semi-empirical dispersion correction approach to semi-local DFT (DFT-D) in accounting for the substantial van der Waals component in the surface bonding. In line with previous findings for benzene and pure azobenzene at coinage metal surfaces, DFT-D significantly overbinds the molecule, but seems to yield an accurate adsorption geometry as far as can be judged from the experimental data. Comparing the trans adsorption geometry of TBA and azobenzene at Au(111) reveals a remarkable insensitivity of the structural and vibrational properties of the -N[double bond, length as m-dash]N- moiety. This questions the established view of the role of the bulky tert-butyl-spacer groups for the switching of TBA in terms of a mere geometric decoupling of the photochemically active diazo-bridge from the gold substrate.

  7. Directed Evolution of Carbonyl Reductase from Rhodosporidium toruloides and Its Application in Stereoselective Synthesis of tert-Butyl (3R,5S)-6-Chloro-3,5-dihydroxyhexanoate.

    Science.gov (United States)

    Liu, Zhi-Qiang; Wu, Lin; Zhang, Xiao-Jian; Xue, Ya-Ping; Zheng, Yu-Guo

    2017-05-10

    tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is a key intermediate of atorvastatin and rosuvastatin synthesis. Carbonyl reductase RtSCR9 from Rhodosporidium toruloides exhibited excellent activity toward tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH). For the activity of RtSCR9 to be improved, random mutagenesis and site-saturation mutagenesis were performed. Three positive mutants were obtained (mut-Gln95Asp, mut-Ile144Lys, and mut-Phe156Gln). These mutants exhibited 1.94-, 3.03-, and 1.61-fold and 1.93-, 3.15-, and 1.97-fold improvement in the specific activity and k cat /K m , respectively. Asymmetric reduction of (S)-CHOH by mut-Ile144Lys coupled with glucose dehydrogenase was conducted. The yield and enantiomeric excess of (3R,5S)-CDHH reached 98 and 99%, respectively, after 8 h bioconversion in a single batch reaction with 1 M (S)-CHOH, and the space-time yield reached 542.83 mmol L -1 h -1 g -1 wet cell weight. This study presents a new carbonyl reductase for efficient synthesis of (3R,5S)-CDHH.

  8. Biosynthesis of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate by carbonyl reductase from Rhodosporidium toruloides in mono and biphasic media.

    Science.gov (United States)

    Liu, Zhi-Qiang; Wu, Lin; Zheng, Ling; Wang, Wen-Zhong; Zhang, Xiao-Jian; Jin, Li-Qun; Zheng, Yu-Guo

    2018-02-01

    tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is the key intermediate for synthesis of atorvastatin and rosuvastatin. Carbonyl reductase exhibits excellent activity toward tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH) to synthesize (3R,5S)-CDHH. In this study, a whole cell biosynthesis reaction system to produce (3R,5S)-CDHH was constructed in organic solvents. A solution of 10% (v/v) Tween-80 was introduced to the reaction system as a co-solvent, which greatly enhanced biotransformation process, giving 98.9% yield, >99% ee and 1.8-fold higher space time yield in 5 h bioconversion of 1 M (S)-CHOH, compared with 98.7% yield and >99% ee in 9 h bioconversion of a purely aqueous reaction system. Moreover, a water-octanol biphasic reaction system was built and 20% of octanol was added as reservoir of substrate resulting in 98% yield, >99% ee and 4.08 mmol L -1  h -1  g -1 (wet cell weight) space time yield. This study paved a way for the whole cell biosynthesis of (3R,5S)-CDHH in mono and biphasic media. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Antioxidant and hepatoprotective effects of Capparis spinosa L. fractions and Quercetin on tert-butyl hydroperoxide- induced acute liver damage in mice

    Directory of Open Access Journals (Sweden)

    Heibatullah Kalantari

    2018-01-01

    Full Text Available The present study investigates the antioxidant and hepatoprotective effects of Capparis spinosa L. and Quercetin in tert-butyl hydroperoxide (t-BHP induced acute liver damage. Different fractions of C. spinosa were examined for total phenolic content and antioxidant property. Among these fractions, hydroalcoholic extract was used to assess the hepatoprotective effect in tert-butyl hydroperoxide (t-BHP induced hepatotoxicity model by determining serum biochemical markers, sleeping time and antioxidant assay such as reduced glutathione (GSH as well as histopathological examination of liver tissues. The total phenolic and Quercetin contents of hydroalcoholic fraction were significantly higher than other fractions. It also showed high antioxidant activity. Pretreatment with hydroalcoholic fraction at the dose of 400 mg/kg and Quercetin at the dose of 20 mg/kg showed liver protection against t-BHP induced hepatic injury, as it was evident by a significant decrease in serum enzymes marker, sleeping time and MDA and an increase in the GSH, SOD and CAT activities confirmed by pathology tests. The final results ascertained the hepatoprotective and antioxidant effects of C. spinosa and Quercetin in a dose-dependent manner. Moreover, this study suggests that possible mechanism of this protection may be associated with its property of scavenging free radicals which may be due to the presence of phenolic compounds.

  10. Protective Effects of Rooibos (Aspalathus linearis and/or Red Palm Oil (Elaeis guineensis Supplementation on tert-Butyl Hydroperoxide-Induced Oxidative Hepatotoxicity in Wistar Rats

    Directory of Open Access Journals (Sweden)

    Olawale R. Ajuwon

    2013-01-01

    Full Text Available The possible protective effects of an aqueous rooibos extract (Aspalathus linearis, red palm oil (RPO (Elaeis guineensis, or their combination on tert-butyl-hydroperoxide-(t-BHP-induced oxidative hepatotoxicity in Wistar rats were investigated. tert-butyl hydroperoxide caused a significant (P<0.05 elevation in conjugated dienes (CD and malondialdehyde (MDA levels, significantly (P<0.05 decreased reduced glutathione (GSH and GSH : GSSG ratio, and induced varying changes in activities of catalase, superoxide dismutase, glutathione peroxidase, and glutathione reductase in the blood and liver. This apparent oxidative injury was associated with histopathological changes in liver architecture and elevated levels of serum alanine aminotransferase (ALT, aspartate aminotransferase (AST, and lactate dehydrogenase (LDH. Supplementation with rooibos, RPO, or their combination significantly (P<0.05 decreased CD and MDA levels in the liver and reduced serum level of ALT, AST, and LDH. Likewise, changes observed in the activities of antioxidant enzymes and impairment in redox status in the erythrocytes and liver were reversed. The observed protective effects when rooibos and RPO were supplemented concomitantly were neither additive nor synergistic. Our results suggested that rooibos and RPO, either supplemented alone or combined, are capable of alleviating t-BHP-induced oxidative hepatotoxicity, and the mechanism of this protection may involve inhibition of lipid peroxidation and modulation of antioxidants enzymes and glutathione status.

  11. 6,6'-(1E,1'E-((1R,2R-1,2-Diphenylethane-1,2-diylbis(azan-1-yl-1-ylidenebis(methan-1-yl-1-ylidenebis(2-tert-butyl-4-((trimethylsilylethynylphenol

    Directory of Open Access Journals (Sweden)

    David Díaz Díaz

    2013-03-01

    Full Text Available Functionalizable salen derivative, 6,6'-(1E,1'E-((1R,2R-1,2-diphenylethane-1,2-diylbis(azan-1-yl-1-ylidenebis(methan-1-yl-1-ylidenebis(2-tert-butyl-4-((trimethylsilyl ethyn-ylphenol (3, was synthesized by condensation between (1R,2R-1,2-diphenylethane-1,2-diamine (2 and 3-tert-butyl-2-hydroxy-5-((trimethylsilylethynyl benzaldehyde (1 under refluxing conditions. The title compound was characterized by 1H-NMR, 13C-NMR, FT-IR, high-resolution mass spectrometry, optical rotation and melting point determination.

  12. Contact allergy to 2-hydroxy-5-tert-butyl benzylalcohol and 2,6-bis(hydroxymethyl)-4-tert-butylphenol, components of a phenolic resin used in marking pens

    DEFF Research Database (Denmark)

    Hagdrup, H; Egsgaard, H; Carlsen, L

    1994-01-01

    2-hydroxy-5-tert-butyl benzylalcohol and 2,6-bis(hydroxymethyl)-4-tert-butylphenol were identified as contact allergens in a phenolic resin used as a tackifier in the ink of a marking pen, which, after being used directly on the skin, caused an acute contact dermatitis on the hand of a 13-year...

  13. Temperature-Induced Desorption of Methyl tert-Butyl Ether Confined on ZSM-5: An In Situ Synchrotron XRD Powder Diffraction Study

    Directory of Open Access Journals (Sweden)

    Elisa Rodeghero

    2017-02-01

    Full Text Available The temperature-induced desorption of methyl tert-butyl ether (MTBE from aqueous solutions onto hydrophobic ZSM-5 was studied by in situ synchrotron powder diffraction and chromatographic techniques. This kind of information is crucial for designing and optimizing the regeneration treatment of such zeolite. The evolution of the structural features monitored by full profile Rietveld refinements revealed that a monoclinic (P21/n to orthorhombic (Pnma phase transition occurred at about 100 °C. The MTBE desorption process caused a remarkable change in the unit-cell parameters. Complete MTBE desorption was achieved upon heating at about 250 °C. Rietveld analysis demonstrated that the desorption process occurred without any significant zeolite crystallinity loss, but with slight deformations in the channel apertures.

  14. Viscosities of binary mixtures of some n-ethoxyethanols with ethyl tert-butyl ether at T = (293.15, 298.15, and 303.15) K

    International Nuclear Information System (INIS)

    Cwiklinska, Aneta; Dzikowski, Tomasz; Szychowski, Dariusz; Kinart, Wojciech J.; Kinart, Cezary M.

    2007-01-01

    Viscosities at T = (293.15, 298.15, and 303.15) K in the binary mixtures of ethyl tert-butyl ether with 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, and 2-[2-(2-ethoxyethoxy)ethoxy]ethanol have been measured over the entire range of mixture compositions. From the experimental data, deviations in the viscosity (Δln η) and excess energies of activation for viscous flow (ΔG *E ) have been calculated. The viscosity data were correlated with equations of Hind et al., Grunberg and Nissan, Auslaender, and McAllister. The results for Δln η and ΔG *E are discussed in terms of intermolecular interactions and structure of studied binary mixtures

  15. Synthesis and dynamic NMR study of ketenimines derived from tert-butyl isocyanide, alkyl 2-arylamino-2-oxo-acetates, and dialkyl acetylenedicarboxylates.

    Science.gov (United States)

    Yavari, Issa; Nasiri, Farough; Djahaniani, Horieh

    2004-01-01

    The adduct produced in the reaction between tert-butyl isocyanide and dialkyl acetylenedicarboxylates was trapped by alkyl 2-arylamino-2-oxo-acetates. When the aryl group is 2-methyl-6-nitrophenyl or 2,6-di-isopropylphenyl, the product exists as two stable rotamers at room temperature as a result of restricted rotation around the Ar-N single bond. When the aryl group is 1-naphthyl or 8-quinolinyl, dynamic NMR effects are observed in the 1H NMR spectra. The calculated free-energy of activation for interconversion of the rotational isomers in 1-naphthyl and 8-quinolinyl derivatives amounts to about 99+/-2 and 68.5+/-2 kJ mol(-1), respectively.

  16. Synthesis, structural characterization and theoretical studies of a new Schiff base 4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl) imino)methyl)phenol

    Science.gov (United States)

    Cuenú, Fernando; Londoño-Salazar, Jennifer; Torres, John Eduard; Abonia, Rodrigo; D'Vries, Richard F.

    2018-01-01

    4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl)imino)methyl)phenol (4-OHFPz) was synthesized and characterized by FT-IR, MS, NMR, and single-crystal X-ray diffraction. Optimization of molecular geometry, vibrational frequencies, and chemical shifts were calculated by using the methods of density functional theory (DFT) with B3LYP and B3PW91 as functionals and Hartree-Fock with 6-311G++(d,p) as basis set using the GAUSSIAN 09 program package. With the VEDA 4 software, the vibrational frequencies were assigned in terms of the potential energy distribution (PED). The equilibrium geometries calculated by all methods were compared with X-ray diffraction results, indicating that the theoretical results matches well with the experimental ones. The data obtained from the vibrational analysis and the calculated NMR are consistent with the experimental spectra.

  17. Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

    Science.gov (United States)

    Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

    2018-05-01

    It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

  18. Poly[[[diisothiocyanatocobalt(II]-bis[μ-4-tert-butyl-2,6-bis(1,2,4-triazol-1-ylmethylphenol

    Directory of Open Access Journals (Sweden)

    2009-03-01

    Full Text Available In the title compound, {[Co(NCS2(C16H20N6O2]·2C3H7NO·2H2O}n, each CoII ion located on an inversion center is six-coordinated by four equatorial N atoms from four different 4-tert-butyl-2,6-bis(1,2,4-triazol-1-ylmethylphenol (L ligands, and by two N atoms from two axial thiocyanate anions [Co—N = 2.104 (3–2.144 (3 Å]. The metal centres are connected via the bidentate L ligands into two-dimensional polymeric layers parallel to bc plane. The dimethylformamide and solvent water molecules participate in intermolecular O—H...O and O—H...S hydrogen bonds, which consolidate the crystal packing.

  19. Metabolism of the fungicide Denmert (S-n-butyl S'-p-tert-butyl-benzyl N-3-pyridyldithiocarbonimidate, S-1358) and Denmert sulfoxides in liver enzyme systems

    International Nuclear Information System (INIS)

    Ohkawa, Hideo; Okihara, Yukiko; Miyamoto, Junshi

    1976-01-01

    On incubation with rat liver microsomes plus MADPH, Denmert (S-n-butyl S'-p-tert-butylbenzyl N-3-pyridyldithiocarbonimidate) underwent at least two different types of oxidation; hydroxylation and sulfoxidation. Hydroxylation of Denmert at the tert-butyl group was one of the major metabolic attacks in mammalian metabolism. Sulfoxidation of Denmert gave two isomers of Denmert sulfoxides which were intermediates in the metabolism and readily transformed into 2-(3'-pyridylimino)-4-carboxylthiazolidine (HM) in the presence of L-cysteine without enzymatic mediation. This type of conjugation with cysteine appears to be a new class of metabolic reactions in mammals. Denmert S-oxide showed increased fungicidal activity when assayed in liquid cultures, but not on plant leaves. (auth.)

  20. Microwave-Assisted Synthesis and Crystal Structure of Oxo(diperoxo(4,4'-di-tert-butyl-2,2'-bipyridine-molybdenum(VI

    Directory of Open Access Journals (Sweden)

    Alírio E. Rodrigues

    2009-09-01

    Full Text Available The oxodiperoxo complex MoO(O22(tbbpy (tbbpy = 4,4'-di-tert-butyl-2,2'- bipyridine was isolated from the reaction of MoO2Cl2(tbbpy in water under microwaveassisted heating at 120 ºC for 4 h. The structure of the oxodiperoxo complex was determined by single crystal X-ray diffraction. The MoVI centre is seven-coordinated with a geometry which strongly resembles a highly distorted bipyramid. Individual MoO(O22(tbbpy complexes are interdigitated along the [010] direction to form a column. The crystal structure is formed by the close packing of the columnar-stacked complexes. Interactions between neighbouring columns are essentially of van der Waals type mediated by the need to effectively fill the available space.

  1. Multi-wall carbon nanotubes supported molybdenyl acetylacetonate: Efficient and highly reusable catalysts for epoxidation of alkenes with tert-butyl hydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Esnaashari, Fariba [Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of); Moghadam, Majid, E-mail: moghadamm@sci.ui.ac.ir [Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of); Mirkhani, Valiollah, E-mail: mirkhani@sci.ui.ac.ir [Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of); Tangestaninejad, Shahram; Mohammadpoor-Baltork, Iraj; Khosropour, Ahmad Reza; Zakeri, Maryam [Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of)

    2012-11-15

    Efficient epoxidation of olefins catalyzed by MoO{sub 2}(acac){sub 2} supported on amines functionalized MWCNTs is reported. The MWCNTs bearing carboxylic acid groups were modified with 2-aminophenol and 2-aminothiophenol. These amine-MWCNTs act as bidentate ligand for attachment of Mo catalyst. These catalysts were characterized by elemental analysis, scanning electron microscopy, FT-IR and diffuse reflectance UV-Vis spectroscopic methods. The prepared catalysts were used for efficient epoxidation of different alkenes such as cyclic and linear ones with tert-butyl hydroperoxide in refluxing 1,2-dichloroethane. These heterogeneous catalysts can be reused several times without significant loss of their catalytic activity. Highlights: Black-Right-Pointing-Pointer Supporting of molybdenyl acetylacetonate on amine-modified MWCNTs. Black-Right-Pointing-Pointer Heterogeneous catalysts were prepared. Black-Right-Pointing-Pointer These catalysts were highly efficient in the epoxidation of alkenes with TBHP. Black-Right-Pointing-Pointer Makes the catalysts reusable.

  2. Multi-wall carbon nanotubes supported molybdenyl acetylacetonate: Efficient and highly reusable catalysts for epoxidation of alkenes with tert-butyl hydroperoxide

    International Nuclear Information System (INIS)

    Esnaashari, Fariba; Moghadam, Majid; Mirkhani, Valiollah; Tangestaninejad, Shahram; Mohammadpoor-Baltork, Iraj; Khosropour, Ahmad Reza; Zakeri, Maryam

    2012-01-01

    Efficient epoxidation of olefins catalyzed by MoO 2 (acac) 2 supported on amines functionalized MWCNTs is reported. The MWCNTs bearing carboxylic acid groups were modified with 2-aminophenol and 2-aminothiophenol. These amine–MWCNTs act as bidentate ligand for attachment of Mo catalyst. These catalysts were characterized by elemental analysis, scanning electron microscopy, FT-IR and diffuse reflectance UV–Vis spectroscopic methods. The prepared catalysts were used for efficient epoxidation of different alkenes such as cyclic and linear ones with tert-butyl hydroperoxide in refluxing 1,2-dichloroethane. These heterogeneous catalysts can be reused several times without significant loss of their catalytic activity. Highlights: ► Supporting of molybdenyl acetylacetonate on amine-modified MWCNTs. ► Heterogeneous catalysts were prepared. ► These catalysts were highly efficient in the epoxidation of alkenes with TBHP. ► Makes the catalysts reusable.

  3. 5-tert-Butyl-2-(4'-[{sup 18}F]fluoropropynylphenyl)-1,3-dithiane oxides: potential new GABA{sub A} receptor radioligands

    Energy Technology Data Exchange (ETDEWEB)

    Li Xuehe; Jung, Yong-Woon; Snyder, Scott E.; Blair, Joseph; Sherman, Philip S.; Desmond, Timothy; Frey, Kirk A. [Department of Radiology, University of Michigan Medical School, Ann Arbor, MI 48109 (United States); Kilbourn, Michael R. [Department of Radiology, University of Michigan Medical School, Ann Arbor, MI 48109 (United States)], E-mail: mkilbour@umich.edu

    2008-07-15

    As potential new ligands targeting the binding site of {gamma}-aminobutyric acid (GABA) receptor ionophore, trans-5-tert-butyl-2-(4'-fluoropropynylphenyl)-2-methyl-1,1-dioxo-1, 3-dithiane (1) and cis/trans-5-tert-butyl-2-(4'-fluoropropynylphenyl)-2-methyl-1,1,3, 3-tetroxo-1,3-dithiane (2) were selected for radiolabeling and initial evaluation as in vivo imaging agents for positron emission tomography (PET). Both compounds exhibited identical high in vitro binding affinities (K{sub i}=6.5 nM). Appropriate tosylate-substituted ethynyl precursors were prepared by multistep syntheses involving stepwise sulfur oxidation and chromatographic isolation of desired trans isomers. Radiolabeling was accomplished in one step using nucleophilic [{sup 18}F]fluorination. In vivo biodistribution studies with trans-[{sup 18}F]1 and trans-[{sup 18}F]2 showed significant initial uptake into mouse brain and gradual washout, with heterogeneous regional brain distributions and higher retention in the cerebral cortex and cerebellum and lower retention in the striatum and pons-medulla. These regional distributions of the new radioligands correlated with in vitro and ex vivo measures of standard radioligands binding to the ionophore- and benzodiazepine-binding sites of GABA{sub A} receptor in rodent brain. A comparison of these results with previously prepared radiotracers for other neurochemical targets, including successes and failures as in vivo radioligands, suggests that higher-affinity compounds with increased retention in target brain tissues will likely be needed before a successful radiopharmaceutical for human PET imaging can be identified.

  4. Synthesis of 4-tert-Butyltoluene by Vapor Phase tert-Butylation of Toluene with tert-Butylalcohol over USY Zeolite

    Directory of Open Access Journals (Sweden)

    Yan Ming Shen

    2015-03-01

    Full Text Available Vapour phase tert-butylation of toluene with tert-butylalcohol was studied over ultra-stable Y zeolite (USY catalyst. The effects of reaction temperature, toluene/TBA molar ratio and liquid space velocity on conversion of toluene and selectivity for 4-tert-butyltoluene were studied. The deactivation and regeneration of the catalyst was also investigated. The results showed that the USY zeolite catalyst offered better toluene conversion of about 30 % and 4-tert-butyltoluene selectivity of about 89 % at the suitable reaction condition as follows: reaction temperature of 120 oC, toluene/TBA ratio of 2:1 and liquid space velocity of 2 ml/g·h. The clogging of mocropores by the formed carbon or oligomers was the main reason for the deactivation of the catalyst. By combustion at 550 oC, the catalyst just lost about 5 % in toluene conversion and about 2 % in PTBT selectivity. © 2015 BCREC UNDIP. All rights reservedReceived: 17th July 2014; Revised: 31st August 2014; Accepted: 3rd September 2014How to Cite: Shen, Y.M., Yuan, S., Fan, L., Liu, D.B., Li, S.F. (2015. Synthesis of 4-tert-Butyltoluene by Vapor Phase tert-Butylation of Toluene with tert-Butylalcohol over USY Zeolite. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 1-7. (doi:10.9767/bcrec.10.1.7140.1-7Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7140.1-7

  5. Simultaneous analysis of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils by normal-phase high performance liquid chromatography.

    Science.gov (United States)

    Li, Jun; Bi, Yanlan; Sun, Shangde; Peng, Dan

    2017-11-01

    A normal-phase high performance liquid chromatography method for the simultaneous determination of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils was investigated. A silica column was used to separate the analytes with the gradient elution. An ultraviolet-visible detector was set at dual wavelengths mode (280 and 310nm). The column temperature was 30°C. The analytes were directly extracted with methanol. Results showed that the normal-phase high performance liquid chromatography method performed well with wide liner ranges (0.10∼500.00μg/mL, R 2 >0.9998), low limits of detection and quantitation (below 0.40 and 1.21μg/mL, respectively), and good recoveries (81.38∼102.34% in soybean oils and 83.03∼100.79% in lard, respectively). The reduction of tert-butylquinone caused by the reverse-phase high performance liquid chromatography during the injection was avoided with the current normal-phase method. The two isomers of butylated hydroxyanisole can also be separated with good resolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al2O3 supported copper and gold nanoparticles

    International Nuclear Information System (INIS)

    Ndolomingo, Matumuene Joe; Meijboom, Reinout

    2017-01-01

    Highlights: • Cu and Au on γ-Al 2 O 3 catalysts were prepared and characterized. • Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide in the absence of any solvent using the prepared catalysts. • The as prepared catalysts exhibited good performance in terms of conversion and selectivity towards benzaldehyde. • The kinetics of the reaction was investigated; k app was proportional to the amount of nano catalyst and oxidant present in the system. • The catalysts was recycled and reused with neither significant loss of activity nor selectivity. - Abstract: Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al 2 O 3 supported copper and gold nanoparticles. Li 2 O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N 2 absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol is occurring as a function of

  7. Highly efficient enzymatic synthesis of tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate with a mutant alcohol dehydrogenase of Lactobacillus kefir.

    Science.gov (United States)

    He, Xiu-Juan; Chen, Shao-Yun; Wu, Jian-Ping; Yang, Li-Rong; Xu, Gang

    2015-11-01

    tert-Butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH) is a valuable chiral synthon, which is used for the synthesis of the cholesterol-lowering drugs atorvastatin and rosuvastatin. To date, only the alcohol dehydrogenases from Lactobacillus brevis (LbADH) and Lactobacillus kefir (LkADH) have demonstrated catalytic activity toward the asymmetric reduction of tert-butyl 6-chloro-3,5-dioxohexanoate (CDOH) to (S)-CHOH. Herein, a tetrad mutant of LkADH (LkTADH), A94T/F147L/L199H/A202L, was screened to be more efficient in this bioreduction process, exhibiting a 3.7- and 42-fold improvement in specific activity toward CDOH (1.27 U/mg) over LbADH (0.34 U/mg) and wild-type LkADH (0.03 U/mg), respectively. The molecular basis for the improved catalytic activity of LkTADH toward CDOH was investigated using homology modeling and docking analysis. Two major issues had a significant impact on the biocatalytic efficiency of this process, including (i) the poor aqueous stability of the substrate and (ii) partial substrate inhibition. A fed-batch strategy was successfully developed to address these issues and maintain a suitably low substrate concentration throughout the entire process. Several other parameters were also optimized, including the pH, temperature, NADP(+) concentration and cell loading. A final CDOH concentration of 427 mM (100 g/L) gave (S)-CHOH in 94 % yield and 99.5 % e.e. after a reaction time of 38 h with whole cells expressing LkTADH. The space-time yield and turnover number of NADP(+) in this process were 10.6 mmol/L/h and 16,060 mol/mol, respectively, which were the highest values ever reported. This new approach therefore represents a promising alternative for the efficient synthesis of (S)-CHOH.

  8. Free radicals in an Adamantane matrix. XI. Electron paramagnetic resonance study of conformations in the β-halo-tert-butyl radicals

    International Nuclear Information System (INIS)

    Lloyd, R.V.; Wood, D.E.

    1975-01-01

    The β-halo-tert-butyl radicals were prepared by x-irradiation of the corresponding isobutyl halides in an adamantane matrix at 77 0 K and their conformations were determined by analysis of their EPR spectra. The radicals are nonplanar at the radical site, the fluoro and chloro radicals trans eclipsed and the bromo and iodo radicals gauche staggered with respect to the relative orientation of the carbon halogen bond and the direction of the singly occupied orbital. Vibration-rotation motions about the favored conformation are much larger for the fluoro radical than for the others. The rate of interconversion of the inequivalent methylene protons is approximately 1.5 x 10 9 sec -1 for the bromo radical at 202 0 K while it is too slow to measure for the iodo radical at the same temperature. The barrier to interconversion has a lower limit of 3 kcal/mol for the bromo radical and higher than that for the iodo radical. The halogen and proton hfsc in gauss and the g values for the XCH 2 C(CH 3 ) 2 radicals are: 19 F = 103.7, CH 2 = 10.4, CH 3 = 23.3, g = 2.0030 at 214 K; 35 Cl = 19.5, CH 2 = 6.3, CH 3 = 21.1, g = 2.0042 at 215 K; 81 Br = 6.7, CH 2 = 21.4, 42.7, CH 3 = 21.4, g = 2.0010 at 202 K; 127 I = 7.0, CH 2 = 21.9, 43.8, CH 3 = 21.9, g = 2.0009 at 208 K. The fluoro radical decays to nonradical products above 318 0 K, the chloro radical converts to 2-methyl allyl radical above 306 0 K, the bromo radical converts to tert-butyl radical by exchange with a matrix proton (or deuteron) at 209 0 K as does the iodo radical above 225 0 K. Photolysis with a Xe lamp converts the bromo and iodo radicals to nonradical products in less than the experimental time constant of 0.3 sec. The hypothesis is put forward that the nonplanarity and high barrier to rotation observed explain the retention of stereochemical configuration in reactions involving β-chloro, β-bromo, and β-iodo alkyl radicals. (auth)

  9. Isothermal (vapor + liquid) equilibria and excess enthalpy data of {1-hexene + methyl butyl ether (MBE)} and {1-hexene + methyl tert-butyl ether (MTBE)} binary systems at several temperatures

    International Nuclear Information System (INIS)

    Hani, Rachida; Solimando, Roland; Negadi, Latifa; Jose, Jacques; Ait Kaci, Ahmed

    2012-01-01

    Highlights: ► Vapor pressures of (1-hexene + methyl butyl ether) or (1-hexene + methyl tert-butyl ether) are reported between (263 and 363) K. ► The two mixtures exhibit positive G E . ► Additionally, molar excess enthalpies, H E , for the two binary systems have been measured at 303.15. - Abstract: The vapor pressures of {1-hexene + methyl butyl ether (MBE)} and {1-hexene + methyl tert-butyl ether (MTBE)} binary mixtures and of the three pure components were measured by means of a static device at temperatures between (263 and 333) K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions were calculated for several constant temperatures and fitted to a third-order Redlich–Kister equation using the Barker’s method. Additionally, molar excess enthalpies, H E , for the two binary systems have been measured at 303.15 K using an isothermal flow calorimeter.

  10. Synthesis of [[sup 123]I]tert-Butyl 8-iodo-5,6-dihydro-5-methyl-6-oxo-4H-imidazo[1,5-a][1,4]benzodiaze pine 3-carboxylate, a potential SPECT imaging agent for diazepam-intensive (DI) benzodiazepine receptors

    Energy Technology Data Exchange (ETDEWEB)

    He, Xiaoshu; Matecka, Dorota; Gu, Ziqiang; Rice, K C; Costa, B.R. de [National Inst. of Diabetes and Digestive and Kidney Diseases, Bethesda, MD (United States); Lee, K S [National Inst. of Mental Health, Washington, DC (United States); Wong, Garry; Skolnick, Phil [National Inst. of Diabetes and Digestive and Kidney Diseases, Bethesda, MD (United States). Lab. of Neuroscience

    1994-01-01

    [[sup 123]I]tert-Butyl 8-iodo-5,6-dihydro-5-methyl-6-oxo-4H-imidazo [1,5-a] [1,4]benzodiazepine 3-carboxylate ([[sup 123]I]3), a high affinity and selective radioligand for the diazepam insensitive (DI) benzodiazepine receptor was synthesized in 2 steps from tert-butyl 8-bromo-5,6-dihydro-5-methyl-6-oxo-4H-imidazo[1,5-a][1,4]benzodiaz epine 3-carboxylate. (Author).

  11. Aerobic degradation of methyl tert-butyl ether in a closed symbiotic system containing a mixed culture of Chlorella ellipsoidea and Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Zhong, Weihong; Li, Yixiao; Sun, Kedan; Jin, Jing; Li, Xuanzhen; Zhang, Fuming; Chen, Jianmeng

    2011-01-30

    The contamination of groundwater by methyl tert-butyl ether (MTBE) is one of the most serious environmental problems around the world. MTBE degradation in a closed algal-bacterial symbiotic system, containing a mixed culture of Methylibium petroleiphilum PM1 and Chlorella ellipsoidea, was investigated. The algal-bacterial symbiotic system showed increased MTBE degradation. The MTBE-degradation rate in the mixed culture (8.808 ± 0.007 mg l(-1) d(-1)) was higher than that in the pure bacterial culture (5.664 ± 0.017 mg l(-1) d(-1)). The level of dissolved oxygen was also higher in the mixed culture than that in the pure bacterial culture. However, the improved efficiency of MTBE degradation was not in proportional to the biomass of the alga. The optimal ratio of initial cell population of bacteria to algae was 100:1. An immobilized culture of mixed bacteria and algae also showed higher MTBE degradation rate than the immobilized pure bacterial culture. A mixed culture with algae and PM1 immobilized separately in different gel beads showed higher degradation rate (8.496 ± 0.636 mg l(-1) d(-1)) than that obtained with algae and PM1 immobilized in the same gel beads (5.424 ± 0.010 mg l(-1) d(-1)). Copyright © 2010 Elsevier B.V. All rights reserved.

  12. Adiabatic compressibility of pseudo-binary aqueous solutions of tert-butyl alcohol and dimethylsulfoxide as a result of ultrasonic investigations

    International Nuclear Information System (INIS)

    Miecznik, Piotr; Kaczmarek, Milena

    2006-01-01

    The tert-butyl alcohol (TBA) and dimethyl sulfoxide (DMSO) are two small molecules geometrically very similar, but having different polar groups. Taking into account the intermolecular interactions in the TBA/H 2 O and DMSO/H 2 O systems, especially in the water-rich region of concentration, the ultrasonic speeds (high accuracy resonance method at the frequency 7.5 MHz) and densities in pseudo-binary mixtures of the system: (TBA + H 2 O + DMSO) with the ratio (TBA + DMSO)/H 2 O = 1/25 have been measured. From these data, various thermodynamical parameters such as adiabatic compressibility, molar volume, thermal expansivity, and the deviation from reference system have been calculated. In addition, the isobaric molar heat capacity to convert adiabatic compressibility to the isothermal one has been measured. All these parameters have been discussed to explain solute-solvent and solute-solute interactions, especially the effect of the complexation process between TBA and DMSO molecules. The composition dependence of these deviations functions was interpreted in the light of the mixing schemes in the aqueous solutions of TBA and DMSO

  13. Adiabatic compressibility of pseudo-binary aqueous solutions of tert-butyl alcohol and dimethylsulfoxide as a result of ultrasonic investigations

    Energy Technology Data Exchange (ETDEWEB)

    Miecznik, Piotr [Institute of Acoustics, Adam Mickiewicz University, Umultowska 85, PL-61-614 Poznan (Poland)]. E-mail: miecznik@main.amu.edu.pl; Kaczmarek, Milena [Institute of Acoustics, Adam Mickiewicz University, Umultowska 85, PL-61-614 Poznan (Poland)

    2006-11-15

    The tert-butyl alcohol (TBA) and dimethyl sulfoxide (DMSO) are two small molecules geometrically very similar, but having different polar groups. Taking into account the intermolecular interactions in the TBA/H{sub 2}O and DMSO/H{sub 2}O systems, especially in the water-rich region of concentration, the ultrasonic speeds (high accuracy resonance method at the frequency 7.5 MHz) and densities in pseudo-binary mixtures of the system: (TBA + H{sub 2}O + DMSO) with the ratio (TBA + DMSO)/H{sub 2}O = 1/25 have been measured. From these data, various thermodynamical parameters such as adiabatic compressibility, molar volume, thermal expansivity, and the deviation from reference system have been calculated. In addition, the isobaric molar heat capacity to convert adiabatic compressibility to the isothermal one has been measured. All these parameters have been discussed to explain solute-solvent and solute-solute interactions, especially the effect of the complexation process between TBA and DMSO molecules. The composition dependence of these deviations functions was interpreted in the light of the mixing schemes in the aqueous solutions of TBA and DMSO.

  14. Fluctuating micro-heterogeneity in water–tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

    International Nuclear Information System (INIS)

    Banerjee, Saikat; Furtado, Jonathan; Bagchi, Biman

    2014-01-01

    Water–tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with x TBA ≈ 0.03–0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at x TBA ≈ 0.05. We note that “islands” of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, x TBA ≈ 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level

  15. Vibrational frequency analysis, FT-IR, DFT and M06-2X studies on tert-Butyl N-(thiophen-2yl)carbamate

    Science.gov (United States)

    Sert, Yusuf; Singer, L. M.; Findlater, M.; Doğan, Hatice; Çırak, Ç.

    2014-07-01

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized tert-Butyl N-(thiophen-2yl)carbamate have been investigated. The experimental FT-IR (4000-400 cm-1) spectrum of the molecule in the solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters (bond lengths and bond angles) have been calculated by using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr) and DFT/M06-2X (the highly parametrized, empirical exchange correlation function) quantum chemical methods with the 6-311++G(d,p) basis set by Gaussian 09W software, for the first time. The vibrational frequencies have been assigned using potential energy distribution (PED) analysis by using VEDA 4 software. The computational optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data, and with related literature results. In addition, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies and the other related molecular energy values have been calculated and are depicted.

  16. FT-IR, FT-Raman spectra, density functional computations of the vibrational spectra and molecular conformational analysis of 2,5-di-tert-butyl-hydroquinone

    Science.gov (United States)

    Subramanian, N.; Sundaraganesan, N.; Dereli, Ö.; Türkkan, E.

    2011-12-01

    The purpose of finding conformer among six different possible conformers of 2,5-di-tert-butyl-hydroquinone (DTBHQ), its equilibrium geometry and harmonic wavenumbers were calculated by the B3LYP/6-31G(d,p) method. The infrared and Raman spectra of DTBHQ were recorded in the region 400-4000 cm -1 and 50-3500 cm -1, respectively. In addition, the IR spectra in CCl 4 at various concentrations of DTBHQ are also recorded. The computed vibrational wavenumbers were compared with the IR and Raman experimental data. Computational calculations at B3LYP level with two different basis sets 6-31G(d,p) and 6-311++G(d,p) are also employed in the study of the possible conformer of DTBHQ. The complete assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA 4 program. The general agreement between the observed and calculated frequencies was established.

  17. Equilibrium surface tension and the interaction energy of DMSO with tert-butyl alcohol or iso-amyl alcohol at various temperatures

    International Nuclear Information System (INIS)

    Bagheri, Ahmad; Moradian, Zohreh

    2014-01-01

    Highlights: • Surface tension of non-ideal binary systems of alcohol/DMSO determined. • The surface tension data of binary mixtures were correlated with five equations. • The interaction energy values were calculated by using LWW model. • The U 12 value shows different behavior for two systems with increasing temperature. - Abstract: Surface tension of binary mixtures of tert-butyl alcohol (TBA) and iso-amyl alcohol (IAA) with DMSO (dimethyl sulfoxide) were measured over the entire concentration range at pressure of 82.5 kPa at temperatures between (298.15 and 328.15) K. Correlating the surface tension and surface tension deviation of the above mentioned binary systems was performed with empirical and thermodynamic based models. The average relative error obtained from the comparison of experimental and calculated surface tension values for the two binary systems with five models at various temperatures is less than 2%. The effect of temperature on the interaction energy values in binary mixtures has been used to obtain information about solute structural effects on DMSO. Also, the experimental data were used to evaluate the nature and type of intermolecular interactions in binary mixtures

  18. Molecular structure, vibrational, UV, NMR, HOMO-LUMO, MEP, NLO, NBO analysis of 3,5 di tert butyl 4 hydroxy benzoic acid

    Science.gov (United States)

    Mathammal, R.; Sangeetha, K.; Sangeetha, M.; Mekala, R.; Gadheeja, S.

    2016-09-01

    In this study, we report a combined experimental and theoretical study on molecular structure and vibrational spectra of 3,5 di tert butyl 4 hydroxy benzoic acid. The properties of title compound have been evaluated by quantum chemical calculation (DFT) using B3LYP functional and 6-31 + G (d, p) as basis set. IR Spectra has been recorded using Fourier transform infrared spectroscopy (FT-IR) in the region 4000-400 cm-1. The vibrational assignment of the calculated normal modes has been made on the basis set. The isotropic chemical shifts computed by 13C and 1H NMR (Nuclear Magnetic Resonance) analyses also show good agreement with experimental observations. The theoretical UV-Vis spectrum of the compound are used to study the visible absorption maxima (λ max). The structure activity relationship have been interpreted by mapping electrostatic potential surface (MEP), which is valuable information for the quality control of medicines and drug receptor interactions. The Mullikan charges, HOMO (Highest Occupied Molecular Orbital) - LUMO (Lowest Unoccupied Molecular Orbital) energy are analyzed. HOMO-LUMO energy gap and other related molecular properties are also calculated. The Natural Bond Orbital (NBO) analysis is carried out to investigate the various intra and inter molecular interactions of molecular system. The Non-linear optical properties such as dipole moment (μ), polarizability (αtot) and molecular first order hyperpolarizability (β) of the title compound are computed with B3LYP/6-31 + G (d,p) level of theory.

  19. Preparation of Langmuir–Blodgett thin films of calix[6]arenes and p-tert butyl group effect on their gas sensing properties

    Energy Technology Data Exchange (ETDEWEB)

    Ozmen, Mustafa, E-mail: musozmen@gmail.com [Department of Chemistry, University of Selcuk, 42075 Konya (Turkey); Ozbek, Zikriye, E-mail: zikriye@comu.edu.tr [Department of Bioengineering, University of Canakkale Onsekiz Mart, 17100 Canakkale (Turkey); Bayrakci, Mevlut [Department of Bioengineering, University of Karamanoglu Mehmetbey, 70200 Karaman (Turkey); Ertul, Seref; Ersoz, Mustafa [Department of Chemistry, University of Selcuk, 42075 Konya (Turkey); Capan, Rifat [Department of Physics, University of Balikesir, 10145 Balikesir (Turkey)

    2015-12-30

    Graphical abstract: - Highlights: • In this work, we prepared Langmuir–Blodgett films of calix[6]arene derivatives. • Then LB films of calixarene compounds were characterized. • Organic vapor sensing properties of prepared LB films were investigated. - Abstract: Organic vapor sensing properties of Langmuir–Blodgett (LB) thin films of p-tert-butyl calix[6]arene and calix[6]arene, and their certain characterization are reported in this work. LB films of these calixarenes have been characterized by contact angle measurement, quartz crystal microbalance (QCM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). QCM system was used for the measurement of sensor response against chloroform, benzene, toluene and ethanol vapors. Forming of stable monolayers was observed at the water surface using surface pressure–area isotherm graph. The results indicate that good quality, uniform LB films can be prepared with a transfer ratio of over 0.95. Due to the adsorption of vapors into the LB film structures; they yield a response to all vapors as of large, fast, and reproducible.

  20. Cytotoxic and DNA-damaging effects of methyl tert-butyl ether and its metabolites on HL-60 cells in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Tang, G.H. [Xian Medical Univ. (China); Shen, Y.; Shen, H.M. [National Univ. of Singapore (Singapore)] [and others

    1996-12-31

    Methyl tert-butyl ether (MTBE) is a widely used oxygenate in unleaded gasoline; however, few studies have been conducted on the toxicity of this compound. This study evaluates the cytotoxic and DNA-damaging effects of MTBE and its metabolites in a human haemopoietic cell line, HL-60. The metabolites of MTBE studied include tertiary butyl alcohol (TBA), {alpha}-hydroxyisobutyric acid (HIBA), and formaldehyde. Comet assay is used to assess DNA damage, and the cytotoxicity is investigated by lactate dehydrogenease (LDH) release. The results show no significant cytotoxic effects of MTBE, TBA, and HIBA over a concentration ranging from 1 to 30 mM. Formaldehyde, in contrast, causes a substantial LDH release at a concentration of 5 {mu}M. Hydrogen peroxide, a known oxidative agent, at concentrations ranging from 10 to 100 {mu}M, produces a significant dose-related increase in DNA damage, whereas a much higher concentration of MTBE (1 to 30 mM) is required to produce a similar observation. The genotoxic effects of TBA and HIBA appear to be identical to that of MTBE. Conversely, DNA damage is observed for formaldehyde at a relatively low concentration range (5 to 100 {mu}M). These findings suggest that MTBE and its metabolites, except formaldehyde, have relatively low cytotoxic and genotoxic effects. 16 refs., 4 figs.

  1. Polypyrrole-Grafted Coconut Shell Biological Carbon as a Potential Adsorbent for Methyl Tert-Butyl Ether Removal: Characterization and Adsorption Capability

    Directory of Open Access Journals (Sweden)

    Shanshan Li

    2017-01-01

    Full Text Available Methyl tert-butyl ether (MTBE has been used as a common gasoline additive worldwide since the late twentieth century, and it has become the most frequently detected groundwater pollutant in many countries. This study aimed to synthesize a novel microbial carrier to improve its adsorptive capacity for MTBE and biofilm formation, compared to the traditional granular activated carbon (GAC. A polypyrrole (PPy-modified GAC composite (PPy/GAC was synthesized, and characterized by Fourier transform infrared spectroscopy (FT-IR and Brunauer-Emmett-Teller (BET surface area analysis. The adsorption behaviors of MTBE were well described by the pseudo-second-order and Langmuir isotherm models. Furthermore, three biofilm reactors were established with PPy/GAC, PPy, and GAC as the carriers, respectively, and the degradation of MTBE under continuous flow was investigated. Compared to the biofilm reactors with PPy or GAC (which both broke after a period of operation, the PPy/GAC biofilm column produced stable effluents under variable treatment conditions with a long-term effluent MTBE concentration <20 μg/L. Pseudomonas aeruginosa and Acinetobacter pittii may be the predominant bacteria responsible for MTBE degradation in these biofilm reactors.

  2. Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

    International Nuclear Information System (INIS)

    Cloud, Andrew N.; Abelson, John R.; Davis, Luke M.; Girolami, Gregory S.

    2014-01-01

    Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300 °C from three recently synthesized M[N(t-Bu) 2 ] 2 precursors, where M = Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200 °C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18 nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities

  3. Protective Effects of Black Rice Extracts on Oxidative Stress Induced by tert-Butyl Hydroperoxide in HepG2 Cells

    Science.gov (United States)

    Lee, Seon-Mi; Choi, Youngmin; Sung, Jeehye; Kim, Younghwa; Jeong, Heon-Sang; Lee, Junsoo

    2014-01-01

    Black rice contains many biologically active compounds. The aim of this study was to investigate the protective effects of black rice extracts (whole grain extract, WGE and rice bran extract, RBE) on tert-butyl hydroperoxide (TBHP)-induced oxidative injury in HepG2 cells. Cellular reactive oxygen species (ROS), antioxidant enzyme activities, malondialdehyde (MDA) and glutathione (GSH) concentrations were evaluated as biomarkers of cellular oxidative status. Cells pretreated with 50 and 100 μg/mL of WGE or RBE were more resistant to oxidative stress in a dose-dependent manner. The highest WGE and BRE concentrations enhanced GSH concentrations and modulated antioxidant enzyme activities (glutathione reductase, glutathione-S-transferase, catalase, and superoxide dismutase) compared to TBHP-treated cells. Cells treated with RBE showed higher protective effect compared to cells treated with WGE against oxidative insult. Black rice extracts attenuated oxidative insult by inhibiting cellular ROS and MDA increase and by modulating antioxidant enzyme activities in HepG2 cells. PMID:25580401

  4. Disposition of 2,6-di-tert-butyl-4-nitrophenol (DBNP), a submarine atmosphere contaminant, in male Sprague-Dawley rats

    International Nuclear Information System (INIS)

    Still, Kenneth R.; Jung, Anne E.; Ritchie, Glenn D.; Jederberg, Warren W.; Wilfong, Erin R.; Briggs, G. Bruce; Arfsten, Darryl P.

    2005-01-01

    The phenol 2,6-di-tert-butyl-4-nitrophenol (DBNP) is a contaminant found onboard submarines and is formed by the nitration of an antioxidant present in turbine lubricating oil TEP 2190. DBNP has been found on submarine interior surfaces, on eating utensils and dishes, and on the skin of submariners. DBNP exposure is a potential health concern because it is an uncoupler of mitochondrial oxidative phosphorylation. Adult male rats were dosed once by oral gavage with 15 or 40 mg/kg DBNP mixed with 14 C-DBNP in kanola oil and 0.8% v/v DMSO (n=16/group). The distribution of 14 C in major tissues was measured over time for up to 240 h post-dose. Unexpectedly, 6/16 (40%) of the rats gavaged with 40 mg/kg DBNP died within 24 h of dosing. Prostration, no auditory startle response, reduced locomotor activity, and muscular rigidity persisted in survivors for up to 8 days after dosing. For animals dosed with 15 mg/kg DBNP, radioactivity levels were significantly elevated in the following tissues 24 h after dosing: fat>>>liver>kidneys>heart>lungs>brain>striated muscle>spleen. Radioactivity levels were elevated for fat, liver, kidney, heart, and lungs of animals euthanized 144 h post-dosing and in the liver of animals euthanized 240 h post-dosing. These findings suggest that DBNP may accumulate in the body as a result of continuous or repeat exposures of short interval to DBNP

  5. Solvent extraction of technetium from alkaline waste media using bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6

    International Nuclear Information System (INIS)

    Bonnesen, P.V.; Presley, D.J.; Moyer, B.A.

    1995-01-01

    The crown ether bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 can be utilized in a solvent-extraction process for the removal of technetium as pertechnetate ion, TcO 4 - from solutions simulating highly radioactive alkaline defense wastes (''tank wastes'') stored at several sites in the United States. The process employs non-halogenated and non-volatile diluents and modifiers and includes an efficient stripping procedure using only water. More than 95% of the pertechnetate present at 6 x 10 -5 M in Melton Valley (Oak Ridge, TN) and Hanford (Washington) tank-waste simulants was removed following two cross-current extraction contacts using 0.02 M bis-4,4'(5')[(tertbutyl)cyclohexano]- 18-crown-6 in 2:1 vol/vol TBP/Isopar reg-sign M diluent at 25 C. Similarly, for both simulants, more than 98% of the pertechnetate contained in the solvent was back-extracted following two cross-current stripping contacts using deionized water

  6. The Synergistic Effects of Heat Shock Protein 70 and Ginsenoside Rg1 against Tert-Butyl Hydroperoxide Damage Model In Vitro

    Directory of Open Access Journals (Sweden)

    Dan Lu

    2015-01-01

    Full Text Available Neural stem cells (NSCs transplanted is one of the hottest research to treat Alzheimer’s disease (AD, but cholinergic neurons from stem cells were also susceptible to cell death which Heat shock protein 70 (HSP70 was affirmed to reverse. Related to cognitive impairment, cholinergic nervous cells should be investigated and ginsenoside Rg1 (G-Rg1 was considered to increase them. We chose tert-butyl hydroperoxide (t-BHP damage model to study in vitro. Functional properties of our recombination plasmid pEGFP-C2-HSP70 were affirmed by SH-SY5Y cells. To opposite the transitory appearance of HSP70, NSCs used as the vectors of HSP70 gene overexpressed HSP70 for at least 7 days in vitro. After transfection for 3 days, G-Rg1 pretreatment for 4 hours, and coculture for 3 days, the expression of acetylcholinesterase (ChAT, synaptophysin, and the ratio of NeuN and GFAP were assessed by western blot; Morphological properties were detected by 3D reconstruction and immunofluorescence. ChAT was markedly improved in the groups contained G-Rg1. In coculture system, the ratio of neurons/astrocytes and the filaments of neurons were increased; apoptosis cells were decreased, compared to monotherapy (P<0.05. In conclusion, we demonstrated that, as a safe cotreatment affirmed in vitro, overexpression of HSP70 in NSCs plus G-Rg1 promoted nervous cells regeneration from chronic oxidative damage.

  7. Evaluation of ethyl tert-butyl ether biodegradation in a contaminated aquifer by compound-specific isotope analysis and in situ microcosms

    Energy Technology Data Exchange (ETDEWEB)

    Bombach, Petra, E-mail: petra.bombach@ufz.de [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Isodetect GmbH Leipzig, Deutscher Platz 5b, D-04103 Leipzig (Germany); Nägele, Norbert [Kuvier the Biotech Company S.L., Ctra. N-I, p.k. 234–P.E. INBISA 23" a, E-09001 Burgos (Spain); Rosell, Mònica [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristallografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), C/Martí i Franquès s/n, 08028 Barcelona (Spain); Richnow, Hans H. [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Fischer, Anko [Isodetect GmbH Leipzig, Deutscher Platz 5b, D-04103 Leipzig (Germany)

    2015-04-09

    Highlights: • In situ biodegradation of ETBE was investigated in a fuel contaminated aquifer. • Degradation was studied by CSIA and in situ microcosms in combination with TLFA-SIP. • ETBE was degraded when ETBE was the main groundwater contaminant. • ETBE was also degraded in the presence of BTEX and MTBE. • Hydrochemical analysis indicated aerobic and anaerobic ETBE biodegradation. - Abstract: Ethyl tert-butyl ether (ETBE) is an upcoming groundwater pollutant in Europe whose environmental fate has been less investigated, thus far. In the present study, we investigated the in situ biodegradation of ETBE in a fuel-contaminated aquifer using compound-specific stable isotope analysis (CSIA), and in situ microcosms in combination with total lipid fatty acid (TLFA)-stable isotope probing (SIP). In a first field investigation, CSIA revealed insignificant carbon isotope fractionation, but low hydrogen isotope fractionation of up to +14‰ along the prevailing anoxic ETBE plume suggesting biodegradation of ETBE. Ten months later, oxygen injection was conducted to enhance the biodegradation of petroleum hydrocarbons (PH) at the field site. Within the framework of this remediation measure, in situ microcosms loaded with [{sup 13}C{sub 6}]-ETBE (BACTRAP{sup ®}s) were exposed for 119 days in selected groundwater wells to assess the biodegradation of ETBE by TLFA-SIP under the following conditions: (i) ETBE as main contaminant; (ii) ETBE as main contaminant subjected to oxygen injection; (iii) ETBE plus other PH; (iv) ETBE plus other PH subjected to oxygen injection. Under all conditions investigated, significant {sup 13}C-incorporation into microbial total lipid fatty acids extracted from the in situ microcosms was found, providing clear evidence of ETBE biodegradation.

  8. Whole-Genome Analysis of the Methyl tert-Butyl Ether-Degrading Beta-Proteobacterium Methylibium petroleiphilum PM1▿ †

    Science.gov (United States)

    Kane, Staci R.; Chakicherla, Anu Y.; Chain, Patrick S. G.; Schmidt, Radomir; Shin, Maria W.; Legler, Tina C.; Scow, Kate M.; Larimer, Frank W.; Lucas, Susan M.; Richardson, Paul M.; Hristova, Krassimira R.

    2007-01-01

    Methylibium petroleiphilum PM1 is a methylotroph distinguished by its ability to completely metabolize the fuel oxygenate methyl tert-butyl ether (MTBE). Strain PM1 also degrades aromatic (benzene, toluene, and xylene) and straight-chain (C5 to C12) hydrocarbons present in petroleum products. Whole-genome analysis of PM1 revealed an ∼4-Mb circular chromosome and an ∼600-kb megaplasmid, containing 3,831 and 646 genes, respectively. Aromatic hydrocarbon and alkane degradation, metal resistance, and methylotrophy are encoded on the chromosome. The megaplasmid contains an unusual t-RNA island, numerous insertion sequences, and large repeated elements, including a 40-kb region also present on the chromosome and a 29-kb tandem repeat encoding phosphonate transport and cobalamin biosynthesis. The megaplasmid also codes for alkane degradation and was shown to play an essential role in MTBE degradation through plasmid-curing experiments. Discrepancies between the insertion sequence element distribution patterns, the distributions of best BLASTP hits among major phylogenetic groups, and the G+C contents of the chromosome (69.2%) and plasmid (66%), together with comparative genome hybridization experiments, suggest that the plasmid was recently acquired and apparently carries the genetic information responsible for PM1's ability to degrade MTBE. Comparative genomic hybridization analysis with two PM1-like MTBE-degrading environmental isolates (∼99% identical 16S rRNA gene sequences) showed that the plasmid was highly conserved (ca. 99% identical), whereas the chromosomes were too diverse to conduct resequencing analysis. PM1's genome sequence provides a foundation for investigating MTBE biodegradation and exploring the genetic regulation of multiple biodegradation pathways in M. petroleiphilum and other MTBE-degrading beta-proteobacteria. PMID:17158667

  9. Oxidation of Commercial Petronas Diesel with Tert-Butyl Hydroperoxide Over Poly molybdate Alumina Supported Catalyst Modified With Alkaline Earth Metals

    International Nuclear Information System (INIS)

    Wan Nazwanie Wan Abdullah; Rusmidah Ali; Wan Azlee Wan Abu Bakar

    2016-01-01

    Due to strict environmental legislation for ultra-low sulfur diesel fuels, increasing technical and operational challenges are imposed to conventional hydrodesulfurization (HDS) technology. Therefore, catalytic oxidative desulfurization (Cat-ODS) has been suggested to be an alternative method to replace a conventional method which is hydrodesulfurization. In this study, catalytic oxidation of commercial diesel was performed using an oil-soluble oxidant, tert-butyl hydroperoxide (TBHP), over poly molybdate supported on alumina MoO_3-PO_4/ Al_2O_3 catalyst. A commercial Petronas diesel with 440 ppm of total sulfur was employed to evaluate the elimination of sulfur compounds. Besides, the percentage of sulfur removal was measured by (GC-FPD). Alkaline earth metals, such as Calcium (Ca), Barium (Ba) and Strontium (Sr) were introduced on the surface of MoO_3-PO_4/ Al_2O_3. The results showed that the catalytic activity decreased in the order, Ca/ MoO_3-PO_4/ Al_2O_3>Sr/ MoO_3-PO_4/ Al_2O_3> Ba/ MoO_3-PO_4/ Al_2O_3. The Ca/ MoO_3-PO_4/ Al_2O_3 catalyst was characterized by XRD and FESEM. XRD results showed that the best catalyst was highly amorphous while FESEM micrograph illustrated an aggregation and agglomeration of various particle sizes. The catalytic activity of Ca/ MoO_3-PO_4/ Al_2O_3 catalyst with various Ca/ Mo ratios were also studied. When the Ca/ Mo ratio was 15:85, the sulfur removal was the highest (79 %) at 45 degree Celsius, 30 min and O/ S molar ratio 3.0 with solvent = dimethylformamide (DMF), diesel/ solvent ratio = 1.0. (author)

  10. Evaluation of ethyl tert-butyl ether biodegradation in a contaminated aquifer by compound-specific isotope analysis and in situ microcosms

    International Nuclear Information System (INIS)

    Bombach, Petra; a, E-09001 Burgos (Spain))" data-affiliation=" (Kuvier the Biotech Company S.L., Ctra. N-I, p.k. 234–P.E. INBISA 23a, E-09001 Burgos (Spain))" >Nägele, Norbert; Rosell, Mònica; Richnow, Hans H.; Fischer, Anko

    2015-01-01

    Highlights: • In situ biodegradation of ETBE was investigated in a fuel contaminated aquifer. • Degradation was studied by CSIA and in situ microcosms in combination with TLFA-SIP. • ETBE was degraded when ETBE was the main groundwater contaminant. • ETBE was also degraded in the presence of BTEX and MTBE. • Hydrochemical analysis indicated aerobic and anaerobic ETBE biodegradation. - Abstract: Ethyl tert-butyl ether (ETBE) is an upcoming groundwater pollutant in Europe whose environmental fate has been less investigated, thus far. In the present study, we investigated the in situ biodegradation of ETBE in a fuel-contaminated aquifer using compound-specific stable isotope analysis (CSIA), and in situ microcosms in combination with total lipid fatty acid (TLFA)-stable isotope probing (SIP). In a first field investigation, CSIA revealed insignificant carbon isotope fractionation, but low hydrogen isotope fractionation of up to +14‰ along the prevailing anoxic ETBE plume suggesting biodegradation of ETBE. Ten months later, oxygen injection was conducted to enhance the biodegradation of petroleum hydrocarbons (PH) at the field site. Within the framework of this remediation measure, in situ microcosms loaded with [ 13 C 6 ]-ETBE (BACTRAP ® s) were exposed for 119 days in selected groundwater wells to assess the biodegradation of ETBE by TLFA-SIP under the following conditions: (i) ETBE as main contaminant; (ii) ETBE as main contaminant subjected to oxygen injection; (iii) ETBE plus other PH; (iv) ETBE plus other PH subjected to oxygen injection. Under all conditions investigated, significant 13 C-incorporation into microbial total lipid fatty acids extracted from the in situ microcosms was found, providing clear evidence of ETBE biodegradation

  11. Solution processable 2-(trityloxy)ethyl and tert-butyl group containing amorphous molecular glasses of pyranylidene derivatives with light-emitting and amplified spontaneous emission properties

    Science.gov (United States)

    Zarins, Elmars; Vembris, Aivars; Misina, Elina; Narels, Martins; Grzibovskis, Raitis; Kokars, Valdis

    2015-11-01

    Small organic molecules with incorporated 4H-pyran-4-ylidene (pyranylidene) fragment as the π-conjugation system which bonds the electron acceptor fragment (A) with electron donor part (D) in the molecule - also well known as derivatives of 4-(dicyano-methylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran (DCM) laser dye-have attracted considerable attention of scientists as potential new generation materials for organic photonics and molecular electronics due to their low-cost fabrication possibility, flexibility and low-weight. Six glassy derivatives of 4H-pyran-4-ylidene (pyranylidene) with attached bulky 2-(trityloxy)ethyl and tert-butyl groups are described in this report. Almost all of the synthesized compounds form good optical quality transparent amorphous films from volatile organic solvents and could be obtained in good yields up to 75%. Their light emission in solution and thin solid films is in the range of 600-700 nm, they are thermally stable and show glass transition in the range of 108-158 °C. The amplified spontaneous emission threshold values of the neat films of the glassy pyranylidene derivatives vary from 155 to 450 μJ/cm2 and their HOMO and LUMO energy levels are between of those of tris(8-hydroxy quinolinato) aluminum (Alq3). The photoluminescence quantum yields of the glassy compounds are in the range from 1% to about 7.7% and their electroluminescence properties have been investigated. Therefore, glassy pyranylidene derivatives could be a very potential low-cost solution processable materials for Alq3 hosted light-amplification and light-emitting application studies.

  12. Solid binary mixtures of neopentanol with tert-Butyl chloride and carbon tetrachloride studied by thermal, X-ray and dielectric techniques

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, Girish; Murthy, S.S.N., E-mail: ssnm0700@gmail.com

    2016-05-10

    Highlights: • DSC, dielectric and X-ray measurements have been done on TBC-NPOH and CTC-NPOH. • The results show the formation of solid solution for concentrations 0.7 ≤ x{sub m} ≤ 0.9. • A primary α-process and two sub-T{sub g} processes are found for TBC-NPOH. • For CTC-NPOH only one sub-T{sub g} process is found. • All the three sub-T{sub g} processes are Johari–Goldstein type. - Abstract: The binary mixtures of Neopentanol (NPOH) with tert-Butyl chloride (TBC) and Carbon tetrachloride (CTC), have been studied using Differential Scanning Calorimetry, Dielectric spectroscopy and X-ray diffraction techniques. The results indicate the formation of the solid solutions. The crystalline solid thus formed is found to be orientationally disordered and supercools easily to form glassy crystal for mole fraction of NPOH in the range of 0.7–0.9. The T{sub g} values are in the range of 140–147 K. In the dielectric study, a primary α-process and two sub-T{sub g} processes are found for TBC-NPOH, whereas for CTC-NPOH only one sub-T{sub g} process is found. The dielectric spectra of α- process follows the Havriliak–Negami equation. The sub-T{sub g} processes follow the Cole–Cole equation, and are found to be of Johari–Goldstein type, indicating intermolecular nature.

  13. Electronic structure and electron dynamics at an organic molecule/metal interface: interface states of tetra-tert-butyl-imine/Au(111)

    International Nuclear Information System (INIS)

    Hagen, Sebastian; Wolf, Martin; Tegeder, Petra; Luo Ying; Haag, Rainer

    2010-01-01

    Time- and angle-resolved two-photon photoemission (2PPE) spectroscopies have been used to investigated the electronic structure, electron dynamics and localization at the interface between tetra-tert-butyl imine (TBI) and Au(111). At a TBI coverage of one monolayer (ML), the two highest occupied molecular orbitals, HOMO and HOMO-1, are observed at an energy of -1.9 and -2.6 eV below the Fermi level (E F ), respectively, and coincide with the d-band features of the Au substrate. In the unoccupied electronic structure, the lowest unoccupied molecular orbital (LUMO) has been observed at 1.6 eV with respect to E F . In addition, two delocalized states that arise from the modified image potential at the TBI/metal interface have been identified. Their binding energies depend strongly on the adsorption structure of the TBI adlayer, which is coverage dependent in the submonolayer (≤1 ML) regime. Thus the binding energy of the lower interface state (IS) shifts from 3.5 eV at 1.0 ML to 4.0 eV at 0.5 ML, which is accompanied by a pronounced decrease in its lifetime from 100 fs to below 10 fs. This is a result of differences in the wave function overlap with electronic states of the Au(111) substrate at different binding energies. This study shows that in order to fully understand the electronic structure of organic adsorbates at metal surfaces, not only adsorbate- and substrate-induced electronic states have to be considered but also ISs, which are the result of a potential formed by the interaction between the adsorbate and the substrate.

  14. Structure of the mercury(II mixed-halide (Br/Cl complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzo[d]imidazole

    Directory of Open Access Journals (Sweden)

    Varsha Rani

    2017-03-01

    Full Text Available The mercury(II complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole, namely catena-poly[[dihalogenidomercury(II]-μ-2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole-κ2N3:N3′], [HgBr1.52Cl0.48(C34H42N4], 2, has a polymeric structure bridging via the N atoms from the benzimidazole moieties of the ligand. The compound crystallizes in the orthorhombic space group Pca21 and is a racemic twin [BASF = 0.402 (9]. The geometry around the HgII atom is distorted tetrahedral, with the HgII atom coordinated to two N atoms, one Br atom, and a fourth coordination site is occupied by a mixed halide (Br/Cl. For the two ligands in the asymmetric unit, there is disorder with one of the two tert-butyl groups and benzimidazole moieties showing twofold disorder, with occupancy factors of 0.57 (2:0.43 (2 for the tert-butyl group and 0.73 (3:0.27 (3 for the benzimidazole group. In addition, there is threefold disorder for two of the four n-pentyl groups, with occupancy factors of 0.669 (4:0.177 (4:0.154 (4 and 0.662 (4:0.224 (4:0.154 (4, respectively. The molecules form a one-dimensional helical polymer propagating in the b-axis direction. The helices are held together by intra-strand C—H...Br and C—H...Cl interactions. Each strand is further linked by inter-strand C—H...Br and C—H...Cl interactions. In addition, there are weak C—H...N inter-strand interactions which further stabilize the structural arrangement.

  15. Ground-State Distortion in N-Acyl-tert-butyl-carbamates (Boc) and N-Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N-C Cross-Coupling.

    Science.gov (United States)

    Szostak, Roman; Shi, Shicheng; Meng, Guangrong; Lalancette, Roger; Szostak, Michal

    2016-09-02

    Amide N-C(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*C═O resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N-C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N-C(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N-C(O) amide bond cleavage as a key step.

  16. Measurement of critical temperatures and critical pressures for binary mixtures of methyl tert-butyl ether (MTBE) + alcohol and MTBE + alkane

    International Nuclear Information System (INIS)

    Han, Kewei; Xia, Shuqian; Ma, Peisheng; Yan, Fangyou; Liu, Tao

    2013-01-01

    Highlights: • The critical properties of seven binary mixtures related to gasoline were measured. • The critical properties of the five systems containing MTBE were reported for the first time. • Binary interaction parameters were fitted by experimental data using PR EOS with Wong–Sandler mixing rule. • Redlich–Kister equation was used to correlate the experimental data. -- Abstract: A set of high-pressure view apparatus was designed for determining the critical properties of chemicals. In order to check the reliability of the apparatus, the critical temperatures (T c ) and critical pressures (P c ) of pure n-heptane, cyclohexane, methanol, ethanol, 1-propanol, methyl tert-butyl ether (MTBE), and binary mixture n-hexane + ethanol were measured. The experimental data were in good agreement with the literature data, which proves the reliability of the apparatus used in the work. The critical temperatures and critical pressures of five binary mixtures containing gasoline additive (MTBE + n-heptane, MTBE + cyclohexane, MTBE + methanol, MTBE + ethanol, MTBE + 1-propanol) were measured using the high-pressure view cell with visual observation. The critical temperatures and critical pressures for the five binary mixtures were all reported for the first time. In addition, the critical temperatures and critical pressures of the binary mixture n-heptane + cyclohexane (two of main components in gasoline) were also measured. All the critical lines for the mixtures studied are continuous which connect the critical points of the two pure components, indicating their phase diagrams belong to type I proposed by Scott and van Konynenburg. The critical points of these systems were calculated by the Peng–Robinson equation of state with the Wong–Sandler mixing rule. This model could calculate the critical properties of the mixtures well with the binary interaction parameter k ij obtained by fitting the experimental critical data. And the experimental data were all

  17. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium

    International Nuclear Information System (INIS)

    Serrano V, E. C.

    2011-01-01

    The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO 3 -3.5 NaNO 3 ) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10 -4 M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10 -4 M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO 2 ) 2 B 8 bL 8 (NO 3 ) 4 (H 2 O) 4 CHCl 3 (CH 3 OH) 3 the methanol molecules come from its purification. It is proposed that B 8 bL 8 calixarene in chloroform medium is a good extractant for the treatment of nuclear wastes or

  18. Linear free energy relationships in heterogeneous catalysis--13. The dehydration of aliphatic alcohols over silica-alumina. [N-butyl alcohol, sec. -butyl or isopropyl alcohol, tert. -butyl alcolol

    Energy Technology Data Exchange (ETDEWEB)

    Take, J; Matsumoto, T; Yoneda, Y

    1978-01-01

    The dehydration of n-butyl alcohol at 120/sup 0/-166/sup 0/C, sec.-butyl or isopropyl alcohol at 100/sup 0/-145/sup 0/C, and tert.-butyl alcohol at 54/sup 0/-80/sup 0/C, over silica/alumina catalyst was zero order in alcohol at 0.01-0.1 atm, and the activation energies were 35.3, 31.7, 32.0, and 29.9 kcal/mol, respectively. The zero-order rate constants were mainly affected by the activation energies since the preexponential factors varied little except for tert.-butyl alcohol. A linear relationship was found between the activation energy or the logarithm of the zero-order rate constant and the heterolytic bond dissociation energy for the carbon-oxygen bond in alcohols D(R/sup +/OH/sup -/). The activation energy increased and the rate constant decreased with increasing D(R/sup +/OH/sup -/). The results indicate that dehydration is E1 over this catalyst, but a similar correlation was observed based on published data for dehydration over alumina, which follows an E2 mechanism, indicating that heterolytic cleavage of the C-O bond is rate-determining in both mechanisms.

  19. Thermally Activated Paramagnets from Diamagnetic Polymers of Biphenyl-3,5-diyl Bis(tert-butyl Nitroxides Carrying Methyl and Fluoro Groups at the 2’- and 5’-Positions

    Directory of Open Access Journals (Sweden)

    Toru Yoshitake

    2016-03-01

    Full Text Available Three new biradicals—2’,5’-dimethyl-, 2’-fluoro-5’-methyl-, and 5’-fluoro-2’-methyl- biphenyl-3,5-diyl bis(tert-butyl nitroxides—were synthesized. The magnetic susceptibility measurements revealed their diamagnetism below and around room temperature. The nitroxide groups are located close to each other in an intermolecular fashion to form a weakly covalent head-to-tail (NO2 ring. Biradical molecules are connected on both radical sites, constructing a diamagnetic chain. The dimethyl derivative underwent a structural phase transition at 83 °C, clarified via differential scanning calorimetry and powder X-ray diffraction, and a paramagnetic solid phase with S = 1 irreversibly appeared. The other analogues exhibited a similar irreversible upsurge of the magnetic susceptibility on heating, but the transition was characterized as the melting.

  20. Improving the Safety of Lithium-Ion Battery via a Redox Shuttle Additive 2,5-Di- tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB).

    Science.gov (United States)

    Leonet, Olatz; Colmenares, Luis C; Kvasha, Andriy; Oyarbide, Mikel; Mainar, Aroa R; Glossmann, Tobias; Blázquez, J Alberto; Zhang, Zhengcheng

    2018-03-21

    2,5-Di- tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) is studied as a redox shuttle additive for overcharge protection for a 1.5 Ah graphite/C-LFP lithium-ion pouch cell for the first time. The electrochemical performance demonstrated that the protecting additive remains inert during the extended standard cycling for 4000 cycles. When a 100% overcharge is introduced in the charging protocol, the baseline cell fails rapidly during the first abusive event, whereas the cell containing DBBB additive withstands 700 overcharge cycles with 87% capacity retention and no gas evolution or cell swelling was observed. It is the first time the effectiveness of the DBBB as overcharge protection additive in a large pouch cell format is demonstrated.

  1. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene; Synthese et proprietes complexantes vis-a-vis de l'ion uranyle de derives carboxyliques du p-tert-butyl-calix[6]arene

    Energy Technology Data Exchange (ETDEWEB)

    Souane, R

    2005-03-15

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO{sub 2}{sup 2+} form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO{sub 2}) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO{sub 2}L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid ({delta}log{beta}110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO{sub 2}{sup 2+}. This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23

  2. Occurrence and temporal variability of methyl tert-butyl ether (MTBE) and other volatile organic compounds in select sources of drinking water : results of the focused survey

    Science.gov (United States)

    Delzer, Gregory C.; Ivahnenko, Tamara

    2003-01-01

    The large-scale use of the gasoline oxygenate methyl tert-butyl ether (MTBE), and its high solubility, low soil adsorption, and low biodegradability, has resulted in its detection in ground water and surface water in many places throughout the United States. Studies by numerous researchers, as well as many State and local environmental agencies, have discovered high levels of MTBE in soils and ground water at leaking underground gasoline-storage-tank sites and frequent occurrence of low to intermediate levels of MTBE in reservoirs used for both public water supply and recreational boating.In response to these findings, the American Water Works Association Research Foundation sponsored an investigation of MTBE and other volatile organic compounds (VOCs) in the Nation's sources of drinking water. The goal of the investigation was to provide additional information on the frequency of occurrence, concentration, and temporal variability of MTBE and other VOCs in source water used by community water systems (CWSs). The investigation was completed in two stages: (1) reviews of available literature and (2) the collection of new data. Two surveys were associated with the collection of new data. The first, termed the Random Survey, employed a statistically stratified design for sampling source water from 954 randomly selected CWSs. The second, which is the focus of this report, is termed the Focused Survey, which included samples collected from 134 CWS source waters, including ground water, reservoirs, lakes, rivers, and streams, that were suspected or known to contain MTBE. The general intent of the Focused Survey was to compare results with the Random Survey and provide an improved understanding of the occurrence, concentration, temporal variability, and anthropogenic factors associated with frequently detected VOCs. Each sample collected was analyzed for 66 VOCs, including MTBE and three other ether gasoline oxygenates (hereafter termed gasoline oxygenates). As part of

  3. Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al{sub 2}O{sub 3} supported copper and gold nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ndolomingo, Matumuene Joe; Meijboom, Reinout, E-mail: rmeijboom@uj.ac.za

    2017-03-15

    Highlights: • Cu and Au on γ-Al{sub 2}O{sub 3} catalysts were prepared and characterized. • Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide in the absence of any solvent using the prepared catalysts. • The as prepared catalysts exhibited good performance in terms of conversion and selectivity towards benzaldehyde. • The kinetics of the reaction was investigated; k{sub app} was proportional to the amount of nano catalyst and oxidant present in the system. • The catalysts was recycled and reused with neither significant loss of activity nor selectivity. - Abstract: Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al{sub 2}O{sub 3} supported copper and gold nanoparticles. Li{sub 2}O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N{sub 2} absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol

  4. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene II. 3,3-Dimethyl-1,2-bis(trimethylsilyl)cyclopropene

    Science.gov (United States)

    Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2003-07-01

    The IR and Raman spectra of 3,3-dimethyl-1,2-bis(trimethylsilyl)cyclopropene (I) (synthesised using standard procedures) were measured in the liquid phase. Total geometry optimisation was performed at the HF/6-31G* level. The HF/6-31G*//HF/6-31G* quantum mechanical force field (QMFF) was calculated and used to determine the theoretical fundamental vibrational frequencies, their predicted IR intensities, Raman activities, and Raman depolarisation ratios. Using Pulay's scaling method and the theoretical molecular geometry, the QMFF of I was scaled by a set of scaling factors used previously for 3,3-dimethyl-1,2-bis(tert-butyl)cyclopropene (17 scale factors for a 105-dimensional problem). The scaled QMFF obtained was used to solve the vibrational problem. The quantum mechanical values of the Raman activities were converted to differential Raman cross sections. The figures for the experimental and theoretical Raman and IR spectra are presented. Assignments of the experimental vibrational spectra of I are given. They take into account the calculated potential energy distribution and the correlation between the estimations of the experimental IR and Raman intensities and Raman depolarisation ratios and the corresponding theoretical values (including Raman cross sections) calculated using the unscaled QMFF.

  5. Effects of intraperitoneal administration of the GABAB receptor positive allosteric modulator 2,6-di tert-butyl-4-(2-hydroxy-2,2-dimethyl-propyl)-phenol (CGP7930) on food intake in non-deprived rats.

    Science.gov (United States)

    Ebenezer, Ivor S

    2012-09-05

    γ-Aminobutyric acid-(B) (GABA(B)) receptor positive allosteric modulators (PAMs) act on an allosteric site on the GABA(B) receptor to potentiate the effects of GABA and GABA(B) receptor agonists. It has previously been demonstrated that the GABA(B) receptor agonist baclofen increases food intake in non-deprived rats. The aim of this study was to investigate whether the GABA(B) receptor PAM 2,6-di tert-butyl-4-(2-hydroxy-2,2-dimethyl-propyl)-phenol (CGP7930) would (i) increase food intake, and (ii) potentiate the hyperphagic effects of baclofen in rats. In Experiment 1, the effects of intraperitoneal (i.p.) administration of CGP7930 (1, 6 and 12 mg/kg) was investigated on food intake in non-deprived male Wistar rats. The 12 mg/kg dose of CGP7930 significantly increased cumulative food intake 30, 60 and 120 min (PGABA and GABA(B) receptor agonists by allosteric modulation of the GABA(B) receptor. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. μ-Carbonato-κ(4) O,O':O',O''-bis-{[2'-(di-tert-butyl-phosphan-yl)biphenyl-2-yl-κ(2) P,C (1)]palladium(II)} dichloro-methane monosolvate.

    Science.gov (United States)

    Muller, Alfred; Holzapfel, Cedric W

    2012-12-01

    The title compound, [(μ2-CO3){Pd(P(t-C4H9)2(C12H8)}2]·CH2Cl2, the first CO3-bridged palladium dimer complex reported to date, was obtained while preparing the Pd(0) complex with (2-biphen-yl)P( (t) Bu)2. In the crystal, each palladium dimer is accompanied by a dichloro-methane solvent mol-ecule. Coordination of the carbonate and chelated phosphane ligands gives distorted square-planar environments at the Pd atoms. Important geometrical parameters include Pd-P(av.) = 2.2135 (4) Å, Pd-C(av.) = 1.9648 (16) Å and P-Pd-C = 84.05 (5) and 87.98 (5)°, and O-Pd-O' = 60.56 (4) and 61.13 (4)°. Bonding with the carbonate O atoms shows values of 2.1616 (11) and 2.1452 (11) Å for the Pd-O-Pd bridge, whereas other Pd-O distances are slightly longer at 2.2136 (11) and 2.1946 (11) Å. One of the tert-butyl groups is disordered over two set of sites with an occupancy ratio of 0.723 (6):0.277 (6). Weak C-H⋯O interactions are observed propagating the molecules along the [100] direction.

  7. Stable carbon and hydrogen isotope analysis of methyl tert-butyl ether and tert-amyl methyl ether by purge and trap-gas chromatography-isotope ratio mass spectrometry: method evaluation and application.

    Science.gov (United States)

    Kujawinski, Dorothea M; Stephan, Manuel; Jochmann, Maik A; Krajenke, Karen; Haas, Joe; Schmidt, Torsten C

    2010-01-01

    In order to monitor the behaviour of contaminants in the aqueous environment effective enrichment techniques often have to be employed due to their low concentrations. In this work a robust and sensitive purge and trap-gas chromatography-isotope ratio mass spectrometry method for carbon and hydrogen isotope analysis of fuel oxygenates in water is presented. The method evaluation included the determination of method detection limits, accuracy and reproducibility of deltaD and delta(13)C values. Lowest concentrations at which reliable delta(13)C values could be determined were 5 microg L(-1) and 28 microg L(-1) for TAME and MTBE, respectively. Stable deltaD values for MTBE and TAME could be achieved for concentrations as low as 25 and 50 microg L(-1). Good long-term reproducibility of delta(13)C and deltaD values was obtained for all target compounds. But deltaD values varying more than 5 per thousand were observed using different thermal conversion tubes. Thus, a correction of deltaD values in the analysis of groundwater samples was necessary to guarantee comparability of the results. The applicability of this method was shown by the analysis of groundwater samples from a gasoline contaminated site. By two dimensional isotope analysis two locations within this site were identified at which anaerobic and aerobic degradation of methyl tert-butyl ether occurred.

  8. Vibrational Spectroscopy Investigation Using Ab Initio and Density Functional Theory Analysis on the Structure of tert-Butyl 3a-Chloroperhydro-2,6a-epoxyoxireno[e]isoindole-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Hakan Arslan

    2013-01-01

    Full Text Available The molecular structure, vibrational frequencies, and infrared intensities of the tert-butyl 3a-chloroperhydro-2,6a-epoxyoxireno[e]isoindole-5-carboxylate were calculated by the HF and DFT (BLYP and B3LYP methods using 6-31G(d and 6-31G(d,p basis sets. The FT infrared spectrum of the solid sample was measured under standard condition. We obtained two stable conformers for the title compound; however Conformer 1 is approximately 0.2 kcal/mol more stable than the Conformer 2. The comparison of the theoretical and experimental geometry of the title compound shows that the X-ray parameters fairly well reproduce the geometry of Conformer 2. Comparison of the observed fundamental vibrational frequencies of the title molecule and calculated results by HF and DFT methods indicates that B3LYP is superior for molecular vibrational problems. The harmonic vibrations computed by the B3LYP/6-31G(d,p method are in a good agreement with the observed IR spectral data. Theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions (PEDs using VEDA 4 program.

  9. FT-IR and Raman vibrational analysis, B3LYP and M06-2X simulations of 4-bromomethyl-6-tert-butyl-2H-chromen-2-one

    Science.gov (United States)

    Sert, Yusuf; Puttaraju, K. B.; Keskinoğlu, Sema; Shivashankar, K.; Ucun, Fatih

    2015-01-01

    In this study, the experimental and theoretical vibrational frequencies of a newly synthesized bacteriostatic and anti-tumor molecule namely, 4-bromomethyl-6-tert-butyl-2H-chromen-2-one have been investigated. The experimental FT-IR (4000-400 cm-1) and Raman spectra (4000-100 cm-1) of the compound in solid phase have been recorded. The theoretical vibrational frequencies and optimized geometric parameters have been calculated using density functional theory (DFT/B3LYP: Becke, 3-parameter, Lee-Yang-Parr and DFT/M06-2X: highly parametrized, empirical exchange correlation function) with 6-311++G(d, p) basis set by Gaussian 03 software, for the first time. The assignments of the vibrational frequencies have been done by potential energy distribution (PED) analysis using VEDA 4 software. The theoretical optimized geometric parameters and vibrational frequencies have been found to be in good agreement with the corresponding experimental data and results in the literature. In addition, the highest occupied molecular orbital (HOMO) energy, the lowest unoccupied molecular orbital (LUMO) energy and the other related molecular energy values of the compound have been investigated using the same theoretical calculations.

  10. Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

    Science.gov (United States)

    Kasumov, Veli T; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

    2013-03-01

    New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μ(B) per Cu(II)) and 6 (2.79 μ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. A Study of the Curing and Flammability Properties of Bisphenol A Epoxy Diacrylate Resin Utilizing a Novel Flame Retardant Monomer, bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl Phosphate

    Directory of Open Access Journals (Sweden)

    Syang-Peng Rwei

    2017-02-01

    Full Text Available A UV-curable, flame-retardant monomer, DAPP (bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl-phosphate, was synthesized based on BPDCP (4-tert-butylphenyl-dichloro phosphate and HEA (2-hydroxy ethyl acrylate. DAPP was blended with regular bisphenol A epoxy acrylate (BAEA in various ratios to yield various phosphorus contents. The TGA-IR (thermogravimetric analyzer interface with an infrared spectrometer results demonstrate that compounding 30 mol % DAPP with BAEA significantly reduced the amount of released CO gas. In contrast, the peak intensity of CO2 is independent of phosphorus content. The limiting oxygen index (LOI, reaching the saturated value of 26, and the heat release rate (HRR measured using a cone-calorimeter, 156.43 KW/m2, confirm the saturation point when 30 mol % DAPP was compounded into BAEA. A study of the kinetics of pyrolysis reveals that Ea decreases as the phosphorus content increases. Both the TGA-IR and pyrolysis results reveal that the phosphorus compound DAPP is easily decomposed during the initial stage of burning to form an insulating layer, which inhibits further burning of the resin and the consequent release of other flammable gases.

  12. γ-aminobutyric acidA (GABAA) receptor regulates ERK1/2 phosphorylation in rat hippocampus in high doses of Methyl Tert-Butyl Ether (MTBE)-induced impairment of spatial memory

    International Nuclear Information System (INIS)

    Zheng Gang; Zhang Wenbin; Zhang Yun; Chen Yaoming; Liu Mingchao; Yao Ting; Yang Yanxia; Zhao Fang; Li Jingxia; Huang Chuanshu; Luo Wenjing; Chen Jingyuan

    2009-01-01

    Experimental and occupational exposure to Methyl Tert-Butyl Ether (MTBE) has been reported to induce neurotoxicological and neurobehavioral effects, such as headache, nausea, dizziness, and disorientation, etc. However, the molecular mechanisms involved in MTBE-induced neurotoxicity are still not well understood. In the present study, we investigated the effects of MTBE on spatial memory and the expression and function of GABA A receptor in the hippocampus. Our results demonstrated that intraventricular injection of MTBE impaired the performance of the rats in a Morris water maze task, and significantly increased the expression of GABA A receptor α1 subunit in the hippocampus. The phosphorylation of ERK1/2 decreased after the MTBE injection. Furthermore, the decreased ability of learning and the reduction of phosphorylated ERK1/2 level of the MTBE-treated rats was partly reversed by bicuculline injected 30 min before the training. These results suggested that MTBE exposure could result in impaired spatial memory. GABA A receptor may play an important role in the MTBE-induced impairment of learning and memory by regulating the phosphorylation of ERK in the hippocampus.

  13. Difunctionalization of alkenes with iodine and tert-butyl hydroperoxide (TBHP) at room temperature for the synthesis of 1-(tert-butylperoxy)-2-iodoethanes.

    Science.gov (United States)

    Wang, Hao; Chen, Cui; Liu, Weibing; Zhu, Zhibo

    2017-01-01

    We developed a direct vicinal difunctionalization of alkenes with iodine and TBHP at room temperature. This iodination and peroxidation in a one-pot synthesis produces 1-( tert -butylperoxy)-2-iodoethanes, which are inaccessible through conventional synthetic methods. This method generates multiple radical intermediates in situ and has excellent regioselectivity, a broad substrate scope and mild conditions. The iodine and peroxide groups of 1-( tert -butylperoxy)-2-iodoethanes have several potential applications and allow further chemical modifications, enabling the preparation of synthetically valuable molecules.

  14. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene IV. 3,3-Dimethyl-1,2-bis(trimethylgermyl)cyclopropene

    Science.gov (United States)

    Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2003-06-01

    The infrared (IR) and Raman spectra of 3,3-dimethyl-1,2-bis(trimethylgermyl)cyclopropene (I) were measured in the liquid phase. Total geometry optimisation was performed at the HF/6-31G* level. The HF/6-31G*//HF6-31G* quantum mechanical force field (QMFF) was calculated and used to determine the theoretical fundamental vibrational frequencies, their predicted IR intensities, Raman activities, and Raman depolarisation ratios. Using Pulay's scaling method and the theoretical molecular geometry, the QMFF of I was scaled by a set of scaling factors comprised of elements transferred from the sets used to correct the QMFF's of 3,3-dimethylbutene-1, and 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene (17 scale factors for a 105-dimensional problem). This set of scale factors was used previously to correct the QMFF of 3,3-dimethyl-1,2-bis(tert-butyl)cyclopropene and 3,3-dimethyl-1,2-bis(trimethylsilyl)cyclopropene. The scaled QMFF obtained was used to solve the vibrational problem. Differential Raman cross-sections were calculated using the quantum mechanical values of the Raman activities. The appropriate theoretical spectrograms for the Raman and IR spectra of I were constructed. Assignments of the experimental vibrational spectra of I are given. They take into account the calculated potential energy distributions and the correlation between the estimations of the experimental IR and Raman intensities and Raman depolarisation ratios and the corresponding theoretical values calculated using the unscaled QMFF.

  15. In vitro and in vivo effect of 2,6-Di-tert-butyl-4-methylphenol as an antibiofilm agent against quorum sensing mediated biofilm formation of Vibrio spp.

    Science.gov (United States)

    Santhakumari, Sivasubramanian; Jayakumar, Rengarajan; Logalakshmi, Ravichandran; Prabhu, Narayanan Marimuthu; Abdul Nazar, Abdul Kuthus; Karutha Pandian, Shunmugiah; Veera Ravi, Arumugam

    2018-05-25

    This study unveils the in vitro and in vivo antibiofilm potential of 2,6-Di-tert-butyl-4-methylphenol (DTBMP) from Chroococcus turgidus against Vibrio spp. In the preliminary study, cell free culture supernatant (CFCS) of C. turgidus inhibited the violacein production in biomarker strain Chromobacterium violaceum and its mutant strain CV026 in a dose dependent manner. The effective biofilm inhibitory concentration (BIC) of pure compound DTBMP from C. turgidus was identified as 250 μg/ml concentration in tested Vibrio species. Furthermore, DTBMP proved to effectively inhibit the bioluminescence production in V. harveyi and other biofilm related virulence traits such as exopolysaccharides (EPS) production, hydrophobicity index, swimming and swarming motility at its BIC concentration in three major pathogenic vibrios: V. harveyi, V. parahaemolyticus and V. vulnificus. The antibiofilm potential of DTBMP was validated through light, confocal laser scanning and scanning electron microscopic analyses. In addition, the non-bactericidal effect of DTBMP was determined through growth curve and 2,3-bis (2-methyloxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide (XTT) assay. Real-time PCR studies revealed the down-regulation of master quorum sensing (QS) regulator genes of V. harveyi such as luxR, luxS, luxP, luxQ and luxO on treatment with DTBMP. In vivo results confirmed that DTBMP augmented the survival rate of Litopenaeus vannamei larvae up to 75, 88 and 66% upon infection with V. harveyi, V. parahaemolyticus and V. vulnificus, respectively. The results of this study ascertain the promising effects of DTBMP as an antibiofilm agent, which could be positively explored to treat biofilm-associated vibrios infections in aquaculture. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. Quantum mechanical study and spectroscopic (FT-IR, FT-Raman, UV-Visible) study, potential energy surface scan, Fukui function analysis and HOMO-LUMO analysis of 3-tert-butyl-4-methoxyphenol by DFT methods.

    Science.gov (United States)

    Saravanan, S; Balachandran, V

    2014-09-15

    This study represents an integral approach towards understanding the electronic and structural aspects of 3-tert-butyl-4-methoxyphenol (TBMP). Fourier-transform Infrared (FT-IR) and Fourier-transform Raman (FT-Raman) spectra of TBMP was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) methods using 6-311++G (d,p) basis set. The most stable conformer of TBMP was identified from the computational results. The assignments of vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of TBMP have been discussed. The stability and charge delocalization of the molecule was studied by Natural Bond Orbital (NBO) analysis. UV-Visible spectrum and effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach with B3LYP/6-311++G (d,p) level of theory. The molecule orbital contributions are studied by density of energy states (DOSs). The reactivity sites are identified by mapping the electron density into electrostatic potential surface (MEP). Mulliken analysis of atomic charges is also calculated. The thermodynamic properties at different temperatures were calculated, revealing the correlations between standard heat capacities, standard entropy and standard enthalpy changes with temperatures. Global hardness, global softness, global electrophilicity and ionization potential of the title compound are determined. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    International Nuclear Information System (INIS)

    Arıcı, Mürsel; Zafer Yeşilel, Okan; Büyükgüngör, Orhan

    2017-01-01

    detection of acetone. Moreover, thermal and optical properties of the complexes were also studied. - Highlights: • Four new 2D and 3D coordination polymers with 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers. • The structural diversity depending on ligands and coordination number of metal centers. • Fluorescent sensor for the detection of acetone.

  18. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Arıcı, Mürsel, E-mail: marici@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Zafer Yeşilel, Okan [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Büyükgüngör, Orhan [Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun (Turkey)

    2017-05-15

    methanol could be used as a fluorescent sensor for the detection of acetone. Moreover, thermal and optical properties of the complexes were also studied. - Highlights: • Four new 2D and 3D coordination polymers with 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers. • The structural diversity depending on ligands and coordination number of metal centers. • Fluorescent sensor for the detection of acetone.

  19. Occurrence and implications of methyl tert-butyl ether and gasoline hydrocarbons in ground water and source water in the United States and in drinking water in 12 Northeast and Mid-Atlantic States, 1993-2002

    Science.gov (United States)

    Moran, Michael J.; Zogorski, John S.; Squillace, Paul J.

    2004-01-01

    The occurrence and implications of methyl tert-butyl ether (MTBE) and gasoline hydrocarbons were examined in three surveys of water quality conducted by the U.S. Geological Survey?one national-scale survey of ground water, one national-scale survey of source water from ground water, and one regional-scale survey of drinking water from ground water. The overall detection frequency of MTBE in all three surveys was similar to the detection frequencies of some other volatile organic compounds (VOCs) that have much longer production and use histories in the United States. The detection frequency of MTBE was higher in drinking water and lower in source water and ground water. However, when the data for ground water and source water were limited to the same geographic extent as drinking-water data, the detection frequencies of MTBE were comparable to the detection frequency of MTBE in drinking water. In all three surveys, the detection frequency of any gasoline hydrocarbon was less than the detection frequency of MTBE. No concentration of MTBE in source water exceeded the lower limit of U.S. Environmental Protection Agency's Drinking-Water Advisory of 20 ?g/L (micrograms per liter). One concentration of MTBE in ground water exceeded 20 ?g/L, and 0.9 percent of drinking-water samples exceeded 20 ?g/L. The overall detection frequency of MTBE relative to other widely used VOCs indicates that MTBE is an important concern with respect to ground-water management. The probability of detecting MTBE was strongly associated with population density, use of MTBE in gasoline, and recharge, and weakly associated with density of leaking underground storage tanks, soil permeability, and aquifer consolidation. Only concentrations of MTBE above 0.5 ?g/L were associated with dissolved oxygen. Ground water underlying areas with high population density, ground water underlying areas where MTBE is used as a gasoline oxygenate, and ground water underlying areas with high recharge has a greater

  20. tert-Butyl 2-(4-nitrophenoxyacetate

    Directory of Open Access Journals (Sweden)

    Qamar Ali

    2011-02-01

    Full Text Available In the title molecule, C12H15NO5, the nitrophenoxy portion is approximately planar (r.m.s. deviation = 0.034 Å and makes an angle of 84.8 (1° with respect to the –CH2–C(=O–O–C fragment. In the crystal, π–π stacking is observed between nearly parallel benzene rings of adjacent molecules, the centroid–centroid distance being 3.6806 (10 Å. Weak intermolecular C—H...O hydrogen bonding is present in the crystal structure.

  1. Solvent extraction of Ca2+, Ba2+, Cu2+, Zn2+, Cd2+, Pb2+, UO22+, Mn2+, Co2+ and Ni2+ into nitrobenzene using strontium dicarbol-lylcobaltate and tetra-tert-butyl p-tert-butylcalix[4]arene tetraacetate

    Directory of Open Access Journals (Sweden)

    E. MAKRLÍK

    2008-12-01

    Full Text Available The exchange extraction constants corresponding to the general equilibrium M2+(aq + SrL2+(nb D ML2+ (nb + Sr2+ (aq occurring in the two-phase water–nitrobenzene system (M2+ = Ca2+, Ba2+, Cu2+, Zn2+, Cd2+, Pb2+, UO22+, Mn2+, Co2+ or Ni2+; L = tetra-tert-butyl p-tert-butylcalix[4]arene tetraacetate; aq = aqueous phase; nb = nitrobenzene phase were evaluated from extraction experiments and -activity measurements. Furthermore, the stability constants of the ML2+ complexes in water saturated nitrobenzene were calculated; they were found to increase in the cation order Ba2+ < Mn2+ < Pb2+, Co2+ < Cu2+, Zn2+ < Cd2+, Ni2+ < UO22+ < Ca2+.

  2. Topological Substituent Descriptors

    Directory of Open Access Journals (Sweden)

    Mircea V. DIUDEA

    2002-12-01

    Full Text Available Motivation. Substituted 1,3,5-triazines are known as useful herbicidal substances. In view of reducing the cost of biological screening, computational methods are carried out for evaluating the biological activity of organic compounds. Often a class of bioactives differs only in the substituent attached to a basic skeleton. In such cases substituent descriptors will give the same prospecting results as in case of using the whole molecule description, but with significantly reduced computational time. Such descriptors are useful in describing steric effects involved in chemical reactions. Method. Molecular topology is the method used for substituent description and multi linear regression analysis as a statistical tool. Results. Novel topological descriptors, XLDS and Ws, based on the layer matrix of distance sums and walks in molecular graphs, respectively, are proposed for describing the topology of substituents linked on a chemical skeleton. They are tested for modeling the esterification reaction in the class of benzoic acids and herbicidal activity of 2-difluoromethylthio-4,6-bis(monoalkylamino-1,3,5-triazines. Conclusions. Ws substituent descriptor, based on walks in graph, satisfactorily describes the steric effect of alkyl substituents behaving in esterification reaction, with good correlations to the Taft and Charton steric parameters, respectively. Modeling the herbicidal activity of the seo of 1,3,5-triazines exceeded the models reported in literature, so far.

  3. Crystal structure of 4-tert-butyl-2-{2-[N-(3,3-dimethyl-2-oxobutyl-N-isopropylcarbamoyl]phenyl}-1-isopropyl-1H-imidazol-3-ium perchlorate

    Directory of Open Access Journals (Sweden)

    Olga V. Hordiyenko

    2015-02-01

    Full Text Available In the title salt, C26H40N3O2+·ClO4−, the positive charge of the organic cation is delocalized between the two N atoms of the imidazole ring. The C...;N bond distances are 1.338 (2 and 1.327 (3 Å. The substituents on the benzene ring are rotated almost orthogonal with respect to this ring due to the presence of the bulky isopropyl substituents. The dihedral angle between the benzene and imidazole rings is 75.15 (12°. Three of the O atoms of the anion are disordered over two sets of sites due to rotation around one of the O—Cl bonds. The ratio of the refined occupancies is 0.591 (14:0.409 (14. In the crystal, the cation and perchlorate anion are bound by an N—H...O hydrogen bond. In addition, the cation–anion pairs are linked into layers parallel to (001 by multiple weak C—H...O hydrogen bonds.

  4. Enterovirus inhibitory activity of C-8-tert-butyl substituted 4-aryl-6,7,8,9-tetrahydrobenzo[4,5]thieno[3,2-e][1,2,4]triazolo[4,3-a]pyrimidin-5(4H)-ones.

    Science.gov (United States)

    Kumar Biswas, Bishyajit; Malpani, Yashwardhan R; Ha, Neul; Kwon, Do-Hyun; Soo Shin, Jin; Kim, Hae-Soo; Kim, Chonsaeng; Bong Han, Soo; Lee, Chong-Kyo; Jung, Young-Sik

    2017-08-01

    Members of a series of 4-aryl-6,7,8,9-tetrahydrobenzo[4,5]thieno[3,2-e][1,2,4]triazolo[4,3-a]pyrimidin-5(4H)-ones (1, Fig. 2) were prepared and tested against representative enteroviruses including Human Coxsackievirus B1 (Cox B1), Human Coxsackievirus B3 (Cox B3), human Poliovirus 3 (PV3), human Rhinovirus 14 (HRV14), human Rhinovirus 21 (HRV 21) and human Rhinovirus 71 (HRV 71). The C-8-tert-butyl group on the tetrahydrobenzene ring in these substances was found to be crucial for their enterovirus activity. One member of this group, 1e, showed single digit micromolar activities (1.6-8.85μM) against a spectrum of viruses screened, and the highest selectivity index (SI) values for Cox B1 (>11.2), for Cox B3 (>11.5), and for PV3 (>51.2), respectively. In contrast, 1p, was the most active analog against the selected HRVs (1.8-2.6μM), and showed the highest selectivity indices among the group of compounds tested. The SI values for 1p were 11.5 for HRV14, 8.4 for HRV21, and 12.1 for HRV71, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Antioxidant action of 3-mercapto-5H-1,2,4-triazino[5,6-b]indole-5-acetic acid, an efficient aldose reductase inhibitor, in a 1,1'-diphenyl-2-picrylhydrazyl assay and in the cellular system of isolated erythrocytes exposed to tert-butyl hydroperoxide.

    Science.gov (United States)

    Prnova, Marta Soltesova; Ballekova, Jana; Majekova, Magdalena; Stefek, Milan

    2015-01-01

    The subject of this study was 3-mercapto-5H-1,2,4-triazino[5,6-b]indole-5-acetic acid (compound 1), an efficient aldose reductase inhibitor of high selectivity. The antioxidant action of 1 was investigated in greater detail by employing a 1,1'-diphenyl-2-picrylhydrazyl (DPPH) test and in the system of isolated rat erythrocytes. First, the compound was subjected to the DPPH test. Second, the overall antioxidant action of the compound was studied in the cellular system of isolated rat erythrocytes oxidatively stressed by free radicals derived from the lipophilic tert-butyl hydroperoxide. The uptake kinetics of 1 was studied and osmotic fragility of the erythrocytes was evaluated. The DPPH test revealed significant antiradical activity of 1. One molecule of 1 was found to quench 1.48 ± 0.06 DPPH radicals. In the system of isolated erythrocytes, the compound was readily taken up by the cells followed by their protection against free radical-initiated hemolysis. Osmotic fragility of the erythrocytes was not affected by 1. The results demonstrated the ability of 1 to scavenge DPPH and to protect intact erythrocytes against oxidative damage induced by peroxyl radicals. By affecting both the polyol pathway and oxidative stress, the compound represents an example of a promising agent for multi-target pharmacology of diabetic complications.

  6. Discovery, Synthesis, And Structure-Based Optimization of a Series of N-(tert-Butyl)-2-(N-arylamido)-2-(pyridin-3-yl) Acetamides (ML188) as Potent Noncovalent Small Molecule Inhibitors of the Severe Acute Respiratory Syndrome Coronavirus (SARS-CoV) 3CL Protease

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Jon [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Grum-Tokars, Valerie [Northwestern Univ., Chicago, IL (United States); Zhou, Ya [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Turlington, Mark [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Saldanha, S. Adrian [Sripps Research Inst. Molecular Screening Center, Jupiter, FL (United States); Chase, Peter [Sripps Research Inst. Molecular Screening Center, Jupiter, FL (United States); Eggler, Aimee [Purdue Univ., West Lafayette, IN (United States); Dawson, Eric S. [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Baez-Santos, Yahira M. [Purdue Univ., West Lafayette, IN (United States); Tomar, Sakshi [Purdue Univ., West Lafayette, IN (United States); Mielech, Anna M. [Loyola Univ. Medical Center, Maywood, IL (United States); Baker, Susan C. [Loyola Univ. Medical Center, Maywood, IL (United States); Lindsley, Craig W. [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Hodder, Peter [Sripps Research Inst. Molecular Screening Center, Jupiter, FL (United States); Mesecar, Andrew [Purdue Univ., West Lafayette, IN (United States); Stauffer, Shaun R. [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States)

    2012-12-11

    A high-throughput screen of the NIH molecular libraries sample collection and subsequent optimization of a lead dipeptide-like series of severe acute respiratory syndrome (SARS) main protease (3CLpro) inhibitors led to the identification of probe compound ML188 (16-(R), (R)-N-(4-(tert-butyl)phenyl)-N-(2-(tert-butylamino)-2-oxo-1-(pyridin-3-yl)ethyl)furan-2-carboxamide, Pubchem CID: 46897844). But, unlike the majority of reported coronavirus 3CLpro inhibitors that act via covalent modification of the enzyme, 16-(R) is a noncovalent SARS-CoV 3CLpro inhibitor with moderate MW and good enzyme and antiviral inhibitory activity. A multicomponent Ugi reaction was utilized to rapidly explore structure–activity relationships within S1', S1, and S2enzyme binding pockets. Moreover, the X-ray structure of SARS-CoV 3CLpro bound with 16-(R) was instrumental in guiding subsequent rounds of chemistry optimization. 16-(R) provides an excellent starting point for the further design and refinement of 3CLpro inhibitors that act by a noncovalent mechanism of action.

  7. Stereoelectronic Substituent Effects

    DEFF Research Database (Denmark)

    Bols, Mikael; Jensen, Henrik Helligsø

    2006-01-01

    An investigation was carried Out on the influence of the stereo-chemistry of substituents, particularly hydroxyl groups, on their electronic effects in piperidines, carbohydrates (pyranosides), and related compounds. Polar groups, such as OH, OR, and F, were found in the 3 and 4 position to be much...... more electron-withdrawing when positioned equatorially rather than axially. In contrast, little difference in electronic effects was observed from apolar groups as a result of epimerization. These observations were believed to be caused by differences in charge-dipole interactions and were used...... to explain why stereoisomeric glycosides hydrolyze with different rates. The conformational changes of hydroxylated piperidines and related compounds as a function of pH were likewise explained from the different substituent effects of axial and equatorial OH groups....

  8. μ-Carbonato-κ4 O,O′:O′,O′′-bis­{[2′-(di-tert-butyl­phosphan­yl)biphenyl-2-yl-κ2 P,C 1]palladium(II)} dichloro­methane monosolvate

    Science.gov (United States)

    Muller, Alfred; Holzapfel, Cedric W.

    2012-01-01

    The title compound, [(μ2-CO3){Pd(P(t-C4H9)2(C12H8)}2]·CH2Cl2, the first CO3-bridged palladium dimer complex reported to date, was obtained while preparing the Pd0 complex with (2-biphen­yl)P(tBu)2. In the crystal, each palladium dimer is accompanied by a dichloro­methane solvent mol­ecule. Coordination of the carbonate and chelated phosphane ligands gives distorted square-planar environments at the Pd atoms. Important geometrical parameters include Pd—P(av.) = 2.2135 (4) Å, Pd—C(av.) = 1.9648 (16) Å and P—Pd—C = 84.05 (5) and 87.98 (5)°, and O—Pd—O′ = 60.56 (4) and 61.13 (4)°. Bonding with the carbonate O atoms shows values of 2.1616 (11) and 2.1452 (11) Å for the Pd—O—Pd bridge, whereas other Pd—O distances are slightly longer at 2.2136 (11) and 2.1946 (11) Å. One of the tert-butyl groups is disordered over two set of sites with an occupancy ratio of 0.723 (6):0.277 (6). Weak C—H⋯O interactions are observed propagating the molecules along the [100] direction. PMID:23468771

  9. Studies on the separation of {sup 89}Sr(II) from irradiated yttria target using 4, 4{sup '}(5{sup '}) di-tert-butyl-cyclohexano-18-crown-6 (DtBuCH18C6) by solvent extraction technique

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Debasish; Vithya, Jayagopal; Kumar, Ramalingam; Venkata Subramani, Canchipuram Ramamoorthy; Vasudeva Rao, Polur Ranga [Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam (India). Chemistry Group

    2016-07-01

    The radioisotope {sup 89}Sr as {sup 89}SrCl{sub 2} is medically useful for bone pain palliation and is produced in fast reactors using the {sup 89}Y(n, p){sup 89}Sr reaction. A procedure for isolation of the radionuclide {sup 89}Sr by chemical processing of the irradiated Y{sub 2}O{sub 3} target has been standardised and trial runs have been carried out at the Fast Breeder Test Reactor (FBTR), Kalpakkam. The chemical processing of the irradiated Y{sub 2}O{sub 3} target involves (i) the removal of target Y(III) by TBP extraction and (ii) further purification of the separated {sup 89}Sr fraction by cationic exchange chromatography. However a selective isolation of {sup 89}Sr by the Sr-specific crown ether makes the above chemical processing faster and relatively simple. This work presents a study on the selective removal of Sr from the irradiated target dissolver solution using the Sr-specific crown ether 4,4{sup '}(5{sup '}) di-tert-butyl-cyclohexano-18-crown-6 (DtBuCH18C6) in octanol medium. The separation behaviour of the other impurities such as Ce(IV), Y(III), Tb(III), Eu(III), Zn(II), Mn(II) and Rb(I) present along with Sr(II) in the irradiated sample was also investigated. The method of separation by using the crown ether DtBuCH18C6 is proved to be a potential tool for the purification of {sup 89}Sr(II) source produced from yttria target in fast reactors.

  10. An octanuclear molybdenum(VI) complex containing coordinatively bound 4,4'-di-tert-butyl-2,2'-bipyridine, [Mo8O22(OH)4(di-tBu-bipy)4]: synthesis, structure, and catalytic epoxidation of bio-derived olefins.

    Science.gov (United States)

    Amarante, Tatiana R; Neves, Patrícia; Tomé, Cátia; Abrantes, Marta; Valente, Anabela A; Paz, Filipe A Almeida; Pillinger, Martyn; Gonçalves, Isabel S

    2012-03-19

    The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(μ(3)-OH)(2)(μ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(μ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP. © 2012 American Chemical Society

  11. Catabolism of methyl ter-butyl ether (MTBE): characterization of the enzymes of Mycobacterium austroafricanum IFP 2012 involved in MTBE degradation; Catabolisme du methyl tert-butyl ether (MTBE): caracterisation des enzymes impliquees dans la degradation du MTBE chez Mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Lopes Ferreira, N

    2005-11-15

    Methyl tert-butyl ether (MTBE) is added to gasoline to meet the octane index requirement. its solubility in water and its poor biodegradability made the use of MTBE a great environmental concern, particularly regarding aquifers. We previously isolated M austroafricanum IFP 2012 able to use MTBE as a sole source of carbon and energy and the MTBE pathway was partially characterized. In the present study, which aimed at isolating the genes involved in MTBE biodegradation in order to use them for estimation of MTBE biodegradation capacities in contaminated environment, we isolated a new M. austroafricanum strain, IFP 2015. A new degradation intermediate, the 2-methyl 1,2-propane-diol (2-M1,2-PD), the product of tert-butanol (TBA) oxidation, was identified. We also determined the enzymes induced during growth of M. austroafricanum IFP 2012 on MTBF. Then, using the tools of protein analysis and of molecular biology, we isolated and cloned the mpd genes cluster in the plasmid pCL4D. Heterologous expression of the recombinant plasmid in M smegmatis tmc2 155, showed the involvement of an 2-M1,2-PD dehydrogenase (MpdB) and a hydroxy-iso-butyr-aldehyde dehydrogenase (MpdC), encoded by mpdB and mpdC, respectively. Both enzymes were responsible for the conversion of 2-M 1,2-PD to hydroxy-isobutyric acid (HIBA). A further survey of different M austroafricanum strains, including IFP 2012, IFP 2015 and JOBS (ex-M vaccae) showed the link between the ability to grow on C{sub 2} to C{sub 16} n-alkanes and the MTBE and TBA degradation capacities. The alkB gene was partially sequenced in all these strains. Expression of alkB was demonstrated in M. austroafricanum IFP 2012 after growth on propane, hexane, hexadecane and TBA. Finally, we identified 2-propanol as the intermediate of HIBA degradation. The gene encoding the 2-propanol:p-N,N'-dimethyl-4-nitroso-aniline (NDMA) oxidoreductase was detected M austroafricanum IFP 2012. (author)

  12. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium; Determinacion de la capacidad extractiva del p-ter-butilocalix[8]areno octa-fosfinoilado hacia iones uranilo de un medio acuo-acido salino

    Energy Technology Data Exchange (ETDEWEB)

    Serrano V, E. C.

    2011-07-01

    The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO{sub 3}-3.5 NaNO{sub 3}) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10{sup -4} M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10{sup -4} M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO{sub 2}){sub 2}B{sub 8}bL{sup 8}(NO{sub 3}){sub 4}(H{sub 2}O){sub 4}CHCl{sub 3}(CH{sub 3}OH){sub 3} the methanol molecules come from its purification. It is proposed that B{sub 8}bL{sup 8} calixarene in

  13. Catabolism of methyl ter-butyl ether (MTBE): characterization of the enzymes of Mycobacterium austroafricanum IFP 2012 involved in MTBE degradation; Catabolisme du methyl tert-butyl ether (MTBE): caracterisation des enzymes impliquees dans la degradation du MTBE chez Mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Lopes Ferreira, N.

    2005-11-15

    Methyl tert-butyl ether (MTBE) is added to gasoline to meet the octane index requirement. its solubility in water and its poor biodegradability made the use of MTBE a great environmental concern, particularly regarding aquifers. We previously isolated M austroafricanum IFP 2012 able to use MTBE as a sole source of carbon and energy and the MTBE pathway was partially characterized. In the present study, which aimed at isolating the genes involved in MTBE biodegradation in order to use them for estimation of MTBE biodegradation capacities in contaminated environment, we isolated a new M. austroafricanum strain, IFP 2015. A new degradation intermediate, the 2-methyl 1,2-propane-diol (2-M1,2-PD), the product of tert-butanol (TBA) oxidation, was identified. We also determined the enzymes induced during growth of M. austroafricanum IFP 2012 on MTBF. Then, using the tools of protein analysis and of molecular biology, we isolated and cloned the mpd genes cluster in the plasmid pCL4D. Heterologous expression of the recombinant plasmid in M smegmatis tmc2 155, showed the involvement of an 2-M1,2-PD dehydrogenase (MpdB) and a hydroxy-iso-butyr-aldehyde dehydrogenase (MpdC), encoded by mpdB and mpdC, respectively. Both enzymes were responsible for the conversion of 2-M 1,2-PD to hydroxy-isobutyric acid (HIBA). A further survey of different M austroafricanum strains, including IFP 2012, IFP 2015 and JOBS (ex-M vaccae) showed the link between the ability to grow on C{sub 2} to C{sub 16} n-alkanes and the MTBE and TBA degradation capacities. The alkB gene was partially sequenced in all these strains. Expression of alkB was demonstrated in M. austroafricanum IFP 2012 after growth on propane, hexane, hexadecane and TBA. Finally, we identified 2-propanol as the intermediate of HIBA degradation. The gene encoding the 2-propanol:p-N,N'-dimethyl-4-nitroso-aniline (NDMA) oxidoreductase was detected M austroafricanum IFP 2012. (author)

  14. Degradation of methyl-tert-butyl ether (MTBE)

    Czech Academy of Sciences Publication Activity Database

    Cajthaml, Tomáš; Baldrian, Petr; Stoychev, I.; Nerud, František

    2004-01-01

    Roč. 53, - (2004), s. 208-209 ISSN 0964-8305. [International Bideterioration and Biodegradation Symposium /12./. Praha, 14.07.2002-18.07.2002] R&D Projects: GA MŠk LN00B030 Institutional research plan: CEZ:AV0Z5020903 Keywords : mtbe Subject RIV: EE - Microbiology, Virology Impact factor: 0.835, year: 2004

  15. Percutaneous Dissolution of Gallstones using Methyl Tert-Butyl Ether

    OpenAIRE

    1990-01-01

    Radiolucent cholesterol gallstones can be dissolved rapidly by methyl terc-buryl ether (MTBE) introduced directly into the gallbladder. Percutaneous transhepatic catheter placement is a well established interventional radiology procedure and is the preferred route for MTBE administration. A small number of patients have been treated using nasobiliary placement of a gallbladder catheter. Rapid stirring automatic pump systems allow dissolution of most cholesterol stones, but s...

  16. tert-Butyl 2-methyl-2-(4-nitrobenzoylpropanoate

    Directory of Open Access Journals (Sweden)

    Chelsey M. Crosse

    2010-02-01

    Full Text Available The title compound, C15H19NO5, is bent with a dihedral angle of 61.8 (2° between the mean planes of the benzene ring and a group encompassing the ester functionality (O=C—O—C. The dihedral angle of 0.8 (2° between the mean planes of the nitro group and the benzene ring indicates near coplanarity. In the crystal, each molecule is linked to four adjacent molecules by weak C—H...O hydrogen-bonding interactions. Both benzene H atoms ortho to the ketone O atom form C—H...O hydrogen bonds with the keto O atoms of two neighboring molecules (of the keto and ester groups, respectively, and the two other interactions involve the H atoms from a methyl group of the dimethyl residue, displaying C—H...O interactions with the O atoms of the nitro groups. These four interactions for each molecule lead to the formation of two-dimensional sheets with a hydrophilic interior, held together by weak hydrogen-bonded interactions, and a hydrophobic exterior composed of protruding methyl groups which interstack with the methyl groups in adjacent sheets.

  17. Pentafluorosulfanyl Substituents in Polymerization Catalysis.

    Science.gov (United States)

    Kenyon, Philip; Mecking, Stefan

    2017-10-04

    Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

  18. Towards a physical interpretation of substituent effect: Quantum chemical interpretation of Hammett substituent constants

    Science.gov (United States)

    Varaksin, Konstantin S.; Szatylowicz, Halina; Krygowski, Tadeusz M.

    2017-06-01

    Quantitative description of substituent effects is of a great importance especially in organic chemistry and QSAR-type treatments. The proposed approaches: substituent effect stabilization energy (SESE) and charge of the substituent active region (cSAR) provide substituent effect characteristics, physically independent of the Hammett's substituent constants, σ. To document abilities of these descriptors the B3LYP/6-311++G(d,p) method is employed to examine changes in properties of a reaction center Y (Y = COOH or COO- groups) and a transmitting moiety (benzene ring) due to substituent effects in a series of meta- and para-X-substituted benzoic acid and benzoate anion derivatives (X = NMe2, NH2, OH, OMe, CH3, H, F, Cl, CF3, CN, CHO, COMe, CONH2, COOH, NO2, NO). The transmitting moiety is described by aromaticity indices HOMA and NICS(1). Furthermore, an advantage of the cSAR characteristic is the ability to use it to describe both electron donating/accepting properties of a substituent as well as a reaction center. It allows demonstration of the reverse substituent effects of COOH and COO- groups on substituent X.

  19. Radiation effects on polyacetylenes having substituents

    International Nuclear Information System (INIS)

    Higashimura, Toshinobu; Tang, Ben-Zhong; Masuda, Toshio; Yamaoka, Hitoshi; Matsuyama, Tomochika.

    1985-01-01

    Effects of γ-ray irradiation on high molecular weight polyacetylenes with various substituents were studied in air and in vacuum. The molecular weights of polymers from aliphatic disubstituted acetylenes (2-octyne and 2-decyne) remarkably reduced with irradiation in air. Their G values for chain scission in air were as high as 3 - 12, whereas no degradation occurred in vacuum. The degraded polymers contain carbonyl and hydroxyl groups, and are soluble in polar solvents such as methyl ethyl ketone and acetone. In contrast, polymers of aromatic disubstituted acetylenes (1-phenyl-1-propyne and 1-chloro-2-phenylacetylene) hardly degraded in air even with irradiation up to 40 Mrad. The degradation behavior of poly(t-butylacetylene) was intermediate between those of the above aliphatic and aromatic polymers. Thus the radiolysis of polyacetylenes was found to be greatly dependent on the kind of substituents. (author)

  20. World Wide Web-based system for the calculation of substituent parameters and substituent similarity searches.

    Science.gov (United States)

    Ertl, P

    1998-02-01

    Easy to use, interactive, and platform-independent WWW-based tools are ideal for development of chemical applications. By using the newly emerging Web technologies such as Java applets and sophisticated scripting, it is possible to deliver powerful molecular processing capabilities directly to the desk of synthetic organic chemists. In Novartis Crop Protection in Basel, a Web-based molecular modelling system has been in use since 1995. In this article two new modules of this system are presented: a program for interactive calculation of important hydrophobic, electronic, and steric properties of organic substituents, and a module for substituent similarity searches enabling the identification of bioisosteric functional groups. Various possible applications of calculated substituent parameters are also discussed, including automatic design of molecules with the desired properties and creation of targeted virtual combinatorial libraries.

  1. 4-[(E-(5-tert-Butyl-2-hydroxyphenyldiazenyl]benzoic acid benzene hemisolvate

    Directory of Open Access Journals (Sweden)

    Edward R. T. Tiekink

    2010-03-01

    Full Text Available The title benzene hemisolvate, C17H18N2O3·0.5C6H6, features an essentially planar (the r.m.s. deviation of the non-H atoms, excluding methyl-C, is 0.071 Å diazo molecule with an E conformation about the N=N bond, and a half-molecule of benzene disposed about a centre of inversion. The dihedral angle formed between the benzene rings of the diazo molecule is 7.69 (12°. In the crystal, centrosymmetrically related dimers associate via the eight-membered carboxylic acid dimer synthon, {...HOC(=O}2, and these are connected into a supramolecular chain along the b axis via C—H...O contacts.

  2. Back-biting termination in methyl methacrylate/tert-butyl acrylate anionic block copolymerization

    Czech Academy of Sciences Publication Activity Database

    Čadová, Eva; Dybal, Jiří; Kříž, Jaroslav; Vlček, Petr; Janata, Miroslav; Toman, Luděk

    2008-01-01

    Roč. 209, č. 16 (2008), s. 1657-1665 ISSN 1022-1352 Institutional research plan: CEZ:AV0Z40500505 Keywords : acrylates * anionic polymerization * spontaneous termination Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.202, year: 2008

  3. Effect of Methyl tert-Butyl Ether in Standard Tests for Mutagenicity and Environmental Toxicity

    Czech Academy of Sciences Publication Activity Database

    Vosáhlíková, M.; Cajthaml, Tomáš; Demnerová, K.; Pazlarová, Jarmila

    2006-01-01

    Roč. 21, č. 6 (2006), s. 599-605 ISSN 1520-4081 Institutional research plan: CEZ:AV0Z50200510 Keywords : toxicity * mtbe * ames test Subject RIV: EE - Microbiology, Virology Impact factor: 1.582, year: 2006

  4. SIRT1 exhibits antioxidative effects in HT22 cells induced by tert-butyl alcohol.

    Science.gov (United States)

    Ma, Junxiang; Song, Dongmei; Zhang, Yuanyuan; Chen, Li; Zhang, Shixuan; Jia, Jiaxin; Chen, Tian; Guo, Caixia; Tian, Lin; Gao, Ai; Niu, Piye

    2018-02-01

    Tertiary butyl alcohol (TBA) is a principal metabolite of methyl tertiary-butyl ether (MTBE), a common pollutant worldwide in the ground or underground water, which is found to produce nervous system damage. Nevertheless, few data regarding the effects of TBA has been reported. Studies indicated that oxidative stress plays a pivotal role in MTBE neurotoxic mechanism. Sirtuin 1 (SIRT1) has been reported to exert a neuroprotective effect on various neurologic diseases via resistance to oxidative stress by deacetylating its substrates. In this study, we examined levels of oxidative stress after exposure to TBA for 6 h in HT22 cells and HT22 cells with SIRT1 silencing (transfected with SIRT1 siRNA) or high expression (preconditioned with agonists SRT1720). We found that TBA activated oxidative stress by increasing generation of intracellular reactive oxygen species (ROS), malondialdehyde (MDA) and Oxidized glutathione (GSSG), and decreasing contents of superoxide dismutase (SOD) and glutathione reductase (GSH). In additional, levels of TBA-induced oxidative stress were aggravated when SIRT1 silenced but alleviated when SIRT1 enhanced. Our study indicated that SIRT1 mitigated oxidative stress induced by TBA. © 2017 Wiley Periodicals, Inc.

  5. Update on dissolution of gallstones with methyl-tert-butyl ether

    International Nuclear Information System (INIS)

    van Sonnenberg, E.; D'Agostino, H.B.; Hofmann, A.F.; Casola, G.; Varney, R.R.; Jinich, H.; Steingart, C.; McQuade, K.; Hoyt, D.

    1989-01-01

    The authors have studied 50 patients who underwent percutaneous MTBE dissolution of gallstones with or without supplemental basketing. All patients had symptomatic gallbladder or ductal stones. Five patients underwent emergency gallbladder drainage for acute calculous cholecystitis; after recovery, their gallstones were dissolved or removed. The other 45 patients had elective gallstone dissolution; preliminary studies on these patients included plain film, US, oral cholecystography, and CT. Follow-up studies were chromatography, US, and cholecystography. Three patients underwent cholecystectomy after MTBE treatment; no averse effects of MTBE were seen histologically. Three patients had stone recurrence. The majority of patients were placed on ursodeoxycholic acid after stone dissolution

  6. Inhibition of Palmityl Carnitine Oxidation in Rat Liver Mitochondria by Tert-Butyl Hydroperoxide

    Czech Academy of Sciences Publication Activity Database

    Červinková, Z.; Rauchová, Hana; Křiváková, P.; Drahota, Zdeněk

    2008-01-01

    Roč. 57, č. 1 (2008), s. 133-136 ISSN 0862-8408 R&D Projects: GA ČR(CZ) GD303/03/H065; GA ČR(CZ) GA305/04/0500; GA MŠk(CZ) 1M0520 Institutional research plan: CEZ:AV0Z50110509 Keywords : liver mitochondria * palmityl carnitine oxidation * tert-butylhydroperoxide Subject RIV: ED - Physiology Impact factor: 1.653, year: 2008

  7. tert-Butyl 6-bromo-1,4-dimethyl-9H-carbazole-9-carboxylate

    Directory of Open Access Journals (Sweden)

    Jean-François Lohier

    2010-08-01

    Full Text Available The title compound, C19H20BrNO2, consists of a carbazole skeleton with methyl groups at positions 1 and 4, a protecting group located at the N atom and a Br atom at position 6. The pyrrole ring is oriented at dihedral angles of 1.27 (7 and 4.86 (7° with respect to the adjacent benzene rings. The dihedral angle between the benzene rings is 5.11 (7. The crystal structure is determined mainly by intramolecular C—H...O and intermolecular π–π interactions. π-stacking between adjacent molecules forms columns with a parallel arrangement of the carbazole ring systems. The presence of the tert-butoxycarbonyl group on the carbazole N atom and the intramolecular hydrogen bond induce a particular conformation of the exocyclic N—C bond within the molecule.

  8. ``Living polymers'' in organic solvents : stress relaxation in bicopper tetracarboxylate/tert-butyl cyclohexane solutions

    Science.gov (United States)

    Terech, P.; Maldivi, P.; Dammer, C.

    1994-10-01

    Viscoelastic solutions of a bicopper tetracarboxylate complex in tert-butylcyclohexane have been studied by dynamic rheology in a wide range of concentrations (0.5-1.5 % volume fraction). The zero shear viscosity, the elastic modulus, the terminal stress relaxation time and the height of the high-frequency dip, in a Cole-Cole representation of the complex elastic modulus, follow scaling laws. The related exponents are discussed in the context of the physics of “living polymers” : a term used to describe worm-like species undergoing scission/recombination reactions competing mainly with the reptation motions of the chains. The current system, made up of molecular threads (17.5 Å diameter) of Cu2(O2C-CH(C2H5)C4H9)4 in the apolar solvent, is representative of a “living polymer” where, instead of mechanisms involving transient star polymeric crosslinks, a reversible scission mechanism prevails. The dynamics in the high-frequency range evolves from a regime where reptation is the dominant relaxation mechanism to a cross-over regime where “breathing” fluctuations and Rouse motions become important. Large modifications of the stress relaxation function occur for more concentrated systems. The binary system is the first example of a “living polymer” in an organic solvent and exhibits elastic moduli (G ≈ ca. 120 Pa à φ = 1 %) which are at least 20 times larger than those found for the aqueous “living polymer” systems. Les solutions viscoélastiques d'un tétracarboxylate binucléaire de cuivre dans le tert-butylcyclohexane sont étudiées par rhéologie en mode dynamique dans une gamme étendue de concentrations (0,5 %-15,5 %). La viscosité à gradient nul, le module élastique, le temps terminal de relaxation et la hauteur du puits à haute fréquence, dans une représentation Cole-Cole du module élastique complexe, suivent des lois d'échelles. Les exposants correspondants sont discutés dans le contexte de la physique des “polymères vivants" : un terme utilisé pour décrire des espèces vermiformes subissant des réactions de scission/recombinaison en compétition principalement avec les mouvements de reptation des chaînes. Le système constitué de fils moléculaires (17,5 Å de diamètre) de Cu2(O2C-CH(C2H5)C4H9)4 dans le solvant apolaire est typique de “polymères vivants” où le mécanisme de scission réversible prévaut plutôt que les mécanismes impliquant des nœuds transitoires branchés. La dynamique dans le domaine des hautes fréquences évolue d'un régime où la reptation est le mécanisme de relaxation dominant vers un régime intermédiaire où les modes de “respiration” et de Rouse deviennent importants. D'importantes modifications de la relaxation de contrainte se produisent pour les systèmes concentrés. Le système binaire est le premier exemple de “polymère vivant” en milieu organique et présente des modules élastiques (G ≈ ca. 120 Pa à φ = 1 %) qui sont au moins 20 fois plus grands que ceux des homologues aqueux.

  9. Diethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzylmalonate

    Directory of Open Access Journals (Sweden)

    Tao Zeng

    2012-02-01

    Full Text Available The title molecule, C37H56O6, possesses twofold symmetry, with the twofold axis passing through the quaternary C atom. In the crystal, neighbouring molecules are linked via O—H...O hydrogen bonds involving the phenol OH group and the carbonyl O atom, forming chains propagating in [101]. Within these chains, rings are formed with an R22(20 motif. There are also C—H...O interactions present within the rings.

  10. Bis{2-[(E-(5-tert-butyl-2-hydroxyphenyldiazenyl]benzoato}dimethyltin(IV

    Directory of Open Access Journals (Sweden)

    Edward R. T. Tiekink

    2011-10-01

    Full Text Available In the title diorganotin dicarboxylate, [Sn(CH32(C17H17N2O32], the tin(IV atom is six-coordinated by four O atoms derived from asymmetrically coordinating carboxylate ligands, and two methyl-C atoms. The resulting C2O4 donor set defines a skew-trapezoidal bipyramid with the Sn—C bonds disposed over the weaker Sn—O bonds. Within each carboxylate ligand, the hydroxyl-H atom forms bifurcated O—H...(O,N hydrogen bonds with carboxylate-O and azo-N atoms. The dihedral angles between the benzene rings in the two ligands are 10.44 (11 and 34.24 (11°. In the crystal, centrosymmetric dimers are formed through pairs of Sn...O interactions [2.8802 (16 Å], and the dimers are linked into supramolecular layers in the ac plane by C—H...π interactions.

  11. 4,4′-Di-tert-butyl-2,2′-bipyridine

    Directory of Open Access Journals (Sweden)

    Tatiana R. Amarante

    2009-08-01

    Full Text Available In the title compound, C18H24N2, the molecular unit adopts a trans conformation around the central C—C bond [N—C—C—N torsion angle of 179.2 (3°], with the two aromatic rings almost coplanar [dihedral angle of only 0.70 (4°]. The crystal packing is driven by co-operative contacts involving weak C—H...N and C—H...π interactions, and also the need to fill effectively the available space.

  12. Ultrasound-assisted oxidative desulfurization of bunker-C oil using tert-butyl hydroperoxide.

    Science.gov (United States)

    Tang, Qiong; Lin, Song; Cheng, Ying; Liu, Sujun; Xiong, Jun-Ru

    2013-09-01

    This work investigated the ultrasonic assisted oxidative desulfurization of bunker-C oil with TBHP/MoO3 system. The operational parameters for the desulfurization procedure such as ultrasonic irradiation time, ultrasonic wave amplitude, catalyst initial concentration and oxidation agent initial concentration were studied. The experimental results show that the present oxidation system was very efficient for the desulfurization of bunker-C oil and ~35% sulfur was removed which was dependent on operational parameters. The application of ultrasonic irradiation allowed sulfur removal in a shorter time. The stronger the solvent polarity is, the higher the sulfur removal rate, but the recovery rate of oil is lower. The sulfur compounds in bunker-C oil reacted with TBHP to produce corresponding sulfoxide, and further oxidation produced the corresponding sulfone. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. rac-tert-Butyl{2-hydroxy-2-[4-hydroxy-3-(hydroxymethylphenyl]ethyl}azanium acrylate

    Directory of Open Access Journals (Sweden)

    Wenju Liu

    2017-08-01

    Full Text Available The title salt, C13H22NO3+·C3H3O2−, comprises one salbutamol cation and an acrylate anion. The acrylate anion is linked to the salbutamol cation via an O—H...O and an N—H...O hydrogen bond. The C=C group of the acrylate anion is disordered over two positions, with refined site occupancies of 0.812 (7 and 0.188 (7. The crystal structure is stabilized by N—H...O and O—H...O hydrogen-bonding interactions.

  14. Rearrangements in the halogenation of tetraalkylethylenes with N-halosuccinimides and tert-butyl hypochlorite

    NARCIS (Netherlands)

    Meijer, E.W.; Kellogg, R.M.; Wynberg, H.

    1982-01-01

    The reaction of N-halosuccinimides and Me3COCl with tetraalkylethylenes involves halo-cation addn. to the double bond in a fast reaction, followed by abstraction of an allylic proton, resulting in a double bond shift. Homoallylic halogenation occurs in tetraalkylethylenes which can not undergo a

  15. TRANSPORT OF METHYL TERT-BUTYL ETHER THROUGH ALFALFA PLANTS. (R825549C062)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. N-(Fluoren-9-ylmethoxycarbonyl-l-aspartic acid 4-tert-butyl ester

    Directory of Open Access Journals (Sweden)

    Kazuhiko Yamada

    2009-11-01

    Full Text Available The bond distances and bond angles of the title compound, C23H25NO6, are consistent with values typically found for fluoren-9-ylmethoxycarbonyl-protected amino acids. The conformations of the backbone and the side chain are slightly different from those of l-aspartic acid. The crystal structure exhibits two intermolecular hydrogen bonds, forming a two-dimensional sheet structure parallel to the ab plane.

  17. tert-Butyl 4-carbamoyl-3-methoxyimino-4-methylpiperidine-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Yucheng Wang

    2008-12-01

    Full Text Available The title compound, C13H23N3O4, was prepared starting from ethyl N-benzyl-3-oxopiperidine-4-carboxylate through a nine-step reaction, including hydrogenation, Boc (tert-butoxycarbonyl protection, methylation, oximation, hydrolysis, esterification and ammonolysis. In the crystal structure, molecules are linked by intermolecular N—H...O hydrogen bonds to form a porous three-dimensional network with solvent-free hydrophobic channels extending along the c axis.

  18. Di-tert-butyl N-[2,6-bis(methoxymethoxyphenyl]iminodiacetate

    Directory of Open Access Journals (Sweden)

    Ben Capuano

    2009-04-01

    Full Text Available The title molecule, C20H31NO8, has pseudo-C2 symmetry about the C—N bond, with the bis(tert-butoxycarbonylamino group twisted from the benzene ring plane by ca 60° and the bulky tert-butoxycarbonyl (Boc groups are orientated away from the substituted aniline group. As part of an antibacterial drug discovery programme furnishing analogues of platensimycin, we unexpectedly synthesized the bis-Boc-protected aniline.

  19. IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) (Preliminary Assessment Materials)

    Science.gov (United States)

    In August 2013, EPA released the draft literature searches and associated search strategies, evidence tables, and exposure response arrays for TBA to obtain input from stakeholders and the public prior to developing the draft IRIS assessment. Specifically, EPA was interested in c...

  20. Absorption, Distribution, and Clearanace o f2,6-Di-tert-Butyl-4-nitrophenol (DBNP)

    National Research Council Canada - National Science Library

    Still, K

    2002-01-01

    .... DBNP is produced when oil mist from synthetic steam turbine lubricants containing the antioxidant 2,6-Di-tert-butylphenol is nitrated during passage through the submarine air filtration system...

  1. Di-tert-butyl-bis(N-isopropyl-N-methyl-dithio-carbamato-κS,S')tin(IV).

    Science.gov (United States)

    Muthalib, Amirah Faizah; Baba, Ibrahim; Samsudin, Mohd Wahid; Ng, Seik Weng

    2010-03-03

    The dithio-carbamate anions in the title compound, [Sn(C(4)H(9))(2)(C(5)H(10)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis. The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.82 (1):0.18 (1).

  2. Synthesis, structure, and sunlight photolysis of benzyl- and tert-butyl-substituted octamethyltitanocene dihydrosulfides

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal; Císařová, I.; Gyepes, R.; Kubišta, Jiří; Pinkas, Jiří; Lamač, Martin; Mach, Karel

    2014-01-01

    Roč. 755, APR 2014 (2014), s. 141-150 ISSN 0022-328X R&D Projects: GA ČR(CZ) GAP207/12/2368; GA ČR GP203/09/P276 Institutional support: RVO:61388955 Keywords : titanium * titanocene * hydrosulphide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.173, year: 2014

  3. Electrorheological Properties of Suspensions Prepared from Poly(Li-tert-butyl methacrylate) Ionomer

    OpenAIRE

    YAVUZ, Mustafa

    2014-01-01

    The synthesis, characterisation and partial hydrolysis of poly(tert-butylmethacrylate), (PTBMA), and the electrorheological (ER) properties of its suspensions were investigated. The polymer was synthesised by radical polymerisation and partially hydrolysed by para-toluenesulphonic acid monohydrate (PTSA.H2O), and then converted to a lithium salt (PTBMA-Li) by washing with a LiOH(aq) solution. From particle size measurements, the average particle size of PTBMA-Li was determined to be ...

  4. Rationalizing substituent effects in 1-azathioxanthone photophysics

    Science.gov (United States)

    Junker, Anne Kathrine R.; Just Sørensen, Thomas

    2018-01-01

    The influence of an electron donating substituent on the photophysical properties of 1-azathioxanthone dyes has been investigated using optical spectroscopy and theoretical models. The motivation behind the study is based on the fact that thioxanthones are efficient triplet sensitizers, and thus promising sensitizers for lanthanide centered emission. By adding an aza group to one of the phenyl ring systems, direct coordination to a lanthanide center becomes possible, which makes azathoixanthones great candidates as antenna chromophores in lanthanide(III) based dyes. Here, three 1-azathioxanthone derivatives have been synthesized targeting efficient triplet formation following absorption in the visible range of the spectrum. This is achieved by adding methoxy groups to the 1-azathioxanthone core. The derivatives were characterized using absorption, emission, and time-gated emission spectroscopy, where fluorescent quantum yields, singlet and triplet excited states lifetimes were determined. The experimentally determined photophysical properties of the three 1-azathioxanthone compounds are contrasted to those of the parent thioxanthone and is rationalized using the Strickler-Berg equation, Hückel MO theory, and Dewar’s rules in combination with computational chemistry. We find that the transition energies follow predictions, but that the overall photophysical properties are determined by the relative energies as well as the nature of the involved states in both the singlet and the triplet excited state manifolds.

  5. Spectroscopic study of 2-, 4- and 5-substituents on p Ka values of imidazole heterocycles prone to intramolecular proton-electrons transfer

    Science.gov (United States)

    Eseola, Abiodun O.; Obi-Egbedi, Nelson O.

    2010-02-01

    New 2-(1H-imidazol-2-yl)phenols ( L1Et- L8tBuPt) bearing a phenolic proton in the vicinity of the imidazole base were prepared and characterized. Experimental studies of the dependence of their protonation/deprotonation equilibrium on substituent identities and intramolecular hydrogen bonding tendencies were carried out using electronic absorption spectroscopy at varying pH values. In order to make comparison, 2-(anthracen-10-yl)-4,5-diphenyl-1H-imidazole ( L9Anthr) bearing no phenolic proton and 4,5-diphenyl-2-(4,5-diphenyl-1H-imidazol-2-yl)-1H-imidazole ( L10BisIm) bearing two symmetrical imidazole base fragments were also prepared and experimentally investigated. DFT calculations were carried out to study frontier orbitals of the investigated molecules. While electron-releasing substituents produced increase in protonation-deprotonation p Kas for the hydroxyl group, values for the imidazole base were mainly affected by polarization of the imidazole ring aromaticity across the 2-imidazole carbon and the 4,5-imidazole carbons axis of the imidazole ring. It was concluded that electron-releasing substituents on the phenol ring and/or electron-withdrawing substituents on 4,5-imidazole carbons negatively affects donor strengths/coordination chemistries of 2-(1H-imidazol-2-yl)phenols, and vice versa. Change of substituents on the phenol ring significantly altered the donor strength of the imidazole base. The understanding of p Ka variation on account of electronic effects of substituents in this work should aid the understanding of biochemical properties and substituent environments of imidazole-containing biomacromolecules.

  6. Long-range carbon-proton spin-spin coupling constants in conformational analysis

    International Nuclear Information System (INIS)

    Spoormaker, T.

    1979-01-01

    The author has collected a reliable set of data on long range 13 C- 1 H coupling constants in aliphatic compounds and developed the use of long range 13 C- 1 H coupling constants as a tool in the conformational analysis of aliphatic compounds. An empirical determination of the torsion angle dependence of the vicinal 13 C- 1 H coupling constant for model compounds is described and the dependence of long range 13 C- 1 H coupling constants on the electronegativity of substituents attached to the coupling pathway reported for the monohalogen substituted ethanes and propanes. The electronegativity dependence of the vicinal 13 C- 1 H coupling was studied in monosubstituted propanes whose substituents are elements from the first row of the periodic table and it is shown that the vicinal 13 C- 1 H coupling constant in aliphatic systems is a constitutive property. The geminal 13 C- 1 H coupling constants in ethyl, isopropyl and tert-butyl compounds, which have been substituted by an element of the first row of the periodic table or a haline atom, are reported and the influence of electronegative substituents on the vicinal 13 C- 1 H coupling constants in the individual rotamers of 13 CH 3 -C(X)H-C(Y)H- 1 H fragments discussed. The application of long range 13 C- 1 H coupling constants to the conformational analysis of CMP-N-Acetylneuraminic acid and 2,6-dichloro-1,4-oxathiane is described. (Auth.)

  7. Effect of substituent structure on pyrimidine electrophilic substitution

    CSIR Research Space (South Africa)

    Van der Westhuyzen, CW

    2007-01-01

    Full Text Available In an investigation into the electrophilic nitrosation reactions of a series of 4,6-disubstituted pyrimidine derivatives, a subtle interplay between the electronic nature of the C-4 and C-6 substituents and reactivity was found where these were...

  8. Effect of substituents on the reactivity of ninhydrin with urea

    NARCIS (Netherlands)

    Jong, Jacobus A.W.; Moret, Marc Etienne; Verhaar, Marianne C.; Hennink, Wim E.; Gerritsen, Karin G.F.; Van Nostrum, Cornelus F.

    2018-01-01

    Ninhydrin, i. e. the stable hydrate of the reactive species indanetrione, is a well-known compound used for the quantification of ammonia and amino acids. However, substituent effects on the reactivity of ninhydrin with nucleophiles are not described. In this work, the kinetics of the reaction of

  9. Vicinal surfaces for functional nanostructures.

    Science.gov (United States)

    Tegenkamp, Christoph

    2009-01-07

    Vicinal surfaces are currently the focus of research. The regular arrangements of atomic steps on a mesoscopic scale reveal the possibility to functionalize these surfaces for technical applications, e.g. nanowires, catalysts, etc. The steps of the vicinal surface are well-defined defect structures of atomic size for nucleation of low-dimensional nanostructures. The concentration and therefore the coupling between the nanostructures can be tuned over a wide range by simply changing the inclination angle of the substrate. However, the coupling of these nano-objects to the substrate is just as important in controlling their electronic or chemical properties and making a functionality useable. On the basis of stepped insulating films, these aspects are fulfilled and will be considered in the first part of this review. Recent results for the epitaxial growth of wide bandgap insulating films (CaF(2), MgO, NaCl, BaSrO) on metallic and semiconducting vicinal substrates (Si(100), Ge(100), Ag(100)) will be presented. The change of the electronic structure, the adsorption behavior as well as the kinetics and energetics of color centers in the presence of steps is discussed. The successful bridging of the gap between the atomic and mesoscopic world, i.e. the functionalization of vicinal surfaces by nanostructures, is demonstrated in the second part by metal adsorption on semiconducting surfaces. For (sub)monolayer coverage these systems have in common that the surface states do not hybridize with the support, i.e. the semiconducting surfaces are insulating. Here I will focus on the latest results of macroscopic transport measurements on Pb quantum wires grown on vicinal Si(111) showing indeed a one-dimensional transport behavior.

  10. Vicinal surfaces for functional nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Tegenkamp, Christoph [Institut fuer Festkoerperphysik, Gottfried Wilhelm Leibniz Universitaet Hannover, Appelstrasse 2, D-30167 Hannover (Germany)], E-mail: tegenkamp@fkp.uni-hannover.de

    2009-01-07

    Vicinal surfaces are currently the focus of research. The regular arrangements of atomic steps on a mesoscopic scale reveal the possibility to functionalize these surfaces for technical applications, e.g. nanowires, catalysts, etc. The steps of the vicinal surface are well-defined defect structures of atomic size for nucleation of low-dimensional nanostructures. The concentration and therefore the coupling between the nanostructures can be tuned over a wide range by simply changing the inclination angle of the substrate. However, the coupling of these nano-objects to the substrate is just as important in controlling their electronic or chemical properties and making a functionality useable. On the basis of stepped insulating films, these aspects are fulfilled and will be considered in the first part of this review. Recent results for the epitaxial growth of wide bandgap insulating films (CaF{sub 2}, MgO, NaCl, BaSrO) on metallic and semiconducting vicinal substrates (Si(100), Ge(100), Ag(100)) will be presented. The change of the electronic structure, the adsorption behavior as well as the kinetics and energetics of color centers in the presence of steps is discussed. The successful bridging of the gap between the atomic and mesoscopic world, i.e. the functionalization of vicinal surfaces by nanostructures, is demonstrated in the second part by metal adsorption on semiconducting surfaces. For (sub)monolayer coverage these systems have in common that the surface states do not hybridize with the support, i.e. the semiconducting surfaces are insulating. Here I will focus on the latest results of macroscopic transport measurements on Pb quantum wires grown on vicinal Si(111) showing indeed a one-dimensional transport behavior. (topical review)

  11. Vicinal surfaces for functional nanostructures

    International Nuclear Information System (INIS)

    Tegenkamp, Christoph

    2009-01-01

    Vicinal surfaces are currently the focus of research. The regular arrangements of atomic steps on a mesoscopic scale reveal the possibility to functionalize these surfaces for technical applications, e.g. nanowires, catalysts, etc. The steps of the vicinal surface are well-defined defect structures of atomic size for nucleation of low-dimensional nanostructures. The concentration and therefore the coupling between the nanostructures can be tuned over a wide range by simply changing the inclination angle of the substrate. However, the coupling of these nano-objects to the substrate is just as important in controlling their electronic or chemical properties and making a functionality useable. On the basis of stepped insulating films, these aspects are fulfilled and will be considered in the first part of this review. Recent results for the epitaxial growth of wide bandgap insulating films (CaF 2 , MgO, NaCl, BaSrO) on metallic and semiconducting vicinal substrates (Si(100), Ge(100), Ag(100)) will be presented. The change of the electronic structure, the adsorption behavior as well as the kinetics and energetics of color centers in the presence of steps is discussed. The successful bridging of the gap between the atomic and mesoscopic world, i.e. the functionalization of vicinal surfaces by nanostructures, is demonstrated in the second part by metal adsorption on semiconducting surfaces. For (sub)monolayer coverage these systems have in common that the surface states do not hybridize with the support, i.e. the semiconducting surfaces are insulating. Here I will focus on the latest results of macroscopic transport measurements on Pb quantum wires grown on vicinal Si(111) showing indeed a one-dimensional transport behavior. (topical review)

  12. Modelling nanostructures with vicinal surfaces

    International Nuclear Information System (INIS)

    Mugarza, A; Schiller, F; Kuntze, J; Cordon, J; Ruiz-Oses, M; Ortega, J E

    2006-01-01

    Vicinal surfaces of the (111) plane of noble metals are characterized by free-electron-like surface states that scatter at one-dimensional step edges, making them ideal model systems to test the electronic properties of periodic lateral nanostructures. Here we use high-resolution, angle-resolved photoemission to analyse the evolution of the surface state on a variety of vicinal surface structures where both the step potential barrier and the superlattice periodicity can vary. A transition in the electron dimensionality is found as we vary the terrace size in single-phase step arrays. In double-phase, periodic faceted surfaces, we observe surface states that characterize each of the phases

  13. Substituent effect on redox potential of nitrido technetium complexes with Schiff base ligand. Theoretical calculations

    International Nuclear Information System (INIS)

    Takayama, T.; Sekine, T.; Kudo, H.

    2003-01-01

    Theoretical calculations based on the density functional theory (DFT) were performed to understand the effect of substituents on the molecular and electronic structures of technetium nitrido complexes with salen type Schiff base ligands. Optimized structures of these complexes are square pyramidal. The electron density on a Tc atom of the complex with electron withdrawing substituents is lower than that of the complex with electron donating substituents. The HOMO energy is lower in the complex with electron withdrawing substituents than that in the complex with electron donating substituents. The charge on Tc atoms is a good measure that reflects the redox potential of [TcN(L)] complex. (author)

  14. Tailoring the Structure of Two-Dimensional Self-Assembled Nanoarchitectures Based on NiII–Salen Building Blocks

    DEFF Research Database (Denmark)

    Viciano-Chumillas, Marta; Li, Dongzhe; Smogunov, Alexander

    2014-01-01

    -butyl) is presented. Their electronic structure and self-assembly was studied. The organic ligands of the salen complexes are functionalized with peripheral carboxylic groups for driving molecular self-assembly through hydrogen bonding. In addition, other substituents, that is, tert-butyl and diamine bridges (2...

  15. Versatile phosphite ligands based on silsesquioxane backbones

    NARCIS (Netherlands)

    van der Vlugt, JI; Ackerstaff, J; Dijkstra, TW; Mills, AM; Kooijman, H; Spek, AL; Meetsma, A; Abbenhuis, HCL; Vogt, D

    Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-di-oxa-1,1'-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting

  16. INFLUENCE OF THE ISOBUTENE METHANOL RATIO AND OF THE METHYL TERT-BUTYL ETHER CONTENT ON THE REACTION-RATE OF THE SYNTHESIS OF METHYL TERT-BUTYL ETHER

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1995-01-01

    The forward reaction rate constant of the MtBE synthesis was determined for different reaction mixture compositions. The forward rate constant decreases continuously with increasing isobutene/methanol ratio, while an increase in reaction rate constant is observed with an increasing amount of MtBE in

  17. Free radical scavenger, N-tert-butyl-alfa-phenylnitrone, affects long-term outcome of status epilepticus in immature rats

    Czech Academy of Sciences Publication Activity Database

    Kubová, Hana; Rejchrtová, Jana; Folbergrová, Jaroslava; Mareš, Pavel

    2005-01-01

    Roč. 46, č. S8 (2005), s. 111-112 [Joint Annual Meeting of the American Epilepsy Society and American Clinical Neurophysiology Society. 02.12.2005-06.12.2005, Washington, DC] R&D Projects: GA ČR(CZ) GA304/05/2582 Institutional research plan: CEZ:AV0Z50110509 Keywords : status epilepticus * PBN * rat Subject RIV: ED - Physiology

  18. Novel Process Windows for the safe and continuous synthesis of tert.-butyl peroxypivalate with micro process technology

    NARCIS (Netherlands)

    Illg, T.

    2013-01-01

    Based on the economy of scale, the classical chemical industry uses large scale reactors to increase production output and to decrease the average unit costs. This results in large footprint plants consuming land and a huge amount of resources. This large scale character bears certain risks for the

  19. Methyl tert-Butyl Ether (MTBE) - Its Movement and Fate in the Environment and Potential for Natural Attenuation

    Science.gov (United States)

    1999-10-01

    but at varying rates, by indigenous microbiota . Normal alkanes of low molecular weight (C-8 to C-22) are metabolized most rapidly, followed by...confirmed that TBA degradation occurred at a rate slower than MTBE degradation. Pure bacterial cultures isolated from activated sludge and the fruit of...isolated from activated sludge and fruit of the Gingko tree. They have been classified as belonging to the genuses Methlobacterium, Rhodococcus, and

  20. Trimethylamine N-oxide (TMAO) and tert-butyl alcohol (TBA) at hydrophobic interfaces: insights from molecular dynamics simulations.

    Science.gov (United States)

    Fiore, Andrew; Venkateshwaran, Vasudevan; Garde, Shekhar

    2013-06-25

    TMAO, a potent osmolyte, and TBA, a denaturant, have similar molecular architecture but somewhat different chemistry. We employ extensive molecular dynamics simulations to quantify their behavior at vapor-water and octane-water interfaces. We show that interfacial structure-density and orientation-and their dependence on solution concentration are markedly different for the two molecules. TMAO molecules are moderately surface active and adopt orientations with their N-O vector approximately parallel to the aqueous interface. That is, not all methyl groups of TMAO at the interface point away from the water phase. In contrast, TBA molecules act as molecular amphiphiles, are highly surface active, and, at low concentrations, adopt orientations with their methyl groups pointing away and the C-O vector pointing directly into water. The behavior of TMAO at aqueous interfaces is only weakly dependent on its solution concentration, whereas that of TBA depends strongly on concentration. We show that this concentration dependence arises from their different hydrogen bonding capabilities-TMAO can only accept hydrogen bonds from water, whereas TBA can accept (donate) hydrogen bonds from (to) water or other TBA molecules. The ability to self-associate, particularly visible in TBA molecules in the interfacial layer, allows them to sample a broad range of orientations at higher concentrations. In light of the role of TMAO and TBA in biomolecular stability, our results provide a reference with which to compare their behavior near biological interfaces. Also, given the ubiquity of aqueous interfaces in biology, chemistry, and technology, our results may be useful in the design of interfacially active small molecules with the aim to control their orientations and interactions.

  1. AN EXPERIMENTAL STUDY OF PHYTOREMEDIATION OF METHYL-TERT-BUTYL-ETHER (MTBE) IN GROUNDWATER. (R825549C062)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  2. The new 3-(tert-butyl)-1-(2-nitrophenyl)-1H-pyrazol-5-amine: Experimental and computational studies

    Science.gov (United States)

    Cuenú, Fernando; Muñoz-Patiño, Natalia; Torres, John Eduard; Abonia, Rodrigo; Toscano, Rubén A.; Cobo, J.

    2017-11-01

    The molecular and supramolecular structure of the title compound, 3-(tertbutyl)-1-(2-nitrophenyl)-1H-pyrazol-5-amine (2NPz) from the single crystal X-ray diffraction (SC-XRD) and spectroscopic data analysis is reported. The computational analysis of the structure, geometry optimization, vibrational frequencies, nuclear magnetic resonance and UV-Vis is also described and compared with experimental data. Satisfactory theoretical aspects were made for the molecule using density functional theory (DFT), with B3LYP and B3PW91 functionals, and Hartree-Fock (HF), with 6-311++G(d,p) basis set, using GAUSSIAN 09 program package without any constraint on the geometry. With VEDA 4 software, vibrational frequencies were assigned in terms of the potential energy distribution while, with the GaussSum software, the percentage contribution of the frontier orbitals at each transition of the electronic absorption spectrum was established. The obtained results indicated that optimized geometry could well reflect the molecular structural parameters from SC-XRD. Theoretical data obtained for the vibrational analysis and NMR spectra are consistent with experimental data.

  3. Preparation and characterization of Pd doped ceria–ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation

    International Nuclear Information System (INIS)

    Seddigi, Zaki S.; Bumajdad, Ali; Ansari, Shahid P.; Ahmed, Saleh A.; Danish, Ekram Y.; Yarkandi, Naeema H.; Ahmed, Shakeel

    2014-01-01

    Highlights: • Novel Pd supported ceria–ZnO photocatalysts were prepared with different amounts of palladium. • The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. • Near complete removal of MTBE was achieved using 1% Pd doped ceria–ZnO catalyst and UV irradiation. • Highest rate constant was obtained in case of 1% Pd doped ceria–ZnO catalyst. • Shape and size of pores are important factors for high photoactivity of catalyst. -- Abstract: A series of binary oxide catalysts (ceria–ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%–1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N 2 sorptiometry study. The XPS results confirmed the structure of the Pd CeO 2−x -ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100 ppm aqueous solution of MTBE upon UV irradiation for 5 h in the presence of 100 mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria–ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N 2 sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction

  4. Crystal structure of 2-tert-butyl-2,3-dihydro-1H-benzo[c]pyrrol-1-one

    Czech Academy of Sciences Publication Activity Database

    Donkeng Dazie, Joel; Ludvík, Jiří; Fábry, Jan; Eigner, Václav

    2017-01-01

    Roč. 73, č. 8 (2017), s. 1184-1188 ISSN 2056-9890 R&D Projects: GA ČR GA13-21704S; GA MŠk(CZ) LO1603 EU Projects: European Commission(CZ) CZ.2.16/3.1.00/24510 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : crystal structure * aromaticity * heterocyclic compounds Subject RIV: CF - Physical ; Theoretical Chemistry; BM - Solid Matter Physics ; Magnetism (FZU-D) OBOR OECD: Physical chemistry; Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D)

  5. alpha-Phenyl-N-tert-butyl nitrone attenuates methamphetamine-induced depletion of striatal dopamine without altering hyperthermia.

    Science.gov (United States)

    Cappon, G D; Broening, H W; Pu, C; Morford, L; Vorhees, C V

    1996-10-01

    Methamphetamine (MA) administration to adult rats (4 x 10 mg/kg s.c.) induces neurotoxicity predominately characterized by a persistent reduction of neostriatal dopamine (DA) content. Hyperthermia following MA administration potentiates the resulting DA depletion. DA-derived free radicals are postulated to be a mechanism through which MA-induced neurotoxicity is produced. The spin trapping agent PBN reacts with free radicals to form nitroxyl adducts, thereby preventing damaging free radical reactions with cellular substrates. MA with saline pretreatment (Sal-MA) reduced neostriatal DA by 55% (P protection. PBN pretreatment did not alter MA-induced hyperthermia. Thus, PBN does not attenuate MA-induced neurotoxicity by reducing MA-induced hyperthermia. These results support a role for free radicals in the generation of MA-induced dopaminergic neurotoxicity.

  6. Bis({tris[2-(3,5-di-tert-butyl-2-oxidobenzylideneaminoethyl]amine}cerium(III diethyl ether solvate

    Directory of Open Access Journals (Sweden)

    Peter Dröse

    2010-11-01

    Full Text Available The title compound, 2[Ce(C51H75N4O3]·C4H10O, was obtained in high yield (92% by reduction of (TRENDSALCeIVCl [TRENDSAL is N,N′,N′′-tris(3,5-di-tert-butylsalicylidenatoaminotriethylamine] with potassium in THF. The bulky tripodal TRENDSAL ligand effectively encapsulates the central CeIII cation with a Ce—N(imine distance of 2.860 (2 Å and an average C—N(amine distance of 2.619 Å within a distorted monocapped octahedral coordination.

  7. Kinetics and Photodegradation Study of Aqueous Methyl tert-Butyl Ether Using Zinc Oxide: The Effect of Particle Size

    Directory of Open Access Journals (Sweden)

    Zaki S. Seddigi

    2013-01-01

    Full Text Available Zinc oxide of different average particle sizes 25 nm, 59 nm, and 421 nm as applied in the photodegradation of MTBE. This study was carried out in a batch photoreactor having a high pressure mercury lamp. Zinc oxide of particle size of 421 nm was found to be the most effective in degrading MTBE in an aqueous solution. On using this type of ZnO in a solution of 100 ppm MTBE, the concentration of MTBE has decreased to 5.1 ppm after a period of five hours. The kinetics of the photocatalytic degradation of MTBE was found to be a first order reaction.

  8. Preparation and characterization of Pd doped ceria–ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation

    Energy Technology Data Exchange (ETDEWEB)

    Seddigi, Zaki S. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Bumajdad, Ali [Chemistry Department, Faculty of Science, Kuwait University (Kuwait); Ansari, Shahid P. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Ahmed, Saleh A., E-mail: saleh_63@hotmail.com [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Danish, Ekram Y. [Chemistry Department, King Abdulaziz University, Jeddah (Saudi Arabia); Yarkandi, Naeema H. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Ahmed, Shakeel [Center for Refining and Petrochemicals, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia)

    2014-01-15

    Highlights: • Novel Pd supported ceria–ZnO photocatalysts were prepared with different amounts of palladium. • The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. • Near complete removal of MTBE was achieved using 1% Pd doped ceria–ZnO catalyst and UV irradiation. • Highest rate constant was obtained in case of 1% Pd doped ceria–ZnO catalyst. • Shape and size of pores are important factors for high photoactivity of catalyst. -- Abstract: A series of binary oxide catalysts (ceria–ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%–1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N{sub 2} sorptiometry study. The XPS results confirmed the structure of the Pd CeO{sub 2−x}-ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100 ppm aqueous solution of MTBE upon UV irradiation for 5 h in the presence of 100 mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria–ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N{sub 2} sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction.

  9. The rapid detection of methyl tert-butyl ether (MtBE) in water using a prototype gas sensor system.

    Science.gov (United States)

    de Lacy Costello, B P J; Sivanand, P S; Ratcliffe, N M; Reynolds, D M

    2005-01-01

    The gasoline additive Methyl-tertiary-Butyl Ether (MtBE) is the second most common contaminant of groundwater in the USA and represents an important soil contaminant. This compound has been detected in the groundwater in at least 27 states as a result of leaking underground storage facilities (gasoline storage tanks and pipelines). Since the health effects of MtBE are unclear the potential threat to drinking water supplies is serious. Therefore, the ability to detect MtBE at low levels (ppb) and on-line at high-risk groundwater sites would be highly desirable. This paper reports the use of 'commercial' and metal oxide sensor arrays for the detection of MtBE in drinking and surface waters at low ppb level (microg.L(-1) range). The output responses from some of the sensors were found to correlate well with MtBE concentrations under laboratory conditions.

  10. Comparison of the effects of tert-butyl hydroperoxide and peroxynitrite on the oxidative damage to isolated beef heart mitochondria

    Czech Academy of Sciences Publication Activity Database

    Kohutiar, Matej; Ivica, Josko; Vytášek, R.; Skoumalová, A.; Illner, Jan; Šantorová, P.; Wilhelm, Jiří

    2016-01-01

    Roč. 65, č. 4 (2016), s. 617-626 ISSN 0862-8408 R&D Projects: GA ČR(CZ) GAP303/11/0298 Institutional support: RVO:67985823 Keywords : oxidative stress * free radicals * lipid peroxidation * lipofuscinlike pigments * nitrotyrosine Subject RIV: ED - Physiology Impact factor: 1.461, year: 2016

  11. Are Vicinal Metal Surfaces Stable?

    DEFF Research Database (Denmark)

    Frenken, J. W. M.; Stoltze, Per

    1999-01-01

    We use effective medium theory to demonstrate that the energies of many metal surfaces are lowered when these surfaces are replaced by facets with lower-index orientations. This implies that the low-temperature equilibrium shapes of many metal crystals should be heavily faceted. The predicted...... instability of vicinal metal surfaces is at variance with the almost generally observed stability of these surfaces. We argue that the unstable orientations undergo a defaceting transition at relatively low temperatures, driven by the high vibrational entropy of steps....

  12. Correlating substituent parameter values to electron transport properties of molecules

    International Nuclear Information System (INIS)

    Vedova-Brook, Natalie; Matsunaga, Nikita; Sohlberg, Karl

    2004-01-01

    There are a vast number of organic compounds that could be considered for use in molecular electronics. Because of this, the need for efficient and economical screening tools has emerged. We demonstrate that the substituent parameter values (σ), commonly found in advanced organic chemistry textbooks, correlate strongly with features of the charge migration process, establishing them as useful indicators of electronic properties. Specifically, we report that ab initio derived electronic charge transfer values for 16 different substituted aromatic molecules for molecular junctions correlate to the σ values with a correlation coefficient squared (R 2 ) of 0.863

  13. Substituent distribution within cross-linked and hydroxypropylated sweet potato starch and potato starch

    NARCIS (Netherlands)

    Zhao, J.; Schols, H.A.; Chen Zenghong,; Jin Zhengyu,; Buwalda, P.L.; Gruppen, H.

    2012-01-01

    Revealing the substituents distribution within starch can help to understand the changes of starch properties after modification. The distribution of substituents over cross-linked and hydroxypropylated sweet potato starch was investigated and compared with modified potato starch. The starches were

  14. Photostability enhancement of the pentacene derivative having two nitronyl nitroxide radical substituents.

    Science.gov (United States)

    Shimizu, Akihiro; Ito, Akitaka; Teki, Yoshio

    2016-02-18

    Pentacene derivatives possessing nitronyl nitroxide radical substituents (1a and 1b) were synthesized, and their photochemical properties were evaluated. 1a with two radical substituents showed a remarkable enhancement of photostability compared with pentacene, 6,13-bis(triisopropylsilylethynyl)pentacene and the monoradical, 1b. This is understood due to the presence of the multiple deactivation pathways in the photoexcited states.

  15. Nanowires and nanoneedles nucleation on vicinal substrate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xu, E-mail: zhangxubetter@gmail.com [Henan Key Laboratory of Laser and Opto-electric Information Technology, School of Information Engineering, Zhengzhou University, Zhengzhou 450052 (China); Xie, Dan; Huang, Genling [Zhengzhou Railway Vocational and Technical College, Zhengzhou 450052 (China); Sun, Xiao-Hong [Henan Key Laboratory of Laser and Opto-electric Information Technology, School of Information Engineering, Zhengzhou University, Zhengzhou 450052 (China)

    2015-01-01

    An analytic stress-driven nucleation model of nanowires (NWs) and nanoneedles (NNs) growing on a mismatched vicinal substrate is proposed. It is demonstrated that the formation enthalpy of NWs and NNs is a function of three independent variables, the base radius, aspect ratio and miscut angle of the vicinal surface. Theoretical analysis shows that the minimum nucleation barrier of an island decreases with increment of substrate misorientation, which means the nucleation of islands on a vicinal substrate is more favorable than that on a flat substrate.

  16. Interaction of albumin with perylene-diimides with aromatic substituents

    Science.gov (United States)

    Farooqi, Mohammed; Penick, Mark; Burch, Jessica; Negrete, George; Brancaleon, Lorenzo

    2015-03-01

    Polyaromatic hydrocarbons (PAH) binding to proteins remains one of the fundamental aspects of research in biophysics. Ligand binding can regulate the function of proteins. Binding to small ligands remains a very important aspect in the study of the function of many proteins. Perylene diimide or PDI derivatives have attracted initial interest as industrial dyes and pigments. Recently, much attention has been focused on their strong π - π stacks resulting from the large PDI aromatic core. These PDI stacks have distinct optical properties, and provide informative models that mimic the light-harvesting system and initial charge separation and charge transfer in the photosynthetic system. The absorption property of PDI derivatives may be largely tuned from visible to near-infrared region by chemical modifications at the bay-positions. We are currently studying a new class of PDI derivatives with substituents made of the side chains of aromatic amino acids (Tyrosine, Tryptophan and Phenylalanine). We have looked at the fluorescence absorption and emission of these PDIs in water and other organic solvents. PDIs show evidence of dimerization and possible aggregation. We also present binding studies of these PDIs with Human Serum Albumin (HSA). The binding was studied using fluorescence emission quenching of the HSA Tryptophan residue. Stern-Volmer equation is used to derive the quenching constants. PDI binding to HSA also has an effect on the fluorescence emission of the PDIs themselves by red shifting the spectra. Funded by RCMI grant.

  17. Interchain interactions in charged diacetylenic oligomers carrying bulk substituents revisited

    International Nuclear Information System (INIS)

    Ottonelli, M.; Izzo, G.M.M.; Comoretto, D.; Musso, G.F.; Dellepiane, G.

    2006-01-01

    We are studying how the electronic properties of an aggregate, built with conjugated oligomers carrying bulk substituents, are affected by intermolecular interactions. In this paper we apply the CEO (Collective Electronic Oscillator) method, on the basis of the semiempirical INDO/S Hamiltonian, to compute the electronic density matrix modifications following the photon absorption in a doubly charged cluster of two units of a fully carbazolyl-substituted oligodiacetylene tetramer, taken as a model system. The picture that had emerged from our previous calculations based on the less sophisticated CIS (Configuration Interaction including Singles) approach is seen to be confirmed. Despite the large separation between the backbones, a through-space charge transfer occurs between the two oligomers due to the fact that the excess charge, contrary to what is generally believed, is not localized on the conjugated backbone, but is spread out over the carbazolyl moieties of the charged molecule. Consideration of this kind of interaction improves the theoretical results obtained for the isolated charged oligomer chain, and aids in better explaining some features of the experimental photoinduced spectra of the corresponding polymer

  18. The investigation of substituent effects on the fragmentation pathways of pentacoordinated phenoxyspirophosphoranes by ESI-MSn.

    Science.gov (United States)

    Cui, Xiaoyan; Sun, Can; Zhao, Pei; Wang, Yanyan; Guo, Yanchun; Zhao, Yufen; Cao, Shuxia

    2018-04-01

    The fragmentation pathways of pentacoordinated phenoxyspirophosphoranes were investigated in the positive mode by electrospray ionization multistage mass spectrometry. The results demonstrate that the sodium adducts of the title compounds undergo two competitive fragmentation pathways, and the fragmentation patterns are heavily dependent on the various substituent patterns at the phenolic group. An electron-withdrawing substituent at the ortho-position always results in the removal of a corresponding phenol analogue, while cleavage by spiroring opening becomes the predominant fragmentation pathway if an electron-donating substituent is at the phenolic group. The substituent effects on the competitive fragmentation pathways were further elucidated by theoretical calculations, single crystal structure analysis, and high-resolution mass spectrometry. The results contribute to the understanding of the gas-phase fragmentation reactions and the structure identification of spirophosphorane analogues by electrospray ionization multistage mass spectrometry. Copyright © 2018 John Wiley & Sons, Ltd.

  19. Effects of the Substituents of Boron Atoms on Conjugated Polymers Containing B←N Units.

    Science.gov (United States)

    Liu, Jun; Wang, Tao; Dou, Chuandong; Wang, Lixiang

    2018-06-15

    Organoboron chemistry is a new tool to tune the electronic structures and properties of conjugated polymers, which are important for applications in organic opto-electronic devices. To investigate the effects of substituents of boron atoms on conjugated polymers, we synthesized three conjugated polymers based on double B←N bridged bipyridine (BNBP) with various substituents on the boron atoms. By changing the substituents from four phenyl groups and two phenyl groups/two fluorine atoms to four fluorine atoms, the BNBP-based polymers show the blue-shifted absorption spectra, decreased LUMO/HOMO energy levels and enhanced electron affinities, as well as the increased electron mobilities. Moreover, these BNBP-based polymers can be used as electron acceptors for all-polymer solar cells. These results demonstrate that the substituents of boron atoms can effectively modulate the electronic properties and applications of conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Towards physical interpretation of substituent effects: the case of N- and C3-substituted pyrrole derivatives

    Czech Academy of Sciences Publication Activity Database

    Zborowski, K. K.; Szatylowicz, H.; Stasyuk, Olga A.; Krygowski, T. M.

    2017-01-01

    Roč. 28, č. 4 (2017), s. 1223-1227 ISSN 1040-0400 Institutional support: RVO:61388963 Keywords : substituent effect * pyrrole derivatives * Hammett equation * charges of the substituent active region Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.582, year: 2016 https://link.springer.com/article/10.1007%2Fs11224-017-0938-7

  1. Substituent effects on geometric and electronic properties of iron tetraphenylporphyrin: a DFT investigation.

    Science.gov (United States)

    Wei, Lu; She, Yuanbin; Yu, Yanmin; Yao, Xiaoqian; Zhang, Suojiang

    2012-06-01

    To investigate the effects of the substituents, substituent positions and axial chloride ligand on the geometric and electronic properties of the iron tetraphenylporphyrin (FeTPP), a series of the substituented iron tetraphenylporphyrins and their chlorides, FeT(o/p-R)PP and FeT(o/p-R)PPCl (R = -H, -Cl, -NO(2), -OH, -OCH(3)), were systematically calculated without any symmetry constraint by using DFT method. For geometric structure, the substituent position and axial Cl ligand change the configuration of the iron porphyrin obviously. The ortho-substituents prefer making the phenyls perpendicular to the porphyrin ring; the axial chloride draws the central Fe ion ~0.500 Å out of the porphyrin plane toward the ligand. With regard to electronic properties, it is found that E(LUMO) could be related to the catalytic activity. The electron-withdrawing group always lowers the energies of both frontier orbitals, while the electron-donating one heightens them simultaneously, but they affect the E(HOMO) and E(LUMO) in the same sequence, -NO(2) < -Cl < -H < -OH < -OCH(3). The substituent effects on the central Fe ion were explored by calculating NBO charge distribution, spin density and natural electron configuration.

  2. TOPICAL REVIEW: Vicinal surfaces for functional nanostructures

    Science.gov (United States)

    Tegenkamp, Christoph

    2009-01-01

    Vicinal surfaces are currently the focus of research. The regular arrangements of atomic steps on a mesoscopic scale reveal the possibility to functionalize these surfaces for technical applications, e.g. nanowires, catalysts, etc. The steps of the vicinal surface are well-defined defect structures of atomic size for nucleation of low-dimensional nanostructures. The concentration and therefore the coupling between the nanostructures can be tuned over a wide range by simply changing the inclination angle of the substrate. However, the coupling of these nano-objects to the substrate is just as important in controlling their electronic or chemical properties and making a functionality useable. On the basis of stepped insulating films, these aspects are fulfilled and will be considered in the first part of this review. Recent results for the epitaxial growth of wide bandgap insulating films (CaF2, MgO, NaCl, BaSrO) on metallic and semiconducting vicinal substrates (Si(100), Ge(100), Ag(100)) will be presented. The change of the electronic structure, the adsorption behavior as well as the kinetics and energetics of color centers in the presence of steps is discussed. The successful bridging of the gap between the atomic and mesoscopic world, i.e. the functionalization of vicinal surfaces by nanostructures, is demonstrated in the second part by metal adsorption on semiconducting surfaces. For (sub)monolayer coverage these systems have in common that the surface states do not hybridize with the support, i.e. the semiconducting surfaces are insulating. Here I will focus on the latest results of macroscopic transport measurements on Pb quantum wires grown on vicinal Si(111) showing indeed a one-dimensional transport behavior.

  3. The effects of characteristics of substituents on toxicity of the nitroaromatics: HiT QSAR study

    Science.gov (United States)

    Kuz'min, Victor E.; Muratov, Eugene N.; Artemenko, Anatoly G.; Gorb, Leonid; Qasim, Mohammad; Leszczynski, Jerzy

    2008-10-01

    The present study applies the Hierarchical Technology for Quantitative Structure-Activity Relationships (HiT QSAR) for (i) evaluation of the influence of the characteristics of 28 nitroaromatic compounds (some of which belong to a widely known class of explosives) as to their toxicity; (ii) prediction of toxicity for new nitroaromatic derivatives; (iii) analysis of the effects of substituents in nitroaromatic compounds on their toxicity in vivo. The 50% lethal dose concentration for rats (LD50) was used to develop the QSAR models based on simplex representation of molecular structure. The preliminary 1D QSAR results show that even the information on the composition of molecules reveals the main tendencies of changes in toxicity. The statistic characteristics for partial least squares 2D QSAR models are quite satisfactory ( R 2 = 0.96-0.98; Q 2 = 0.91-0.93; R 2 test = 0.89-0.92), which allows us to carry out the prediction of activity for 41 novel compounds designed by the application of new combinations of substituents represented in the training set. The comprehensive analysis of toxicity changes as a function of substituent position and nature was carried out. Molecular fragments that promote and interfere with toxicity were defined on the basis of the obtained models. It was shown that the mutual influence of substituents in the benzene ring plays a crucial role regarding toxicity. The influence of different substituents on toxicity can be mediated via different C-H fragments of the aromatic ring.

  4. Substituent Effects on the Hydrogen Bonding Between Phenolate and HF, H2O and NH3

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    B3LYP/6-31+g(d) calculations were performed on the hydrogen bonded complexes between substituted phenolates and HF, H2O as well as NH3. It was found that some properties of the non-covalent complexes, including the interaction energies, donor-acceptor (host-guest) distances, bond lengths, and vibration frequencies, could show well-defined substituent effects. Thus, from the substituent studies we can not only understand the mechanism of a particular non-covalent interaction better, but also easily predict the interaction energies and structures of a particular non-covalent complex, which might otherwise be very hard or resource-consuming to be known. This means that substituent effect is indeed a useful tool to be used in supramolecular chemistry and therefore, many valuable studies remain to be carried out.

  5. The substituent and solvent effects on the antioxidant activity of the ferulic acid derivations

    International Nuclear Information System (INIS)

    Najafi, M.; Bukhari, S.A.

    2014-01-01

    The antioxidant activity of ortho and meta substituted ferulic acid derivatives have been investigated in the gas phase and water. The reaction enthalpies of antioxidant activity of studied derivatives have been calculated and compared with corresponding values of ferulic acid. Results show that EWG substituents increase the BDE, IP, while EDG ones cause a rise in the PA. The ferulic acid derivatives with lowest BDE, IP and PA values were identified as the compounds with high antioxidant activity. Results show that the substituents at ortho position have high potential for synthesis of novel ferulic acid derivatives. Results show that ferulic acid derivatives can process their protective role via HAT and SPLET mechanism in gas phase and solvent, respectively. The calculated reaction enthalpies of the substituted ferulic acids have linear dependences with Hammett constants and EHOMO that can be utilized in the selection of suitable substituents for the synthesis of novel antioxidants based on ferulic acid. (author)

  6. Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

    Science.gov (United States)

    Yamazaki, Shin-ichi; Yamada, Yusuke; Takeda, Sahori; Goto, Midori; Ioroi, Tsutomu; Siroma, Zyun; Yasuda, Kazuaki

    2010-08-21

    Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.

  7. Effect of substituents on polarizability and hyperpolarizability values of benzimidazole metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Praveen, P. A.; Babu, R. Ramesh, E-mail: rampap2k@yahoo.co.in [Crystal Growth and Thin films Laboratory, Department of Physics, Bharathidasan University, Tiruchirappalli - 620 024, Tamilnadu (India)

    2016-05-23

    In this report, the polarizability and first and second order hyperpolarizability values of bis benzimidazole Zn(II)-2R and bis benzimidazole Cd(II)-2R complexes, with different electron donating moieties R (R= Cl, Br, I, Acetate) were calculated using time dependent Hartree-Fock (TDHF) formalism embedded in MOPAC2012 package. Further the role of substituents on polarizability and hyperpolarizability values is investigated for the first time by analyzing the frontier molecular orbitals of the complexes with respect to the electronegativity of the substituents. It is found that the increase in electronegativity of the substituents correspondingly increases the energy gap of the molecules, which in turn reduces the polarizability values of both Zn and Cd benzimidazole complexes. Similarly, increase in electronegativity reduces the electric quadrupole moments of both the metal complexes, which in turn reduces the hyperpolarizability values.

  8. Quantum-corrected geometry of horizon vicinity

    Energy Technology Data Exchange (ETDEWEB)

    Park, I.Y. [Department of Applied Mathematics, Philander Smith College, Little Rock, AR (United States)

    2017-12-15

    We study the deformation of the horizon-vicinity geometry caused by quantum gravitational effects. Departure from the semi-classical picture is noted, and the fact that the matter part of the action comes at a higher order in Newton's constant than does the Einstein-Hilbert term is crucial for the departure. The analysis leads to a Firewall-type energy measured by an infalling observer for which quantum generation of the cosmological constant is critical. The analysis seems to suggest that the Firewall should be a part of such deformation and that the information be stored both in the horizon-vicinity and asymptotic boundary region. We also examine the behavior near the cosmological horizon. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Step patterns on vicinal reconstructed surfaces

    Science.gov (United States)

    Vilfan, Igor

    1996-04-01

    Step patterns on vicinal (2 × 1) reconstructed surfaces of noble metals Au(110) and Pt(110), miscut towards the (100) orientation, are investigated. The free energy of the reconstructed surface with a network of crossing opposite steps is calculated in the strong chirality regime when the steps cannot make overhangs. It is explained why the steps are not perpendicular to the direction of the miscut but form in equilibrium a network of crossing steps which make the surface to look like a fish skin. The network formation is the consequence of competition between the — predominantly elastic — energy loss and entropy gain. It is in agreement with recent scanning tunnelling microscopy observations on vicinal Au(110) and Pt(110) surfaces.

  10. Quantum-corrected geometry of horizon vicinity

    International Nuclear Information System (INIS)

    Park, I.Y.

    2017-01-01

    We study the deformation of the horizon-vicinity geometry caused by quantum gravitational effects. Departure from the semi-classical picture is noted, and the fact that the matter part of the action comes at a higher order in Newton's constant than does the Einstein-Hilbert term is crucial for the departure. The analysis leads to a Firewall-type energy measured by an infalling observer for which quantum generation of the cosmological constant is critical. The analysis seems to suggest that the Firewall should be a part of such deformation and that the information be stored both in the horizon-vicinity and asymptotic boundary region. We also examine the behavior near the cosmological horizon. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Functional electrolyte for lithium-ion batteries

    Science.gov (United States)

    Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

    2015-04-14

    Functional electrolyte solvents include compounds having at least one aromatic ring with 2, 3, 4 or 5 substituents, at least one of which is a substituted or unsubstituted methoxy group, at least one of which is a tert-butyl group and at least one of which is a substituted or unsubstituted polyether or poly(ethylene oxide) (PEO) group bonded through oxygen to the aromatic ring, are provided.

  12. Delocalization does not always stabilize : a quantum chemical analysis of -substituent effects on 54 alkyl and vinyl cations

    NARCIS (Netherlands)

    Alem, van K.; Lodder, G.; Zuilhof, H.

    2002-01-01

    The effects of -substituents on alkyl and vinyl cations are studied using high-level ab initio calculations. The geometries, stabilities, and electronic properties of 27 alkyl cations and 27 vinyl cations with -substituents are computed at the B3LYP/6-311 G(d,p), MP2/6-311 G(d,p), and CBS-Q levels.

  13. Identification of substituent groups and related genes involved in salecan biosynthesis in Agrobacterium sp. ZX09.

    Science.gov (United States)

    Xu, Linxiang; Cheng, Rui; Li, Jing; Wang, Yang; Zhu, Bin; Ma, Shihong; Zhang, Weiming; Dong, Wei; Wang, Shiming; Zhang, Jianfa

    2017-01-01

    Salecan, a soluble β-1,3-D-glucan produced by a salt-tolerant strain Agrobacterium sp. ZX09, has been the subject of considerable interest in recent years because of its multiple bioactivities and unusual rheological properties in solution. In this study, both succinyl and pyruvyl substituent groups on salecan were identified by an enzymatic hydrolysis following nuclear magnetic resonance (NMR), HPLC, and MS analysis. The putative succinyltransferase gene (sleA) and pyruvyltransferase gene (sleV) were determined and cloned. Disruption of the sleA gene resulted in the absence of succinyl substituent groups on salecan. This defect could be complemented by expressing the sleA cloned in a plasmid. Thus, the sleA and sleV genes located in a 19.6-kb gene cluster may be involved in salecan biosynthesis. Despite the lack of succinyl substituents, the molecular mass of salecan generated by the sleA mutant did not substantially differ from that generated by the wild-type strain. Loss of succinyl substituents on salecan changed its rheological characteristics, especially a decrease in intrinsic viscosity.

  14. Molecules with Linear π-Conjugated Pathways between All Substituents : Omniconjugation

    NARCIS (Netherlands)

    Veen, Marleen H. van der; Rispens, Minze T.; Jonkman, Harry T.; Hummelen, Jan C.

    2004-01-01

    In this paper, omniconjugation is introduced as a topological phenomenon in π-conjugated systems. Omniconjugated molecules are defined by the fact that they provide direct and fully π-conjugated pathways between all substituents attached to them. Surprisingly, until now such topologies have never

  15. Functional dependency of structures of ionic liquids: do substituents govern the selectivity of enzymatic glycerolysis?

    DEFF Research Database (Denmark)

    Guo, Zheng; Chen, Biqiang; Murillo, Rafael López

    2006-01-01

    hydrophobic substituents and hydrophilic ethoxyl or hydroxyl moieties is found, respectively, to be essential for triglycerides (TG) dissolving and equilibrium shifting. The reactions in the ILs with cations consisting of long chain and free hydroxyl groups gave markedly higher conversion of TG and better...

  16. Substituent effif ects on hydrogen bonding in Watson-Crick base pairs. A theoretical study

    NARCIS (Netherlands)

    Fonseca Guerra, C.; van der Wijst, T.; Bickelhaupt, F.M.

    2005-01-01

    We have theoretically analyzed Watson-Crick AT and GC base pairs in which purine C8 and/or pyrimidine C6 positions carry a substituent X = H, F, Cl or Br, using the generalized gradient approximation (GGA) of density functional theory at BP86/TZ2P. The purpose is to study the effects on structure

  17. Evaluation of achiral templates with fluxional Brønsted basic substituents in enantioselective conjugate additions.

    Science.gov (United States)

    Adachi, Shinya; Takeda, Norihiko; Sibi, Mukund P

    2014-12-19

    Enantioselective conjugate addition of malononitrile to pyrazolidinone-derived enoates proceeds in excellent yields and high enantioselectivities. A comparison of fluxional substituents with and without a Brønsted basic site and their impact on selectivity is detailed. Molecular sieves as an additive were found to be essential to achieve high enantioselectivity.

  18. Role of substituents on the reactivity and electron density profile of ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 5. Role of substituents on the reactivity and electron density profile of diimine ligands: A density functional theory based study. Bhakti S Kulkarni Deepti Mishra Sourav Pal. Volume 125 Issue 5 September 2013 pp 1247-1258 ...

  19. Substituent effects on the excited states of phenyl-capped phenylene vinylene tetramers

    NARCIS (Netherlands)

    Candeias, L.P.; Gelinck, G.H.; Piet, J.J.; Piris, J.; Wegewijs, B.; Peeters, E.; Wildeman, J.; Hadziioannou, G.; Müllen, K.

    2001-01-01

    The singlet and triplet excited states of phenyl-capped tetramers of phenylene vinylene with different alkyl, alkoxy or cyano substituents, were investigated in benzene solution. The lowest singlet states were studied by laser flash-photolysis with time-resolved microwave conductivity and

  20. Substituent effects in the ortho position: Model compounds with a removed reaction centre

    Czech Academy of Sciences Publication Activity Database

    Böhm, S.; Exner, Otto

    2007-01-01

    Roč. 81, 5/6 (2007), s. 993-1006 ISSN 0137- 5083 Institutional research plan: CEZ:AV0Z40550506 Keywords : substituent effect * density functional theory * ortho effect * steric effect Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.483, year: 2007

  1. Changes in vicine, con vicine and oligosaccharides contents during germination of broad bean

    International Nuclear Information System (INIS)

    Al-Kaisey, T. M.; Al-Hadithi, R. T.; Sahead, A. B.

    1997-01-01

    Seeds of three cultivars of broad beans were subjected to germination at 25 deg. for 24, 48 and 72 hours. Also, three sets of experiments were germinated for 48 hour se and each one was subjected to different concentrations of gibberellin (100), 200 ppm) as growth regulator. Significant levels of variation were found in the contents of vicine and con vicine during seeds germination. Meanwhile, a complete disappearance of raffinose, scythe's and verbascose (the flatus factors in broad beans) were observed. No significant differences were found in the non-flatulent sugars, protein, ash and oil in the un germinated and germinated seed. (authors). 19 refs., 3 tabs

  2. Mount Zirkel Wilderness and vicinity, Colorado

    International Nuclear Information System (INIS)

    Snyder, G.L.; Patten, L.L.

    1984-01-01

    Several areas of metallic and nonmetallic mineralization have been identified from surface occurrences within the Mount Zirkel Wilderness and vicinity, Colorado. Three areas of probable copper-lead-zinc-silver-gold resource potential, two areas of probable chrome-platinum resource potential, four areas of probable uranium-thorium resource potential, two areas of probable molybdenum resource potential, and one area of probable fluorspar potential were identified by studies in 1965-1973 by the USGS and USBM. No potential for fossil fuel or geothermal resources was identified

  3. Methyl tert-butyl ether (MTBE) detected in abnormally high concentrations in postmortem blood and urine from two persons found dead inside a car containing a gasoline spill.

    Science.gov (United States)

    Karinen, Ritva; Vindenes, Vigdis; Morild, Inge; Johnsen, Lene; Le Nygaard, Ilah; Christophersen, Asbjørg S

    2013-09-01

    Two deep frozen persons, a female and a male, were found dead in a car. There had been an explosive fire inside the car which had extinguished itself. On the floor inside the car were large pools of liquid which smelled of gasoline. The autopsy findings and routine toxicological analyses could not explain the cause of death. Carboxyhemoglobin levels in the blood samples were gasoline as a fuel oxygenate. Gasoline poisoning is likely to be the cause of the death in these two cases, and MTBE can be a suitable marker of gasoline exposure, when other volatile components have vaporized. © 2013 American Academy of Forensic Sciences.

  4. Tert-butyl 3-oxo-2,3,4,5,6,7-hexahydro-1H-pyrazolo[4,3-c]pyridine-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Tara Shahani

    2010-01-01

    Full Text Available In the title compound, C11H17N3O3, the pyrazole ring is approximately planar, with a maximum deviation of 0.005 (2 Å, and forms a dihedral angle of 5.69 (13° with the plane through the six atoms of the piperidine ring. In the crystal, pairs of intermolecular N—H...O hydrogen bonds form dimers with neighbouring molecules, generating R22(8 ring motifs. These dimers are further linked into two-dimensional arrays parallel to the bc plane by intermolecular N—H...O and C—H...O hydrogen bonds.

  5. Synthesis of densely grafted copolymers with tert-butyl methacrylate/2-(dimethylamino ethyl) methacrylate side chains as precursors for brush polyelectrolytes and polyampholytes

    Czech Academy of Sciences Publication Activity Database

    Gromadzki, Daniel; Štěpánek, Petr; Makuška, R.

    2013-01-01

    Roč. 137, č. 3 (2013), s. 709-715 ISSN 0254-0584 R&D Projects: GA ČR GA202/09/2078 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymers * fourier transform infrared spectroscopy (FTIR) * nuclear magnetic resonance (NMR) Subject RIV: BO - Biophysics Impact factor: 2.129, year: 2013

  6. Experimental and Theoretical Investigation of the Function of 4- tert-Butyl Pyridine for Interface Energy Level Adjustment in Efficient Solid-State Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Yang, Lei; Lindblad, Rebecka; Gabrielsson, Erik; Boschloo, Gerrit; Rensmo, Håkan; Sun, Licheng; Hagfeldt, Anders; Edvinsson, Tomas; Johansson, Erik M J

    2018-04-11

    4- tert-Butylpyridine ( t-BP) is commonly used in solid state dye-sensitized solar cells (ssDSSCs) to increase the photovoltaic performance. In this report, the mechanism how t-BP functions as a favorable additive is investigated comprehensively. ssDSSCs were prepared with different concentrations of t-BP, and a clear increase in efficiency was observed up to a maximum concentration and for higher concentrations the efficiency thereafter decreases. The energy level alignment in the complete devices was measured using hard X-ray photoelectron spectroscopy (HAXPES). The results show that the energy levels of titanium dioxide are shifted further away from the energy levels of spiro-OMeTAD as the t-BP concentration is increased. This explains the higher photovoltage obtained in the devices with higher t-BP concentration. In addition, the electron lifetime was measured for the devices and the electron lifetime was increased when adding t-BP, which can be explained by the recombination blocking effect at the surface of TiO 2 . The results from the HAXPES measurements agree with those obtained from density functional theory calculations and give an understanding of the mechanism for the improvement, which is an important step for the future development of solar cells including t-BP.

  7. Isothermal Vapour-Liquid Equilibria in the Ternary System tert-Butyl Methyl Ether + tert-Butanol + 2,2,4-Trimethylpentane and the Three Binary Subsystems

    Czech Academy of Sciences Publication Activity Database

    Bernatová, Svatoslava; Wichterle, Ivan

    2001-01-01

    Roč. 180, 1-2 (2001), s. 235-245 ISSN 0378-3812 R&D Projects: GA ČR GA104/99/0136 Institutional research plan: CEZ:AV0Z4072921 Keywords : vapourůliquid equilibrium * experimental data * molar excess volume Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.217, year: 2001

  8. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene . VI: Application of observed trends to stannyl derivatives

    Science.gov (United States)

    Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2004-09-01

    The effects of substitution of X=C by Si or Ge in X(CH 3) 3 moieties attached to the formal double bond of 3,3-dimethylcyclopropene are examined. Regularities in observed trends of vibrational frequencies implicating the moieties containing the X atom, as the X atomic mass is increased, are extrapolated to X=Sn. The results of this extrapolation made it possible to assign the known experimental vibrational frequencies of 3,3-dimethyl-1-(trimethylstannyl)cyclopropene and 3,3-dimethyl-1,2-bis(trimethylstannyl)cyclopropene.

  9. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene III. 3,3-Dimethyl-1-(trimethylsilyl)cyclopropene

    Science.gov (United States)

    De Maré, G. R.; Panchenko, Yu. N.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2003-07-01

    The experimental Raman and IR vibrational spectra of 3,3-dimethyl-1-(trimethylsilyl)cyclopropene in the liquid phase were recorded. Total geometry optimisation was carried out at the HF/6-31G* level and the HF/6-31G*//HF/6-31G* force field was computed. This force field was corrected by scale factors determined previously (using Pulay's method) for correction of the HF/6-31G*//HF/6-31G* force fields of 3,3-dimethylbutene-1, 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene. The theoretical vibrational frequencies calculated from the scaled quantum mechanical force field and the theoretical intensities obtained from the quantum mechanical calculation were used to construct predicted spectra and to perform the vibrational analysis of the experimental spectra.

  10. Effect of free-radical spin trap N-tert-butyl-alpha-phenylnitrone on seizures induced in immature rats by homocysteic acid

    Czech Academy of Sciences Publication Activity Database

    Folbergrová, Jaroslava; Druga, Rastislav; Otáhal, Jakub; Haugvicová, Renata; Mareš, Pavel; Kubová, Hana

    2005-01-01

    Roč. 46, č. S6 (2005), s. 375-375 ISSN 0013-9580. [International Epilepsy Congress /26./. 28.08.2005-01.09.2005, Paris] R&D Projects: GA ČR(CZ) GA309/02/1238; GA ČR(CZ) GA309/05/2015 Keywords : free radical scavenger * epilepsy * immature rats * homocysteic acid Subject RIV: ED - Physiology

  11. MALDI-TOF MS analysis of the self-termination products in the anionic methyl methacrylate/tert-butyl acrylate block copolymerization

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Čadová, Eva; Horský, Jiří; Janata, Miroslav

    2015-01-01

    Roč. 72, č. 9 (2015), s. 2227-2239 ISSN 0170-0839 Institutional support: RVO:61389013 Keywords : anionic polymerization * acrylates * block copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.371, year: 2015

  12. Thermodynamic and kinetic analysis of phase separation of temperature-sensitive poly(vinyl methyl ether) in the presence of hydrophobic tert-butyl alcohol

    Czech Academy of Sciences Publication Activity Database

    Velychkivska, Nadiia; Bogomolova, Anna; Filippov, Sergey K.; Starovoytova, Larisa; Labuta, J.

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1419-1428 ISSN 0303-402X R&D Projects: GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : phase separation * coil-globule transition * poly(vinyl methyl ether) Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

  13. Simulation of methyl tert-butyl ether (MTBE) transport to ground water from immobile sources of gasoline in the vadose zone

    Science.gov (United States)

    Lahvis, M.A.; Rehmann, L.C.

    1999-01-01

    The mathematical model, R-UNSAT, developed to simulate the transport of benzene and MTBE in representative sand and clay hydrogeologic systems was evaluated. The effects on groundwater were simulated for small, chronic-, and single-volume releases of gasoline trapped in unsaturated soil. Hydrocarbon biodegradation was simulated by using a dual Monod-type kinetics model that includes oxygen and the reactive constituents. MTBE was assumed to be non-reactive. For MTBE, infiltration had the greatest effect on transport to groundwater. Infiltration also affected mass losses of MTBE to the atmosphere, particularly, in fine-grained soils. Depth to groundwater and soil type primarily affected travel times of MTBE to groundwater, but could affect mass-loading rates to groundwater if infiltration is insignificant. For benzene, transport to groundwater was significant only if the depth to the water table was groundwater were generally smaller for benzene than for MTBE by more than two orders of magnitude. Thus, water that recharges an aquifer beneath a spill can be enriched in MTBE relative to benzene when compared to the composition of water in equilibrium with gasoline.

  14. Effect of γ radiation on the solution of potassium permanganate complex with di-tert.-butyl-dibenzo-18-crown-6 in benzene

    International Nuclear Information System (INIS)

    Makhlyarchuk, V.V.; Zatonskij, S.V.; Mikhajlenko, I.E.; Saraeva, V.V.

    1987-01-01

    Effect of 60 Co gamma-radiation on benzene containing KMnO 4 solubilized with crown-ether is studied. Radiation was carried out at room temperature with doses up to 28 kGy at dose rate of 3.9 Gy/s. Sharp increase of diphenyl yield and absence of phenylcyclohexadiene (PCH) in radiolysis products points out interaction of permanganate-ion with predecessors of PCH formation. High yield of permanganate decomposition results from reactions with excited molecules of the solvent

  15. [2,6-Bis(di-tert-butyl-phosphinometh-yl)-phen-yl-κP,C,P'](nitrato-κO)nickel(II).

    Science.gov (United States)

    Boro, Brian J; Dickie, Diane A; Duesler, Eileen N; Goldberg, Karen I; Kemp, Richard A

    2008-10-15

    The Ni(II) atom in the title compound, [Ni(C(24)H(43)P(2))(NO(3))], adopts a distorted square-planar geometry with the P atoms in a trans arrangement. The compound contains a twofold rotational axis with the nitrate group offset from this axis, except for an O atom of the nitrate group, generating two positions of 50% occupancy for the other atoms of the nitrate group.

  16. 5-tert-Butyl 3-ethyl 1-isopropyl-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine-3,5-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Huan-Mei Guo

    2011-12-01

    Full Text Available In the title compound, C17H27N3O4, the six-membered ring adopts a half-chair conformation with the N atom and the adjacent methylene C atom displaced by −0.391 (2 and 0.358 (2 Å, respectively, from the plane of the other four atoms. In the crystal, molecules are linked by weak C—H...O interactions.

  17. (6S-2-tert-Butyl-6-[(4S,5R-3,4-dimethyl-5-phenyloxazolidin-2-yl]phenol

    Directory of Open Access Journals (Sweden)

    Alexander E. Anderson

    2010-04-01

    Full Text Available The title compound, C21H27NO2, exhibits hydrogen bonding between the phenolic H atom and the heterocyclic N atom. The absolute configuration of the molecule is known from the synthetic procedure.

  18. Study of 2-methyl -2-oxo-3,5-di-tert.-butyl-Δ4-1,3,2-oxazaphospholine interaction with lanthanide shifting reagents

    International Nuclear Information System (INIS)

    Turov, A.V.; Povolotskij, M.I.; Balitskij, Yu.V.; Kornilov, M.Yu.; Boldeskul, I.E.

    1983-01-01

    2-methyl-2-oxo-3.5-di-tret.-butyl-Δ 4 -1, 3, 2-oxazaphospholine in CDCl 3 solution reacts with lanthanide shifting reagents-tris (dipivaloylmethanates) of europium (3) and praseodymium (3)-with the formation of adducts of constant composition. At that, in ( + H, 13 C) NMR spectra considerable pseudocontact induced shifts of substratum signals take place. Geometry of the adducts formed is calculated

  19. Administration of PBN (N-tert-butyl-alfa-phenylnitrone) during status epilepticus reduces neuronal injury, improves cognitive functions but enhances epileptogenesis in immature rats

    Czech Academy of Sciences Publication Activity Database

    Kubová, Hana; Folbergrová, Jaroslava; Otáhal, Jakub; Mareš, Pavel

    2007-01-01

    Roč. 59, Suppl. 1 (2007), s. 10-10 ISSN 1734-1140. [Day of neuropsychopharmacology /16./. 06.09.2007-08.09.2007, Wroclaw] Institutional research plan: CEZ:AV0Z50110509 Keywords : PBN * status epilepticus * immature rats Subject RIV: ED - Physiology

  20. Surface-Initiated Atom Transfer Radical Polymerization of Magnetite Nanoparticles with Statistical Poly(tert-butyl acrylate-poly(poly(ethylene glycol methyl ether methacrylate Copolymers

    Directory of Open Access Journals (Sweden)

    Patcharin Kanhakeaw

    2015-01-01

    Full Text Available This work presented the surface modification of magnetite nanoparticle (MNP with poly[(t-butyl acrylate-stat-(poly(ethylene glycol methyl ether methacrylate] copolymers (P[(t-BA-stat-PEGMA] via a surface-initiated “grafting from” atom transfer radical polymerization (ATRP. Loading molar ratio of t-BA to PEGMA was systematically varied (100 : 0, 75 : 25, 50 : 50, and 25 : 75, resp. such that the degree of hydrophilicity of the copolymers, affecting the particle dispersibility in water, can be fine-tuned. The reaction progress in each step of the synthesis was monitored via Fourier transform infrared spectroscopy (FTIR. The studies in the reaction kinetics indicated that PEGMA had higher reactivity than that of t-BA in the copolymerizations. Gel permeation chromatography (GPC indicated that the molecular weights of the copolymers increased with the increase of the monomer conversion. Transmission electron microscopy (TEM revealed that the particles were spherical with averaged size of 8.1 nm in diameter. Dispersibility of the particles in water was apparently improved when the copolymers were coated as compared to P(t-BA homopolymer coating. The percentages of MNP and the copolymer in the composites were determined via thermogravimetric analysis (TGA and their magnetic properties were investigated via vibrating sample magnetometry (VSM.

  1. Crystal structure of (1R,4R-tert-butyl 3-oxo-2-oxa-5-azabicyclo[2.2.2]octane-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Suvratha Krishnamurthy

    2015-07-01

    Full Text Available In the title compound, C11H17NO4, commonly known as N-tert-butoxycarbonyl-5-hydroxy-d-pipecolic acid lactone, the absolute configuration is (1R,4R due to the enantiomeric purity of the starting material which remains unchanged during the course of the reaction. In the crystal there no intermolecular hydrogen bonds.

  2. Effect of free radical spin trap N-tert-butyl-alpha-phenylnitrone (PBN) on seizures induced in immature rats by homocysteic acid

    Czech Academy of Sciences Publication Activity Database

    Folbergrová, Jaroslava; Druga, Rastislav; Otáhal, Jakub; Haugvicová, Renata; Mareš, Pavel; Kubová, Hana

    2006-01-01

    Roč. 201, č. 1 (2006), s. 105-119 ISSN 0014-4886 R&D Projects: GA ČR(CZ) GA309/05/2015; GA ČR(CZ) GA309/02/1238 Institutional research plan: CEZ:AV0Z50110509; CEZ:AV0Z50200510 Keywords : DL-homocysteic acid induced seizures * neuronal damage * protection Subject RIV: ED - Physiology Impact factor: 4.156, year: 2006

  3. Electron exchange by hexakis(tert-butyl-isocyanide)- and hexakis(cyclohexyl isocyanide)manganese(I,II). Solvent effect on the rate constant and the volume of activation

    International Nuclear Information System (INIS)

    Stebler, M.; Nielson, R.M.; Siems, W.F.; Hunt, J.P.; Dodgen, H.W.; Wherland, H.W.

    1988-01-01

    The rate of electron self-exchange of Mn(CNC(CH 3 ) 3 ) 6 +/2+ and Mn(CNC 6 H 11 ) 6 +/2+ as the BF 4 - salts has been measured by 55 Mn NMR line broadening as a function of pressure, temperature, and concentration in acetonitrile, bromobenzene, benzonitrile, acetone, diethyl ketone, methanol, ethanol, methylene chloride, and trimethyl phosphate, and various binary mixtures of methylene chloride, bromobenzene, and acetonitrile. The values of ΔV double dagger obtained are negative and cover a range of ca. 12 cm 3 /mol, which is limited by ion pairing in the solvents of lower dielectric constant. The variation of the ambient pressure rate constant with solvent is qualitatively different for Mn(CNC(CH 3 ) 3 ) 6 +/2+ reaction than was observed for the Mn(CNC 6 H 11 ) 6 +/2+ reaction. This is taken as further evidence for a significant influence of rather subtle differences in solvation on the molecular level that are not approximated by dielectric continuum models. 30 references, 3 tables

  4. Di-tert-butyl­bis(N-isopropyl-N-methyl­dithio­carbamato-κ2 S,S′)tin(IV)

    Science.gov (United States)

    Muthalib, Amirah Faizah; Baba, Ibrahim; Samsudin, Mohd Wahid; Ng, Seik Weng

    2010-01-01

    The dithio­carbamate anions in the title compound, [Sn(C4H9)2(C5H10NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol­ecule lies across a twofold rotation axis. The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.82 (1):0.18 (1). PMID:21580471

  5. Fine-Tuning of Saponification-Triggered Gelation by Strategic Modification of Peripheral Substituents: Gelation Regulators.

    Science.gov (United States)

    Kumar, Ashish; Singh, Roop Shikha; Kumar, Amit; Ali, Afsar; Biswas, Arnab; Pandey, Daya Shankar

    2016-09-19

    A pioneering approach towards controlling the efficiency of saponification assisted gelation in ethyl ester based Zn II -complexes have been described. Using four new ester containing bis-salen Zn II complexes (C1-C4) involving different para-azo phenyl substituted ligands it has been clearly shown that gelation efficiency is greatly influenced by the electronic effects of the substituents (-H (C1), -CH 3 (C2), -NO 2 (C3), and -OCH 3 (C4)). Morphological, photophysical, and rheological investigations corroborated the experimental observations well and established that gelation efficiency was enhanced with electron-withdrawing characteristics of substituents (C4

  6. Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch

    DEFF Research Database (Denmark)

    Hansen, Mia Harring; Elm, Jonas; Olsen, Stine Tetzschner

    2016-01-01

    We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent dihydroazu......We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent...... on the substitution pattern, and based on these results, we have outlined molecular design considerations for obtaining new desired target structures exhibiting long energy storage times. Selected candidate systems have also been investigated in terms of optical properties to elucidate how sensitive the absorption...

  7. Study of GRBs Hosts Galaxies Vicinity Properties

    Science.gov (United States)

    Bernal, S.; Vasquez, N.; Hoyle, F.

    2017-07-01

    The study of GRBs host galaxies and its vicinity could provide constrains on the progenitor and an opportunity to use these violent explosions to characterize the nature of the highredshift universe. Studies of GRB host galaxies reveal a population of starforming galaxies with great diversity, spanning a wide range of masses, star formation rate, and redshifts. In order to study the galactic ambient of GRBs we used the S. Savaglio catalog from 2015 where 245 GRBs are listed with RA-Dec position and z. We choose 22 GRBs Hosts galaxies from Savaglio catalog and SDSS DR12, with z range 0population characteristics. We calculate the volumetric density populatation of glalaxies around the GRB Hosts within a volume of an sphere whit radius of 10 h-1 Mpc and find a low density compared with a typical group of galaxies. In order to know the galaxies stellar formation state, in regions where GRBs are formed, we made an analysis of color index using SDSS data of μ [λ 3543], r[λ 6231] and calculate the indexes μ-r. We find a value μ-r=2.63, it means that the galactic ambient of GRBs Host regions are statistically redder than void and wall regions on a indirect way (Voids:μ-r=2.043; Walls:μ-r=2.162). Futhermore, we used a inverse concentration index analysis, ICI=R50/R90 and find that galaxies in GRBs Hosts vicinity are also of slightly early type than void and wall galaxies. With this work we provide characteristics on the regions for future works related with highredsift universe that using the GRBs.

  8. Anaerobic C1 metabolism of the O-methyl-14C-labeled substituent of vanillate

    International Nuclear Information System (INIS)

    Frazer, A.C.; Young, L.Y.

    1986-01-01

    The O-methyl substituents of aromatic compounds constitute a C 1 growth substrate for a number of taxonomically diverse anaerobic acetogens. In this study, strain TH-001, an O-demethylating obligate anaerobe, was chosen to represent this physiological group, and the carbon flow when cells were grown on O-methyl substituents as a C 1 substrate was determined by 14 C radiotracer techniques. O-[methyl- 14 C]vanillate (4-hydroxy-3-methoxy-benzoate) was used as the labeled C 1 substrate. The data showed that for every O-methyl carbon converted to [ 14 C]acetate, two were oxidized to 14 CO 2 . Quantitation of the carbon recovered in the two products, acetate and CO 2 , indicated that acetate was formed in part by the fixation of unlabeled CO 2 . The specific activity of 14 C in acetate was 70% of that in the O-methyl substrate, suggesting that only one carbon of acetate was derived from the O-methyl group. Thus, it is postulated that the carboxyl carbon of the product acetate is derived from CO 2 and the methyl carbon is derived from the O-methyl substituent of vanillate

  9. Heavy Atom Substituents as Molecular Probes for Solvent Effects on the Dynamics of Short-lived Triplet Exciplexes

    OpenAIRE

    Winter, Gerhard; Steiner, Ulrich

    1980-01-01

    The influence of heavy atom substituents (Br, I) in the electron donor aniline on the electron transfer reaction with thiopyronine triplet is investigated by flash spectroscopy in solvents of different viscosity and polarity. Triplet quenching constants and radical yields are determined. The results are analysed in terms of decay constants of an intermediate triplet exciplex where the heavy atom substituents significantly enhance the intersystem crossing process leading to singlet ground stat...

  10. Determining the energetics of vicinal perovskite oxide surfaces

    NARCIS (Netherlands)

    Wessels, W.A.; Bollmann, Tjeerd Rogier Johannes; Koster, Gertjan; Zandvliet, Henricus J.W.; Rijnders, Augustinus J.H.M.

    2017-01-01

    The energetics of vicinal SrTiO3(001) and DyScO3(110), prototypical perovskite vicinal surfaces, has been studied using topographic atomic force microscopy imaging. The kink formation and strain relaxation energies are extracted from a statistical analysis of the step meandering. Both perovskite

  11. Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study.

    Science.gov (United States)

    Lu, Jia-Syun; Yang, Ming-Chung; Su, Ming-Der

    2017-07-05

    Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH₃, SiH₃, SiMe(Si t Bu₃)₂, Si i PrDis₂, Tbt (=C₆H₂-2,4,6-(CH(SiMe₃)₂)₃), and Ar* (=C₆H₃-2,6-(C₆H₂-2, 4,6- i -Pr₃)₂)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint.

  12. Substituent effects on the optical properties of naphthalenediimides: A frontier orbital analysis across the periodic table.

    Science.gov (United States)

    Mulder, Joshua R; Guerra, Célia Fonseca; Slootweg, J Chris; Lammertsma, Koop; Bickelhaupt, F Matthias

    2016-01-15

    A comprehensive theoretical treatment is presented for the electronic excitation spectra of ca. 50 different mono-, di-, and tetrasubstituted naphthalenediimides (NDI) using time-dependent density functional theory (TDDFT) at ZORA-CAM-B3LYP/TZ2P//ZORA-BP86/TZ2P with COSMO for simulating the effect of dichloromethane (DCM) solution. The substituents -XHn are from groups 14-17 and rows 2-5 of the periodic table. The lowest dipole-allowed singlet excitation (S0 -S1 ) of the monosubstituted NDIs can be tuned from 3.39 eV for -F to 2.42 eV for -TeH, while the S0 -S2 transition is less sensitive to substitution with energies ranging between 3.67 eV for -CH3 and 3.44 eV for -SbH2 . In the case of NDIs with group-15 and -16 substituents, the optical transitions strongly depend on the extent to which -XHn is planar or pyramidal as well as on the possible formation of intramolecular hydrogen bonds. The accumulative effect of double and quadruple substitution leads in general to increasing bathochromic shifts, but the increased steric hindrance in tetrasubstituted NDIs can lead to deformations that diminish the effectiveness of the substituents. Detailed analyses of the Kohn-Sham orbital electronic structure in monosubstituted NDIs reveal the mesomeric destabilization of the HOMO as the primary cause of the bathochromic shift of the S0-S1 transition. © 2015 Wiley Periodicals, Inc.

  13. Carborane-stilbene dyads: the influence of substituents and cluster isomers on photoluminescence properties.

    Science.gov (United States)

    Ferrer-Ugalde, A; Cabrera-González, J; Juárez-Pérez, E J; Teixidor, F; Pérez-Inestrosa, E; Montenegro, J M; Sillanpää, R; Haukka, M; Núñez, R

    2017-02-14

    Two novel styrene-containing meta-carborane derivatives substituted at the second carbon cluster atom (C c ) with either a methyl (Me) or a phenyl (Ph) group are introduced herein along with a new set of stilbene-containing ortho- (o-) and meta- (m-) carborane dyads. The latter set of compounds have been prepared from styrene-containing carborane derivatives via a Heck coupling reaction. High regioselectivity has been achieved for these compounds by using a combination of palladium complexes [Pd 2 (dba) 3 ]/[Pd(t-Bu 3 P) 2 ] as a catalytic system, yielding exclusively E isomers. All compounds have been fully characterised and the crystal structures of seven of them were analysed by X-ray diffraction. The absorption spectra of these compounds are similar to those of their respective fluorophore groups (styrene or stilbene), showing a very small influence of the substituent (Me or Ph) linked to the second C c atom or the cluster isomer (o- or m-). On the other hand, fluorescence spectroscopy revealed high emission intensities for Me-o-carborane derivatives, whereas their Ph-o-carborane analogues evidenced an almost total lack of fluorescence, confirming the significant role of the substituent bound to the adjacent C c in o-carboranes. In contrast, all the m-carborane derivatives display similar photoluminescence (PL) behavior regardless of the substituent attached to the second C c , demonstrating its small influence on emission properties. Additionally, m-carborane derivatives are significantly more fluorescent than their o-counterparts, reaching quantum yield values as high as 30.2%. Regarding solid state emission, only stilbene-containing Ph-o-carborane derivatives, which showed very low fluorescence in solution, exhibited notable PL emission in films attributed to aggregation-induced emission. DFT calculations were performed to successfully complement the photoluminescence studies, supporting the experimentally observed photophysical behavior of the styrene and

  14. The Influence of Substituents on the Tautomerism of Symmetrically Substituted 2,2'-Bis-benzimidazoles

    Directory of Open Access Journals (Sweden)

    Dall'Oglio Evandro

    2002-01-01

    Full Text Available The tautomerism of five symmetrically substituted 2,2'-bis-benzimidazoles [5(6,5'(6'-tetramethyl- (1; 5(6,5'(6'-dimethyl-(2; 5(6,5'(6'-dichloro- (3; 5(6,5'(6'-dimethoxy- (4 and 4(7,4'(7'-dimethyl-2,2'-bis-benzimidazole (5], was studied by means of ¹H NMR spectroscopy at variable temperatures, and the influence of the substituents on the energy barriers for tautomeric interconversion was interpreted with the aid of theoretical calculations.

  15. Excited-state dynamics of pentacene derivatives with stable radical substituents.

    Science.gov (United States)

    Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio

    2014-06-23

    The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electronic effects of substituents in o-hydroxyazo compounds and azoquinone-hydrazone tautomerism

    International Nuclear Information System (INIS)

    Raikhshtat, M.M.; Zhogina, V.V.; Savvin, S.B.

    1987-01-01

    The authors have investigated the electronic structure of p-substituted phenylazonaphthol and some o-hydroxyazo compounds of the general structure X-N=N-Y. The influence of structural changes of the X and Y radicals on the electronic structure of the o-hydroxyazo group was studied. The results are compared with experimental data, obtained by NMR 13 C, by tautomerism of these compounds in solution in CDCl 3 . The electronic structure of o-hydroxyazo compounds was calculated by the PPDP/2 method. This method satisfactorily describes the electronic structure of organic compounds and correctly reproduces electronic effects of the substituents

  17. A Computational Study of Structure and Reactivity of N-Substitued-4-Piperidones Curcumin Analogues and Their Radical Anions

    Directory of Open Access Journals (Sweden)

    Maximiliano Martínez-Cifuentes

    2016-12-01

    Full Text Available In this work, a computational study of a series of N-substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated. N-substituents include methyl and benzyl groups, while substituents on the aromatic rings cover electron-donor and electron-acceptor groups. Substitutions at the nitrogen atom do not significantly affect the geometry and frontier molecular orbitals (FMO energies of these molecules. On the other hand, substituents on the aromatic rings modify the distribution of FMO. In addition, they influence the capability of these molecules to attach an additional electron, which was studied through adiabatic (AEA and vertical electron affinities (VEA, as well as vertical detachment energy (VDE. To study electrophilic properties of these structures, local reactivity indices, such as Fukui (f+ and Parr (P+ functions, were calculated, and show the influence of the aromatic rings substituents on the reactivity of α,β-unsaturated ketones towards nucleophilic attack. This study has potential implications for the design of curcumin analogues based on a 4-piperidone core with desired reactivity.

  18. Photoelectron spectra and electronic structure of nitrogen analogues of boron β-diketonates with aromatic substituents

    Energy Technology Data Exchange (ETDEWEB)

    Tikhonov, Sergey A., E-mail: allser@bk.ru [Far Eastern Federal University, 8 Sukhanova St., Vladivostok, 690950 (Russian Federation); Vovna, Vitaliy I. [Far Eastern Federal University, 8 Sukhanova St., Vladivostok, 690950 (Russian Federation); Borisenko, Aleksandr V. [Vladivostok Branch of Russian Customs Academy, 16v Strelkovaya St., Vladivostok, 690034 (Russian Federation)

    2016-11-15

    Highlights: • The electronic structures of three nitrogen analogues of boron β-diketonates have been investigated. • UV photoelectron spectra have been interpreted. • The structure of the UV photoelectron spectra is in good agreement with the energies and compositions of Kohn-Sham orbitals. - Abstract: The electronic structure of three nitrogen analogoues of boron β-diketonates containing aromatic substituents was studied by the ultraviolet photoelectron spectroscopy and within the density functional theory. In order to determine effects of heteroatom substitution in the chelate ligand, a comparative analysis was carried out for the electronic structure of three model compounds. In a range of model compounds, the HOMO's nature was revealed to be the same. The HOMO-1 orbital of nitrogen containing compounds is determined by the presence of lone electron pairs of nitrogen. In a range of the complexes under study, the influence of aromatic substituents on the electronic structure was defined. In the imidoylamidinate complex, in contrast to formazanates and β-diketonates, it was found the absence of any noticeable mixing of π-orbitals of the chelate and benzene rings. It was shown that within energy range to 11 eV, the calculated results reproduce well the energy differences between the ionized states of complexes.

  19. The Influence of Substituent Orientation on the Photovoltaic Performance of Phthalocyanine-Sensitized Solar Cells.

    Science.gov (United States)

    Tejerina, Lara; Martínez-Díaz, M Victoria; Nazeeruddin, Mohammad Khaja; Torres, Tomas

    2016-03-18

    Phthalocyanines (Pcs) are used as sensitizers in dye-sensitized solar cells (DSSCs) because of their stability and intense absorption in the red and near-IR regions. Impressive progress has been made in photovoltaic efficiencies by introduction of bulky peripheral substituents to help suppress macrocycle aggregation. To reach benchmark efficiencies reported for other related dyes, new designs need to be explored. Single carboxy-ZnPc regioisomers substituted at the non-peripheral positions by rigid aryl groups have now been studied, which has shed light on the influence of steric hindrance and/or orientation of the substituent around the anchoring group on the photovoltaic response. The regioisomer bearing the aryl group far away from the anchoring group produces a more effective sensitization of the TiO2 films and higher short-circuit photocurrent density (Jsc). Taking advantage of the good photovoltaic performance in the near-IR region of this ZnPc, it was combined with another appropriate dye for panchromatic sensitization of the mesoporous photoelectrode and an increase of the overall device efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. DFT study on the effect of exocyclic substituents on the proton affinity of 1-methylimidazole

    International Nuclear Information System (INIS)

    Liu, Haining; Bara, Jason E.; Turner, C. Heath

    2013-01-01

    Highlights: • DFT calculations are used to predict the proton affinity of 1-methylimidazoles. • The electron-withdrawing groups dominate the predicted proton affinity. • The effects of multiple substituents on the proton affinity can be accurately predicted. • Large compound libraries can be screened for imidazoles with tailored reactivity. - Abstract: A deeper understanding of the acid/base properties of imidazole derivatives will aid the development of solvents, polymer membranes and other materials that can be used for CO 2 capture and acid gas removal. In this study, we employ density functional theory calculations to investigate the effect of various electron-donating and electron-withdrawing groups on the proton affinity of 1-methylimidazole. We find that electron-donating groups are able to increase the proton affinity relative to 1-methylimidazole, i.e., making the molecule more basic. In contrast, electron-withdrawing groups cause a decrease of the proton affinity. When multiple substituents are present, their effects on the proton affinity were found to be additive. This finding offers a quick approach for predicting and targeting the proton affinities of this series of molecules, and we show the strong correlation between the calculated proton affinities and experimental pK a values

  1. Stability Analysis of Spacecraft Motion in the Vicinity of Asteroids

    Data.gov (United States)

    National Aeronautics and Space Administration — The objective of my proposal is to determine the stability of a spacecraft when in the vicinity of an asteroid. Orbiting an asteroid is a difficult task. The unique...

  2. Effect of substituents on electronic properties, thin film structure and device performance of dithienothiophene-phenylene cooligomers

    International Nuclear Information System (INIS)

    Zhang Shiming; Guo Yunlong; Xi Hongxia; Di Chongan; Yu Jian; Zheng Kai; Liu Ruigang; Zhan Xiaowei; Liu Yunqi

    2009-01-01

    Dithienothiophene-phenylene cooligomers with n-hexyloxy or n-dodecyloxy substituents have been synthesized and compared to the previously reported unsubstituted parent compound. The effect of substituents on the thermal, electronic, optical, thin film structure and field-effect transistor (OFET) properties was investigated. Structural phase transitions from highly-ordered nanocrystalline to liquid crystalline were observed at 241 and 213 deg. C for n-hexyloxy- and n-dodecyloxy-substituted compounds respectively, different from the parent compound. For the alkoxy-substituted compounds, the absorption spectra in thin film blue shift 50 nm, while the fluorescence spectra in thin film red shift 88-100 nm compared to those in solution. The OFET devices based on the alkoxy-substituted compounds exhibit mobilities as high as ca 0.02 cm 2 V -1 s -1 and their performance is sensitive to the alkoxy substituents and substrate temperatures

  3. MAJOR OIL PLAYS IN UTAH AND VICINITY

    International Nuclear Information System (INIS)

    Chidsey, Thomas C.; Morgan, Craig D.; McClure, Kevin; Willis, Grant C.

    2003-01-01

    found in the stratigraphically equivalent Navajo Sandstone of southern Utah which displays large-scale dunal cross-strata with excellent reservoir properties and interdunal features such as oases, wadi, and playa lithofacies with poor reservoir properties. Hydrocarbons in the Paradox Formation are stratigraphically trapped in carbonate buildups (or phylloid-algal mounds). Similar carbonate buildups are exposed in the Paradox along the San Juan River of southeastern Utah. Reservoir-quality porosity may develop in the types of facies associated with buildups such as troughs, detrital wedges, and fans, identified from these outcrops. When combined with subsurface geological and production data, these outcrop analogs can improve (1) development drilling and production strategies such as horizontal drilling, (2) reservoir-simulation models, (3) reserve calculations, and (4) design and implementation of secondary/tertiary oil recovery programs and other best practices used in the oil fields of Utah and vicinity. During this quarter, technology transfer activities consisted of exhibiting the project plans, objectives, and products at a booth at the 2003 annual convention of the American Association of Petroleum Geologists. The project home page was updated on the Utah Geological Survey Internet web site

  4. Substituent effects on the electron affinities and ionization energies of tria-, penta-, and heptafulvenes: a computational investigation

    DEFF Research Database (Denmark)

    Dahlstrand, Christian; Yamazaki, Kaoru; Kilså, Kristine

    2010-01-01

    (TCNQ) and tetrathiafulvalene (TTF) as representing strong electron-acceptor and -donor compounds, respectively. The substituents X at the exocyclic positions of the fulvenes were either NH(2), H, or CN, while the substituents Y at the ring positions were H, Cl, F, CN, or NH(2). The variations...... of bis(fulvene)s, i.e., compounds composed of a donor-type heptafulvene fused with an acceptor-type pentafulvene, and it was revealed that these bis(fulvene)s can be designed so that the IE and EA of the two separate fulvene segments are retained, potentially allowing for the design of compact donor...

  5. Novel non-symmetrical bifunctionally-substituted phthalonitriles and corresponding d-metal phthalocyaninates

    Science.gov (United States)

    Vashurin, Artur; Maizlish, Vladimir; Tikhomirova, Tatiyana; Nemtseva, Marina; Znoyko, Serafima; Aleksandriiskii, Viktor

    2018-05-01

    The work reports synthesis of 4-(2-tert-butyl-4,5-dicyanophenylsulfonyl)benzene and its analogue containing carboxyl group in phenyl fragment by nucleophilic substitution of nitro-group of 4-tert-butyl-5-nitrophthalonitrile. Unique structure of the obtained compounds is explained by presence of bulky tert-butyl substituent in combination with carboxyl group, which being part of phthalocyanine molecule impart it higher solubility within different solvents (organic and water mediums) and act as anchoring groups. Based on obtained nitriles phthalocyanine complexes of copper, nickel, cobalt and magnesium are synthesized with good yields. Demetallization of initial magnesium phthalocyanine by hydrochloric acid was performed in order to obtain ligand of phthalocyanine. Synthetic and purification techniques are described in detail. Obtained substances are of specific structure making them to be applied in sensorics for smart materials production, as sensitizers or part of molecular magnets. The structure, NMR and IR spectra are modeled using special software. Resulting experimental and theoretical data are compared. The results show sufficient correlation that confirms correctness of chosen methods and its applicability for theoretical studying compounds related to investigated ones.

  6. Theoretical research on effects of substituents and the solvent on quadruple hydrogen bonded complexes

    Directory of Open Access Journals (Sweden)

    Lingjia Xu

    2007-04-01

    Full Text Available Semiempirical AM1 and INDO/CIS methods were used to study the structures and spectroscopy of hydrogen bonded complexes formed by the oligophenyleneethynylene (monomer A with isophthalic acid (monomer B. The binding energies of the complexes are lowered by increasing electron-donating abilities of the substituents near the hydrogen bonds on monomer A. The first absorptions in the electronic spectra and the vibration frequencies of the N-H bonds in the IR spectra for the complexes are both red-shifted compared with those of the monomers. The presence of dimethylsulfoxide (DMSO can reduce the binding energy of the complex through hydrogen bonding. This results in a blue-shift for the first absorption in the electronic spectrum and red-shift for the vibration frequencies of the N-H bonds in the IR spectrum of the complex.

  7. Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

    Science.gov (United States)

    Asgharzadeh, Somaie; Vahedpour, Morteza

    2018-06-01

    Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

  8. Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces

    Science.gov (United States)

    Hu, Peiguang; Chen, Limei; Deming, Christopher P.; Lu, Jia-En; Bonny, Lewis W.; Chen, Shaowei

    2016-06-01

    Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent

  9. Exothermic or Endothermic Decomposition of Disubstituted Tetrazoles Tuned by Substitution Fashion and Substituents.

    Science.gov (United States)

    Jia, Yu-Hui; Yang, Kai-Xiang; Chen, Shi-Lu; Huang, Mu-Hua

    2018-01-11

    Nitrogen-rich compounds such as tetrazoles are widely used as candidates in gas-generating agents. However, the details of the differentiation of the two isomers of disubstituted tetrazoles are rarely studied, which is very important information for designing advanced materials based on tetrazoles. In this article, pairs of 2,5- and 1,5-disubstituted tetrazoles were carefully designed and prepared for study on their thermal decomposition behavior. Also, the substitution fashion of 2,5- and 1,5- and the substituents at C-5 position were found to affect the endothermic or exothermic properties. This is for the first time to the best of our knowledge that the thermal decomposition properties of different tetrazoles could be tuned by substitution ways and substitute groups, which could be used as a useful platform to design advanced materials for temperature-dependent rockets. The aza-Claisen rearrangement was proposed to understand the endothermic decomposition behavior.

  10. Major Oil Plays in Utah and Vicinity

    Energy Technology Data Exchange (ETDEWEB)

    Thomas C. Chidsey; Craig D. Morgan; Kevin McClure; Douglas A. Sprinkel; Roger L. Bon; Hellmut H. Doelling

    2003-12-31

    fractured and sealed by overlying argillaceous and non-fractured units. The best outcrop analogs for Twin Creek reservoirs are found at Devils Slide and near the town of Peoa, Utah, where fractures in dense, homogeneous non-porous limestone beds are in contact with the basal siltstone units (containing sealed fractures) of the overlying units. The shallow marine, Mississippian Leadville Limestone is a major oil and gas reservoir in the Paradox Basin of Utah and Colorado. Hydrocarbons are produced from basement-involved, northwest-trending structural traps with closure on both anticlines and faults. Excellent outcrops of Leadville-equivalent rocks are found along the south flank of the Uinta Mountains, Utah. For example, like the Leadville, the Mississippian Madison Limestone contains zones of solution breccia, fractures, and facies variations. When combined with subsurface geological and production data, these outcrop analogs can improve (1) development drilling and production strategies such as horizontal drilling, (2) reservoir-simulation models, (3) reserve calculations, and (4) design and implementation of secondary/tertiary oil recovery programs and other best practices used in the oil fields of Utah and vicinity. In the southern Green River Formation play of the Uinta Basin, optimal drilling, development, and production practices consist of: (1) owning drilling rigs and frac holding tanks; (2) perforating sandstone beds with more than 8 percent neutron porosity and stimulate with separate fracture treatments; (3) placing completed wells on primary production using artificial lift; (4) converting wells relatively soon to secondary waterflooding maintaining reservoir pressure above the bubble point to maximize oil recovery; (5) developing waterflood units using an alternating injector--producer pattern on 40-acre (16-ha) spacing; and (6) recompleting producing wells by perforating all beds that are productive in the waterflood unit. As part of technology transfer

  11. Tunable photoluminescent materials based on two phenylcarbazole-based dimers through the substituent groups

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Gui-Mei, E-mail: meiguit@163.com; Chi, Rui-Hai; Wan, Wen-Zhu; Chen, Zhi-Qiang; Yan, Ting-Xiang; Dong, Yan-Ping; Wang, Yong-Tao, E-mail: ceswyt@qlu.edu.cn; Cui, Yue-Zhi

    2017-05-15

    Two phenylcarbazole-based dimers, namely, 9,9'-diphenyl-9H,9'H−3,3'-bicarbazole (1) and 9,9'-bis(4-bromophenyl)−9H,9'H−3,3'-bicarbazole (2), have been obtained through the oxidation of 9-phenylcarbazole and 9-(4’-bromophenyl) in the presence of FeCl{sub 3}, respectively, which show strong photoluminescent properties with the fluorescence quantum yields of 0.2 and 0.21 based on the reference of Quinin sulfate, respectively. The maximal emission peak of compounds 1 and 2 were observed at 465 and 413 nm in the solid state, respectively, revealing that the luminescent properties were tuned by the substituent group. The title compounds were characterized by FI-IR, UV–vis, {sup 1}H-NMR, {sup 13}C-NMR, {sup 1}H−{sup 13}C NMR, mass spectra, elemental analysis (EA) and single-crystal X-ray diffraction. Both compounds 1 and 2 crystallize in space group P-1, and supramolecular hydrogen bondings and stacking interactions between aromatic rings are observed. Compounds 1 and 2 display trans- and cis-formation structures, respectively. Two compounds show high thermal stabilities, in which the decomposition temperature is 414 and 363 °C for 1 and 2, respectively. - Graphical abstract: Two phenylcarbazole-based dimers have been obtained through the oxidation of 9-phenylcarbazole and 9-(4’-bromophenyl) in the presence of FeCl{sub 3}, respectively. The maximal emission peaks of compounds 1 and 2 were observed at 465 and 413 nm, respectively, revealing that the luminescent properties were tuned by the substituent group. Compounds 1 and 2 display trans- and cis-formation structures, respectively, and they show high thermal stabilities.

  12. Ring substituents mediate the morphology of PBDTTPD-PCBM bulk-heterojunction solar cells

    KAUST Repository

    Warnan, Julien

    2014-04-08

    Among π-conjugated polymer donors for efficient bulk-heterojunction (BHJ) solar cell applications, poly(benzo[1,2-b:4,5-b′]dithiophene- thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill-factors (FF, ca. 70%) in conventional (single-cell) BHJ devices with PCBM acceptors. In PBDTTPD, side chains of varying size and branching affect polymer self-assembly, nanostructural order, and impact material performance. However, the role of the polymer side-chain pattern in the intimate mixing between polymer donors and PCBM acceptors, and on the development of the BHJ morphology is in general less understood. In this contribution, we show that ring substituents such as furan (F), thiophene (T) and selenophene (S)-incorporated into the side chains of PBDTTPD polymers-can induce significant and, of importance, very different morphological effects in BHJs with PCBM. A combination of experimental and theoretical (via density functional theory) characterizations sheds light on how varying the heteroatom of the ring substituents impacts (i) the preferred side-chain configurations and (ii) the ionization, electronic, and optical properties of the PBDTTPD polymers. In parallel, we find that the PBDT(X)TPD analogs (with X = F, T, or S) span a broad range of power conversion efficiencies (PCEs, 3-6.5%) in optimized devices with improved thin-film morphologies via the use of 1,8-diiodooctane (DIO), and discuss that persistent morphological impediments at the nanoscale can be at the origin of the spread in PCE across optimized PBDT(X)TPD-based devices. With their high VOC ∼1 V, PBDT(X)TPD polymers are promising candidates for use in the high-band gap cell of tandem solar cells. © 2014 American Chemical Society.

  13. Ring substituents mediate the morphology of PBDTTPD-PCBM bulk-heterojunction solar cells

    KAUST Repository

    Warnan, Julien; El Labban, Abdulrahman; Cabanetos, Clement; Hoke, Eric T.; Shukla, Pradeep Kumar; Risko, Chad; Bré das, Jean Luc; McGehee, Michael D.; Beaujuge, Pierre

    2014-01-01

    Among π-conjugated polymer donors for efficient bulk-heterojunction (BHJ) solar cell applications, poly(benzo[1,2-b:4,5-b′]dithiophene- thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill-factors (FF, ca. 70%) in conventional (single-cell) BHJ devices with PCBM acceptors. In PBDTTPD, side chains of varying size and branching affect polymer self-assembly, nanostructural order, and impact material performance. However, the role of the polymer side-chain pattern in the intimate mixing between polymer donors and PCBM acceptors, and on the development of the BHJ morphology is in general less understood. In this contribution, we show that ring substituents such as furan (F), thiophene (T) and selenophene (S)-incorporated into the side chains of PBDTTPD polymers-can induce significant and, of importance, very different morphological effects in BHJs with PCBM. A combination of experimental and theoretical (via density functional theory) characterizations sheds light on how varying the heteroatom of the ring substituents impacts (i) the preferred side-chain configurations and (ii) the ionization, electronic, and optical properties of the PBDTTPD polymers. In parallel, we find that the PBDT(X)TPD analogs (with X = F, T, or S) span a broad range of power conversion efficiencies (PCEs, 3-6.5%) in optimized devices with improved thin-film morphologies via the use of 1,8-diiodooctane (DIO), and discuss that persistent morphological impediments at the nanoscale can be at the origin of the spread in PCE across optimized PBDT(X)TPD-based devices. With their high VOC ∼1 V, PBDT(X)TPD polymers are promising candidates for use in the high-band gap cell of tandem solar cells. © 2014 American Chemical Society.

  14. Amides with nitrogenous heterocyclic substituent, their manufacturing process and their use to draw out selectively Actinium series (III) and to separate them in particular from Lanthanides (III)

    International Nuclear Information System (INIS)

    Cuillerdier, C.; Musikas, C.

    1993-01-01

    Present invention is concerned with new amides with nitrogenous heterocyclic substituent utilizable to separate trivalent actinium series from trivalent lanthanides. In these molecules, it is possible to obtain particularly covalent liaison which has more affinity with 5f series, that is to say actinium series; included a manufacturing process for these amides with nitrogenous heterocyclic substituent

  15. New photoresponsive (meth)acrylate (co)polymers containing azobenzene pendant sidegroups with carboxylic and dimethylamino substituents .1. Synthesis and characterization of the monomers

    NARCIS (Netherlands)

    Haitjema, HJ; Buruma, R; VanEkenstein, GORA; Tan, YY; Challa, G

    1996-01-01

    New azobenzene-based (az.b.) monomers with CO2H (acid) or N(CH3)(2) (basic) substituents were synthesized. For some of these compounds new synthetic routes had to be developed, especially for the az.b. monomers with a CO2H substituent (azoacids) where their synthesis, purification and (thermal)

  16. Bipolar Alq3-based complexes: Effect of hole-transporting substituent on the properties of Alq3-center

    International Nuclear Information System (INIS)

    Luo Jianxin; Lu Mangeng; Yang Chaolong; Tong Bihai; Liang Liyan

    2012-01-01

    Two bipolar Alq 3 -based complexes, tris{5-[(carbazole-9'-yl)methyl]-8-hydroxyquinoline} aluminum (Al(CzHQ) 3 ) and tris{5-[(phenothiazine-9'-yl)methyl]-8-hydroxyquinoline} aluminum (Al(PHQ) 3 ), involving an Alq 3 -center and three hole-transporting substituents (carbazole or phenothiazine), were prepared and characterized. Effects of hole-transporting substituent on the properties of Alq 3 -center were investigated in detail. It is found that the two complexes have improved hole-transporting performance and appropriate thermal stability (the 5%-weight-loss temperatures T 5% >260 °C). Photoluminescence (PL) spectra indicate that both energy transfer and electron transfer can take place simultaneously in the PL process of these complexes. Both thermodynamics and dynamics of the electron transfer were studied and corresponding parameters were calculated. Energy transfer is favorable for the PL of Alq 3 -center, while electron transfer is unfavorable for the PL of Alq 3 -center. These results will be useful to explore novel OLEDs material with increased efficiency. - Highlights: ► Effects of substituent on the properties of Alq 3 -center were investigated. ► Energy transfer and electron transfer can transfer from substituent to Alq 3 -center. ► The thermodynamics and dynamics of electron transfer were studied. ► The mechanisms of PL and EL of Al(CzHQ) 3 were studied and compared with each other.

  17. Supramolecular Switches Based on the Guanine–Cytosine (GC) Watson–Crick Pair: Effect of Neutral and Ionic Substituents

    NARCIS (Netherlands)

    Guerra, C.F.; van der Wijst, T.; Bickelhaupt, F.M.

    2006-01-01

    We have theoretically analyzed Watson–Crick guanine–cytosine (GC) base pairs in which purine-C8 and/or pyrimidine-C6 positions carry a substituent X = NH−, NH2, NH3+ (N series), O−, OH, or OH2+ (O series), using the generalized gradient approximation (GGA) of density functional theory at the

  18. Substituent Effects Dehalogenation of Aryl Bromides with NaAlH2(OCH2CH2OCH3)2

    Czech Academy of Sciences Publication Activity Database

    Czakoová, Marie; Hetflejš, Jiří; Včelák, Jaroslav

    2001-01-01

    Roč. 72, č. 2 (2001), s. 277-287 ISSN 0133-1736 R&D Projects: GA ČR GA203/97/1173 Institutional research plan: CEZ:AV0Z4072921 Keywords : substituent effects * aryl bromides * Co-assisted debromination Subject RIV: CC - Organic Chemistry Impact factor: 0.475, year: 2001

  19. Synthesis and Crystal Structures of Dimethylsilylene-Bridged (Amidocyclopentadienyl)Dichlorotitanium(IV) Complexes with Various Substituents on the Cyclopentadienyl Ligand

    Czech Academy of Sciences Publication Activity Database

    Zemánek, Jaroslav; Štěpnička, P.; Fejfarová, K.; Gyepes, R.; Císařová, I.; Horáček, Michal; Kubišta, Jiří; Varga, V.; Mach, Karel

    2001-01-01

    Roč. 66, č. 4 (2001), s. 605-620 ISSN 0010-0765 R&D Projects: GA AV ČR IBS4040017 Institutional research plan: CEZ:AV0Z4040901 Keywords : titanium * (amidocyclopentadienyl)dichlorotitanium(IV) complexes * substituent effects Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.778, year: 2001

  20. The proton transfer reaction in malonaldehyde derivatives: Substituent effects and quasi-aromaticity of the proton bridge

    International Nuclear Information System (INIS)

    Palusiak, Marcin; Simon, Silvia; Sola, Miquel

    2007-01-01

    The proton transfer in malonaldehyde and in some of its derivatives have been considered in order to study the interrelation between the reaction barrier and the π-delocalization in the quasi-ring. A set of simple and mostly common substituents having different properties in resonance effect according to values of substituents constants were chosen in order to simulate the influence of substitution in position 2 or in position 1 (or 3) of malonaldehyde on the quasi-aromaticity and H-bonding. The following substituents have been taken into consideration: NO, NO 2 , CN, CHO, F, H, CH 3 , OCH 3 , OH, and NH 2 . Our results show that when the substituent is attached at position 2 of the quasi-ring, the resonance effect predominates over the field/inductive effect which leads to changes in H-bonding and quasi-aromaticity of the ring motif, while in the case of 1(3) substitution the field/inductive effect is significantly more effective influencing the HB strength, and thus, the proton transfer barrier. Somehow counterintuitively, for the 1(3) substituted systems, the most stable isomer is the one having the weakest HB and lower aromaticity. The reason for this surprising behaviour is discussed

  1. Effect of Polyhedral Oligomeric Silsesquioxane (POSS) Substituents on the Rheological Behavior in Butyl Methacrylate/POSS Copolymers

    Science.gov (United States)

    2008-10-27

    was repeated twice, dissolving the product in chloroform and diethyl ether, respectively. The polymer was dried at 60 °C under vacuum overnight...the Tg of the i Bu remains the same. Table 1. Tg for Butyl Methacrylate-co- Propyl Methacryl POSS Polymers with Various POSS Substituents

  2. Kinetics and mechanism of the oxidation of some vicinal and non ...

    Indian Academy of Sciences (India)

    Kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers, by tetrabutylammonium tribromide (TBATB) has been studied. The vicinal diols yield products arising out of glycol-bond fission, while the non-vicinal diols produce the hydroxycarbonyl compounds. The reaction is first-order with ...

  3. Uranium Mill Tailings Remedial Action Project Vicinity Property Program

    International Nuclear Information System (INIS)

    Little, L.E.; Potter, R.F.; Arpke, P.W.

    1988-01-01

    The Department of Energy Uranium Mill Tailings Remedial Action (UMTRA) Grand Junction Project Vicinity Property Program is a $165 million program for the removal and disposal of uranium mill tailings that were used in the construction of approximately 4,000 residences, commercial buildings, and institutional facilities in the City of Grand Junction and surrounding Mesa County, Colorado. This paper discusses the UMTRA Vicinity Property Program and the economic benefits of this program for the City of Grand Junction and Mesa County, Colorado. The Bureau of Reclamation Economic Assessment Model (BREAM) was used to estimate the increases in employment and increases in personal income in Mesa County that result from the Vicinity Property Program. The effects of program-related changes in income and taxable expenditures on local and state tax revenue are also presented

  4. Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2 H-azirines

    Science.gov (United States)

    Gómez-Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana L.; Pinho e Melo, Teresa M. V. D.; Fausto, Rui

    2007-05-01

    In this study, the UV induced photochemical reactions of two 2 H-azirines - methyl 2-chloro-3-methyl-2 H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2 H-azirine-2-carboxylate (MMAC) - isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) C sbnd C bond cleavage, with production of nitrile ylides (P1-type products), and (b) C sbnd N bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a C dbnd N +dbnd C - group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC. The C sbnd N photochemical cleavage is an unusual process in aliphatic 2 H-azirines. In the studied compounds, its preference over the commonly observed C sbnd C azirine-ring bond photocleavage is attributed to the presence of electron withdrawing substituents (methylcarboxy group in both azirines and also the chlorine atom in MCMAC), which accelerates intersystem crossing towards the triplet state from where the cleavage of the C sbnd N bond takes place. The lack of the chlorine atom in MMAC may be partially compensated by the significantly higher stabilization of the P2-type photoproduct derived from this molecule ( ca. -52 kJ mol -1) relatively to the reactant, when

  5. The decoration of vicinal copper polycrystalline surface by Antimony

    CSIR Research Space (South Africa)

    Ndlovu, GF

    2011-07-01

    Full Text Available in the vicinity of the step edges illustrative of the Frank van der Merwe type of growth. Kinks provide for the adsorbates a site with a coordination that is higher than for sites at the straight step edge. Thus, kinks act as efficient nucleation sites...

  6. Gamma Radiation Assessment In Kartini Reactor And Its Vicinity

    International Nuclear Information System (INIS)

    Yazid, M.; Supriyatni, E.; Maryono; Bastianudin, Aris

    2000-01-01

    Measurement to calculate dose assesment for gamma radiation in Kartini Reactor and its vicinity has been done whether on operated or un operated condition. Measurement was performed using height pressured ionization chamber, Reuther Stokes RS-112 production. Measurement location was determined based on distance variation inwardly and outwardly of reactor building and its vicinity. The result showed that the average dose rate in the reactor building when un operated is in the range of 11.4-38.6 mu rad/hour and when the reactor operated is 166.4-1910.9 mu rad/hour. While the vicinity of the reactor on operated condition the average dose rate is 34.4-38.6 mu rad/hour in un operated condition is 6.9-7.0 mu rad/hour. This result showed that the reactor operated did not rise the radiation exposure level in its vicinity. From the personnel assesment dose rate of gamma radiation is 28.54 mrem/week on operated condition, 0.90 mrem.week on un operated condition. While dose rate outside the reactor is 0.44 and 0.27 mrem/week for operated and un operated condition consecutively. This dose rate is still below maximum permissible dose than recommended by the national regulation of radiation protection from BAPETEN No. 01/Ka.BAPETEN/V-99

  7. "Equilibrium structure of monatomic steps on vicinal Si(001)

    NARCIS (Netherlands)

    Zandvliet, Henricus J.W.; Elswijk, H.B.; van Loenen, E.J.; Dijkkamp, D.

    1992-01-01

    The equilibrium structure of monatomic steps on vicinal Si(001) is described in terms of anisotropic nearest-neighbor and isotropic second-nearest-neighbor interactions between dimers. By comparing scanning-tunneling-microscopy data and this equilibrium structure, we obtained interaction energies of

  8. Molecular binding thermodynamics of spherical guests by β-cyclodextrins bearing aromatic substituents

    Energy Technology Data Exchange (ETDEWEB)

    Li, Nan; Chen, Yong; Zhang, Ying-Ming; Wang, Li-Hua; Mao, Wen-Zhao; Liu, Yu, E-mail: yuliu@nankai.edu.cn

    2014-01-20

    Graphical abstract: - Highlights: • Different conformation of β-CD derivatives. • Enthalpy gain. • High binding ability. - Abstract: The molecular binding behaviors of two β-cyclodextrin (β-CD) derivatives bearing 1,2,3-triazole moieties, i.e. mono-6-deoxy-6-{4-(8-oxymethylquinolino)[1,2,3]triazolyl}-β-CD (1) and mono-6-deoxy-6-{4-(8-oxymethylnaphthol)[1,2,3]triazolyl}-β-CD (3), and their analogs without 1,2,3-triazole moieties, i.e. mono-6-deoxy-6-(8-oxymethylquinolino)-β-CD (2) and mono-6-deoxy-6-(8-oxymethylnaphthol)-β-CD (4) toward spherical guests (±)-borneol and (±)-camphor were investigated to elucidate how substituent moiety of host affects the binding abilities by 2D NMR as well as microcalorimetric titrations in aqueous phosphate buffer solution (pH 7.20) at 298.15 K. The binding modes of host–guest interactions obtained from 2D NMR displayed that host CDs without triazole moieties gave better induce-fit efficiency between hosts and guests, leading to stronger binding abilities. Thermodynamically, the inclusion complexation was driven by enthalpy with the stoichiometry of 1:1. Another factor contributed to the enhanced binding abilities was the enthalpy gain with the smaller entropy loss.

  9. Influence of substituents in vinyl groups on reactivity of parylene during polymerization process

    International Nuclear Information System (INIS)

    Freza, Sylwia; Skurski, Piotr; Bobrowski, Maciej

    2010-01-01

    The MCSCF calculations indicate that both triplet and singlet state of biradical di-para-xylylene can exist during polymerization of parylene in gas phase and both can potentially react with vinyl molecules. The singlet-state open-shell dimer turned out to exhibit multiconfigurational character. In the case of triplet state of the dimer two mechanisms of the reactions with various species containing vinyl groups have been examined at the B3LYP/6-31G level. The kinetic and thermodynamical barriers have been estimated for the reaction path involving the π-bond cleavage as well as for the route describing the hydrogen atom transfer. It was found that the overall reactions are thermodynamically favorable, whereas appropriate kinetic barriers for certain derivatives are very small (close to 0 kcal/mol) which in turn makes allowances for easy reactivity under accessible conditions. The calculated mechanisms indicate the influence of substituents in vinyl groups for reactivity of parylene during LPCVD process.

  10. Infrared matrix isolation study of hydrogen bonds involving C-H bonds: Substituent effects

    International Nuclear Information System (INIS)

    Jeng, M.L.H.; Ault, B.S.

    1989-01-01

    The matrix isolation technique combined with infrared spectroscopy has been employed to isolate and characterize hydrogen-bonded complexes between a series of substituted alkynes and several oxygen and nitrogen bases. Distinct evidence for hydrogen bond formation was observed in each case, with a characteristic red shift of the hydrogen stretching motion ν r . Shifts between 100 and 300 cm -1 were observed, the largest being for the complex of CF 3 CCH with (CH 3 ) 3 N. The perturbed carbon-carbon triple bond stretching vibration was observed for most complexes, as was the alkynic hydrogen bending motion. Attempts were made to correlate the magnitude of the red shift of ν s with substituent constants for the different substituted alkynes; a roughly linear correlation was found with the Hammett σ parameter. Lack of correlation Δν s with either σ 1 or σ R alone suggests that both inductive and resonance contributions to the strength of the hydrogen-bonding interaction are important

  11. Substituent effects on furan-phenylene copolymer for photovoltaic improvement: A density functional study

    Science.gov (United States)

    Janprapa, Nuttaporn; Vchirawongkwin, Viwat; Kritayakornupong, Chinapong

    2018-06-01

    The structural, electronic and photovoltaic properties of furan-phenylene copolymer ((Fu-co-Ph)4) and its derivatives were evaluated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The calculated band gaps of pristine furan and phenylene are in good agreement with the available experimental data. The lower band gap value of 2.72 eV was obtained from -NO2 and -NHCH3 substituents, leading to broader solar absorption range. With respected to the reorganization energy, -OCH3, -NHCH3, -OH, -SCH3, -CH3, -CF3, -NO2, and -F substituted (Fu-co-Ph)4 structures were classified as better electron donor materials. For combination with PC61BM, -NO2, -CN, -CF3 and -F functionalized copolymers demonstrated significantly higher open circuit voltage (Voc) values ranging from 1.07 to 2.10 eV. Our results revealed that electron withdrawing group substitution on furan-phenylene copolymers was an effective way for improving electronic and optical properties of donor materials used in photovoltaic applications.

  12. Competitive/co-operative interactions in acid base sandwich: role of cation vs. substituents.

    Science.gov (United States)

    Kalpana, Ayyavoo; Akilandeswari, Lakshminarayanan

    2017-11-15

    The cation-π interaction can be envisaged as a lewis acid base interaction, and it is in line with Pearson's acid base concept. The critical examination of interactions between the π-acids (alkali metal cations - Li + , Na + and alkaline earth metal cations Mg 2+ , Ca 2+ ) on one face and tripodal Cr(CO) 3 moiety on the other π face of substituted arenes demonstrates the role of cation and substitutents in manipulating the interactions between them. The interaction of the two π acids on both faces of arene is not expectedly additive, rather it shows either depreciation of interaction energy revealing the competition of acids toward the base or enhancement of interaction energy denoting a cooperative effect. Among the metal cations under study, Mg 2+ shows a cooperative gesture. Although the substituents play a meek role, they unfailingly exert their electronic effects and are amply documented by excellent correlation of various parameters with the Hammett constant σ m . The elusive switching of λ max from the UV to IR region on binding Mg 2+ with substituted arene-Cr(CO) 3 complex is a characteristic clue that TDDFT can help design the ionic sensors for Mg 2+ cations.

  13. Influence of Introduced Substituents on the Anion-selectivity of [14]Tetraazaannulene Complexes.

    Science.gov (United States)

    Moriuchi-Kawakami, Takayo; Obita, Minako; Tsujinaka, Toshiki; Shibutani, Yasuhiko

    2015-01-01

    Nickel(II) complexes of [14]tetraazaannulene derivatives incorporating aromatic rings into their azaannulene framework were synthesized, and the anion-selectivity of the [14]tetraazaannulene nickel complexes 1 - 4 was evaluated by potentiometric measurements with solvent polymeric membrane electrodes. All of the [14]Tetraazaannulene nickel complexes, except 3, were found to exhibit high selectivity for the I(-) ion over the SCN(-) ion, although considerable interference of the ClO4(-) ion was observed in all 1 - 4 complexes. Concerning the anion-selectivities of 1 and 4, the incorporation of naphthalene rings into the azaannulene framework decreased not only the interference of the ClO4(-) ion but also the I(-) ion-selectivity over the SCN(-) ion. Comparison studies between the dibenzotetraaza[14]annulene nickel complexes 1 - 3 indicated that differences in the attached substituents of the [14]tetraazaannulene nickel complexes greatly influenced the ion-selectivity as ionophores. According to our computational results, the ionophoric properties of [14]tetraazaannulene nickel complexes 1 - 4 were influenced by their electrostatic properties rather than their topological properties.

  14. Influence of substituents of nickel(II) complexes of Schiff bases of substituted (S)-2-N-(benzylpropyl)aminobenzophenones and amino-acids on their asymmetric induction

    International Nuclear Information System (INIS)

    Nadvornik, M.; Lycka, A.; Gee, A.; Popkov, A.

    1999-01-01

    The aim of this work was to study of influence of substituents on benzophenone substituent on thermodynamic controlled induction of complexes as well as influence of substituents on benzyl group and on benzophenone on kinetically controlled asymmetric induction of complexes. [ 13 C]methyl iodide was used in the synthesis. Replace of benzyl group by 2,4,6-trimethylbenzyl group increase kinetically controlled asymmetric induction of synthesis of (S)-α-[ 13 C]methylalanine from 43% d.e. to 66% d.e

  15. Substituent Effects on the Hydrogen Bonding between 4-Substituted Phenols and HF, H2O, NH3

    Institute of Scientific and Technical Information of China (English)

    程宇辉; 傅尧; 刘磊; 郭庆祥

    2003-01-01

    Density function theory UB3LYP/6-31+g(d) calculations were performed to study the hydrogen bonds between para-substituted phenols and HF, H2O, or NH3. It revealed that many properties of the non-covalent complexes, such as the interaction energies, donor-acceptor distances, bond lengths and vibration frequencies, showed well-defined substituent effects. Therefore, from the substituent effects not only the mechanism of a certain non-covalent interaction can be better understood, but also the interaction energies and structures of a certain non-covalent complex, which otherwise might be very hard or resource-consuming to estimate, can be easily predicted.

  16. Substituent effects on the redox states of locally functionalized single-walled carbon nanotubes revealed by in situ photoluminescence spectroelectrochemistry.

    Science.gov (United States)

    Shiraishi, Tomonari; Shiraki, Tomohiro; Nakashima, Naotoshi

    2017-11-09

    Single-walled carbon nanotubes (SWNTs) with local chemical modification have been recognized as a novel near infrared (NIR) photoluminescent nanomaterial due to the emergence of a new red-shifted photoluminescence (PL) with enhanced quantum yields. As a characteristic feature of the locally functionalized SWNTs (lf-SWNTs), PL wavelength changes occur with the structural dependence of the substituent structures in the modified aryl groups, showing up to a 60 nm peak shift according to an electronic property difference of the aryl groups. Up to now, however, the structural effect on the electronic states of the lf-SWNTs has been discussed only on the basis of theoretical calculations due to the very limited amount of modifications. Herein, we describe the successfully-determined electronic states of the aryl-modified lf-SWNTs with different substituents (Ar-X SWNTs) using an in situ PL spectroelectrochemical method based on electrochemical quenching of the PL intensities analyzed by the Nernst equation. In particular, we reveal that the local functionalization of (6,5)SWNTs induced potential changes in the energy levels of the HOMO and the LUMO by -23 to -38 meV and +20 to +22 meV, respectively, compared to those of the pristine SWNTs, which generates exciton trapping sites with narrower band gaps. Moreover, the HOMO levels of the Ar-X SWNTs specifically shift in a negative potential direction by 15 meV according to an enhancement of the electron-accepting property of the substituents in the aryl groups that corresponds to an increase in the Hammet substituent constants, suggesting the importance of the dipole effect from the aryl groups on the lf-SWNTs to the level shift of the frontier orbitals. Our method is a promising way to characterize the electronic features of the lf-SWNTs.

  17. Fluoroalkyl Amino Reagents (FARs: A General Approach towards the Synthesis of Heterocyclic Compounds Bearing Emergent Fluorinated Substituents

    Directory of Open Access Journals (Sweden)

    Bruno Commare

    2017-06-01

    Full Text Available Fluorinated heterocycles are important building blocks in pharmaceutical, agrochemical and material sciences. Therefore, organofluorine chemistry has witnessed high interest in the development of efficient methods for the introduction of emergent fluorinated substituents (EFS onto heterocycles. In this context, fluoroalkyl amino reagents (FARs—a class of chemicals that was slightly forgotten over the last decades—has emerged again recently and proved to be a powerful tool for the introduction of various fluorinated groups onto (heteroaromatic derivatives.

  18. Fluoroalkyl Amino Reagents (FARs): A General Approach towards the Synthesis of Heterocyclic Compounds Bearing Emergent Fluorinated Substituents.

    Science.gov (United States)

    Commare, Bruno; Schmitt, Etienne; Aribi, Fallia; Panossian, Armen; Vors, Jean-Pierre; Pazenok, Sergiy; Leroux, Frédéric R

    2017-06-12

    Fluorinated heterocycles are important building blocks in pharmaceutical, agrochemical and material sciences. Therefore, organofluorine chemistry has witnessed high interest in the development of efficient methods for the introduction of emergent fluorinated substituents (EFS) onto heterocycles. In this context, fluoroalkyl amino reagents (FARs)-a class of chemicals that was slightly forgotten over the last decades-has emerged again recently and proved to be a powerful tool for the introduction of various fluorinated groups onto (hetero)aromatic derivatives.

  19. Archetypes for actinide-specific chelating agents

    International Nuclear Information System (INIS)

    Smith, W.L.

    1980-01-01

    The complexes of uranium and thorium with monomeric hydroxamic acids can serve as archetypes for an optimized macrochelate designed for tetravalent actinides. The eight-coordinate complexes, Th(i-PrN(O)C(O)R) 4 , where R = tert-butyl or R = neopentyl, have been synthesized and their structures have been determined by x-ray diffraction. The bulky alkyl substituents impart remarkable volatility and hydrocarbon solubility to these complexes, and the steric interactions of these substituents largely determine the structures. When R = tert-butyl, the substituents occupy the corners of a tetrahedron and force the complex into a distorted cubic geometry with crystallographic S 4 symmetry. Insertion of a methylene group between the carbonyl carbon and the tert-butyl group relaxes the steric requirements, and the coordination polyhedron of the neopentyl derivative is close to the mmmm isomer of the trigonal-faced dodecahedron. Uranium tetrachloride was quantitatively oxidized via an oxygen transfer reaction with two equivalents of N-phenylbenzohydroxamic acid anion (PBHA) in tetrahydrofuran (THF) to form UO 2 Cl(PBHA)(THF) 2 and benzanilide. The structure of the uranyl complex has been determined from x-ray diffraction data; the linear uranyl ion is surrounded by a planar pentagonal array composed of two hydroxamate oxygen atoms, a chloride ion and two THF oxygens, such that the chloride ion is opposite the hydroxamate group. That the THF and phenyl rings are twisted from this equatorial plane limits the molecular geometry to that of the C 1 point group. Some aspects of the chemistry of hydroxamic acids and of their incorporation into molecules that may serve as precursors of tetravalent actinide specific sequestering agents have also been investigated

  20. Substituent Inductive Effects on the Electrochemical Oxidation of Flavonoids Studied by Square Wave Voltammetry and Ab Initio Calculations.

    Science.gov (United States)

    Arroyo-Currás, Netzahualcóyotl; Rosas-García, Víctor M; Videa, Marcelo

    2016-10-27

    Flavonoids are natural products commonly found in the human diet that show antioxidant, anti-inflammatory and anti-hepatotoxic activities. These nutraceutical properties may relate to the electrochemical activity of flavonoids. To increase the understanding of structure-electrochemical activity relations and the inductive effects that OH substituents have on the redox potential of flavonoids, we carried out square-wave voltammetry experiments and ab initio calculations of eight flavonoids selected following a systematic variation in the number of hydroxyl substituents and their location on the flavan backbone: three flavonols, three anthocyanidins, one anthocyanin and the flavonoid backbone flavone. We compared the effect that the number of -OH groups in the ring B of flavan has on the oxidation potential of the flavonoids considered, finding linear correlations for both flavonols and anthocyanidins ( R 2 = 0.98 ). We analyzed the effects that position and number of -OH substituents have on electron density distributions via ab initio quantum chemical calculations. We present direct correlations between structural features and oxidation potentials that provide a deeper insight into the redox chemistry of these molecules.

  1. Interaction between D-fructose dehydrogenase and methoxy-substituent-functionalized carbon surface to increase productive orientations

    International Nuclear Information System (INIS)

    Xia, Hong-qi; Hibino, Yuya; Kitazumi, Yuki; Shirai, Osamu; Kano, Kenji

    2016-01-01

    Highlights: • Methoxy-functionalized surface improves the DET-type bioelectrocatalysis of FDH. • Methoxy-functionalized surface increases productive orientations. • The total catalytic activity of FDH is almost independent of the modification. • High current density as well as good stability is useful for biofuel cells. - Abstract: D-Fructose dehydrogenase (FDH) from Gluconobacter japonicus NBRC3260 catalyzes the two-electron oxidation of D-fructose to 5-keto-D-fructose, and it is widely used in biofuel cells and biosensors. In this study, methoxy-substituent-functionalized carbon electrodes are constructed by electrochemical oxidation of methoxy-aniline derivatives on Ketjen Black (KB)-modified electrodes to improve the immobilization and bioelectrocatalysis of FDH. It is proposed that the specific interaction between FDH, especially the heme c moiety, and methoxy substituent(s) of amines on carbon electrode increases the proportion of the productively oriented FDH molecules to the total FDHs. Consequently, the limiting catalytic current density of the D-fructose oxidation increases to as much as 23 ± 2 mA cm −2 in FDH/2,4-dimethoxyaniline/KB/glassy carbon electrode, for example.

  2. The unique role of halogen substituents in the design of modern agrochemicals.

    Science.gov (United States)

    Jeschke, Peter

    2010-01-01

    The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.

  3. Pentiptycene-derived light-driven molecular brakes: substituent effects of the brake component.

    Science.gov (United States)

    Sun, Wei-Ting; Huang, Yau-Ting; Huang, Guan-Jhih; Lu, Hsiu-Feng; Chao, Ito; Huang, Shou-Ling; Huang, Shing-Jong; Lin, Ying-Chih; Ho, Jinn-Hsuan; Yang, Jye-Shane

    2010-10-11

    Five pentiptycene-derived stilbene systems (1 R; R = H, OM, NO, Pr, and Bu) have been prepared and investigated as light-driven molecular brakes that have different-sized brake components (1 Hbrake component in the trans form ((E)-1 R), which corresponds to the brake-off state. When the brake is turned on by photoisomerization to the cis form ((Z)-1 R), the pentiptycene rotation can be arrested on the NMR spectroscopic timescale at temperatures that depend on the brake component. In the cases of (Z)-1 NO, (Z)-1 Pr, and (Z)-1 Bu, the rotation is nearly blocked (k(rot)=2-6 s(-1)) at 298 K. It is also demonstrated that the rotation is slower in [D(6)]DMSO than in CD(2)Cl(2). A linear relationship between the free energies of the rotational barrier and the steric parameter A values is present only for (Z)-1 H, (Z)-1 OM, and (Z)-1 NO, and it levels off on going from (Z)-1 NO to (Z)-1 Pr and (Z)-1 Bu. DFT calculations provide insights into the substituent effects in the rotational ground and transition states. The molar reversibility of the E-Z photoswitching is up to 46%, and both the E and Z isomers are stable under the irradiation conditions. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. New aminoporphyrins bearing urea derivative substituents: synthesis, characterization, antibacterial and antifungal activity

    Directory of Open Access Journals (Sweden)

    Gholamreza Karimipour

    2015-06-01

    Full Text Available This work studied the synthesis of 5,10,15-tris(4-aminophenyl-20-(N,N-dialkyl/diaryl-N-phenylurea porphyrins (P1-P4 with alkyl or aryl groups of Ph, iPr, Et and Me, respectively and also the preparation of their manganese (III and cobalt (II complexes (MnP and CoP. The P1-P4 ligands were characterized by different spectroscopic techniques (1H NMR, FTIR, UV-Vis and elemental analysis, and metalated with Mn and Co acetate salts. The antibacterial and antifungal activities of these compounds in vitro were investigated by agar-disc diffusion method against Escherichia coli (-, Pseudomonas aeruginosa (-, Staphylococcus aureus(+, Bacillus subtilis (+ and Aspergillus oryzae and Candida albicans. Results showed that antibacterial and antifungal activity of the test samples increased with increase of their concentrations and the highest activity was obtained when the concentration of porphyrin compounds was 100 µg/mL. The activity for the porphyrin ligands depended on the nature of the urea derivative substituents and increased in the order P1 > P2 > P3 >P4, which was consistent with the order of their liposolubility. MnP and CoP complexes exhibited much higher antibacterial and antifungal activity than P1-P4ligands. Further, the growth inhibitory effects of these compounds was generally in the order CoP complexes > MnP complexes > P1-P4 ligands. Among these porphyrin compounds, CoP1displayed the highest antibacterial and antifungal activity, especially with a concentration of 100 µg/mL, against all the four tested bacteria and two fungi, and therefore it could be potential to be used as drug.

  5. Inertia of rough and vicinal surfaces of helium-4 crystals

    International Nuclear Information System (INIS)

    Amrit, J.; Legros, P.; Poitrenaud, J.

    1995-01-01

    This paper reports a study of the inertia of rough and vicinal of 4 He crystals. We have measured the transmission coefficient of ultrasonic waves at frequencies 10, 30, 50 and 70 MHz, across the liquid-solid interface. The experiments are carried out at temperatures ranging between 0.4 and 1.0 K for four crystallographic orientations. Two important phenomena are put to evidence for the first time. We have found the first experimental evidence that the inertia of rough surfaces depends on temperature. For vicinal surfaces, we have shown the strong increase of the inertia as the tilt angle decreases. Our experimental results agree very well with the theoretical predictions

  6. Effect of bulky substituents on thiopyrylium polymethine aggregation in the solid state: A theoretical evaluation of the implications for all-optical switching applications

    KAUST Repository

    Gieseking, Rebecca L.

    2014-11-25

    Polymethine dyes in dilute solutions display many of the optical properties required for all-optical switching applications. However, in thin films, aggregation and polymethine-counterion interactions can substantially modify their properties and limit their utility. Here, we examine the impact of a series of bulky substituents on the solid-state molecular packing of thiopyrylium polymethines by using a theoretical approach combining molecular-dynamics simulations and quantum-chemical calculations. Importantly, it is found that the positions of the substituents near the center and/or ends of the dye determine the extent to which aggregation is reduced; in particular, substituents near the polymethine center primarily modify the type of aggregation that is observed, while substituents near the polymethine ends reduce aggregation and aid in maintaining solution-like properties in the solid state. Our theoretical study elucidates relationships between molecular structure and bulk optical properties and provides design guidelines for all-optical switching materials.

  7. Effect of bulky substituents on thiopyrylium polymethine aggregation in the solid state: A theoretical evaluation of the implications for all-optical switching applications

    KAUST Repository

    Gieseking, Rebecca L.; Mukhopadhyay, Sukrit; Risko, Chad; Marder, Seth R.; Bredas, Jean-Luc

    2014-01-01

    and limit their utility. Here, we examine the impact of a series of bulky substituents on the solid-state molecular packing of thiopyrylium polymethines by using a theoretical approach combining molecular-dynamics simulations and quantum

  8. Environmental monitoring in the vicinity of nuclear facilities

    International Nuclear Information System (INIS)

    Jacomino, V.M.F.; Maduar, M.F.

    1992-02-01

    The purpose of this manual is to provide guidance for setting up programmes of environmental monitoring in the vicinity of establishments in a normal condition of operation. It intends to contribute for trainning of technicians working in the nuclear field. In order to illustrate the application of the basic principles described in this manual, the routine environmental monitoring programme carried out in the IPEN-CNEN/SP is presented. (author)

  9. Mass-spectrometric study of volatile uranyl β-diketonates and their adducts

    International Nuclear Information System (INIS)

    Adamov, V.M.; Belyaev, B.N.; Berezinskij, S.O.; Sidorenko, G.V.; Suglobov, D.N.

    1985-01-01

    The mass spectra of a number of uranyl β-diketonates containing methyl, trifluoromethyl and tert-butyl substituents in β-diketonate anion, and their adducts are measured. The form of the unsolvated β-diketonates and their adducts in gas phase is studied. The ways of fragmentation of uranyl β-diketonates and their adducts are investigated. The data concerning the thermal and chemical side reactions proceeding with uranyl β-diketonates and their addicts in an ion source are obtained. The mass spectra of the samples of neptunyl and plutonyl β-diketonate adducts synthesized for the first time are measured

  10. Asymmetric oxidation of 1,3-dithianes to 1,3-dithiane 1-oxides

    OpenAIRE

    Yoshihiko, Watanabe; Yojiro, Ono; Yoshio, Ueno; Takeshi, Toru

    1998-01-01

    Oxidation of 2-(1-hydroxy-1-methylethyl)-1,3-dithiane with the Sharpless reagent has been examined under various reaction conditions. Oxidation of 2-(1-hydroxy-1-methylethyl)-1,3-dithiane with Ti(OPri)4-diethyl L-(+)-tartrate-tert-butyl hydroperoxide (1:2:1.5) in CH2Cl2 in the presence of 4 A molecular sieves gives (1S,2S)-2-(1-hydroxy-1-methylethyl)-1,3-dithiane 1-oxide with high trans selectivity and with moderate enantioselectivity. The enantioselectivity depends upon the substituent at t...

  11. Structure of a putative fluorinated natural product from Streptomyces sp. TC1.

    Science.gov (United States)

    Aldemir, Hülya; Kohlhepp, Stefanie V; Gulder, Tanja; Gulder, Tobias A M

    2014-11-26

    Fluorine-containing natural products are extremely rare. The recent report on the isolation and biological activity of the bacterial secondary metabolite 3-(3,5-di-tert-butyl-4-fluorophenyl)propionic acid was thus highly remarkable. The compound contained the first aromatic fluorine substituent known to date in any natural product. The promise to discover an enzyme capable of aromatic fluorination in the producing strain Streptomyces sp. TC1 prompted our immediate interest. A close inspection of the originally reported analytical data of the fluoro metabolite revealed inconsistencies that triggered us to validate the reported structure. The results of these efforts are presented in this communication.

  12. The unexpected influence of aryl substituents in N-aryl-3-oxobutanamides on the behavior of their multicomponent reactions with 5-amino-3-methylisoxazole and salicylaldehyde

    Directory of Open Access Journals (Sweden)

    Volodymyr V. Tkachenko

    2014-12-01

    Full Text Available The switchable three-component reactions of 5-amino-3-methylisoxazole, salicylaldehyde and N-aryl-3-oxobutanamides under different conditions were studied and discussed. The unexpected influence of the aryl substituent in N-aryl-3-oxobutanamides on the behavior of the reaction was discovered. The key influence of ultrasonication and Lewis acid catalysts led to an established protocol to selectively obtain two or three types of heterocyclic scaffolds depending on the substituent in the N-aryl moiety.

  13. Ground water geochemistry in the vicinity of the Jabiluka deposits

    International Nuclear Information System (INIS)

    Deutscher, R.L.; Mann, A.W.; Giblin, A.

    1980-01-01

    Seventeen exploration drill holes in the vicinity of the Jabiluka One and Jabiluka Two deposits were logged for Eh-pH and conductivity at 5 metre intervals to depths of up to 195 metres below ground surface. Forty-seven water samples from exploration drill holes, augered holes on the Magela flood plain and from two billabongs in the vicinity of the deposits were collected and analyzed. Analyses for pH and Fe were conducted in the field, and further analyses for major ions Ca 2+ , Mg 2+ , Na + , K + , SO 4 2- , Cl - , HCO 3 - and Si and minorelements Zn, Cd, Pb, Cu and U were conducted in the laboratory. The in situ Eh-pH and conductivity measurements, and analyses for major and minor elements of ground waters suggest that deep-lying chlorite-graphite schists containing the uranium mineralization are well protected from, or do not react rapidly with, ground water under present-day conditions, i.e. the schists of the Cahill Formation are a stable host for uranium mineralization at depth. In the vicinity of the Magela flood plain where the Cahill Formation and the permanent water table are close to the surface, some samples were found to contain high concentrations of sulphate, zinc, lead and iron. These same samples were characterized by low pH's in the pH range 3.0-4.0. The anomalies suggest weathering of sulphides associated with the mineralized Cahill Formation, where the schists are at shallow depths and in an oxidizing environment. The anomalies are not, however, necessarily indicative of zones of uranium enrichment in this formation. (author)

  14. Nuclear threats in the vicinity of the Nordic countries

    International Nuclear Information System (INIS)

    Eikelmann, I.M.H.; Moeller, B.

    1999-01-01

    This project is one of the new cross-disciplinary studies in the NKS (Nordic Nuclear Safety) research program 1998-2001. The main task for the project is to aggregate knowledge of nuclear threats in the vicinity of the Nordic countries, a 'base of knowledge', and make this available for the Nordic authorities as a supplement for the national emergency preparedness work. The project will focus on potential events in nuclear installations and the consequences for the Nordic countries especially on: vulnerable food chains; doses to man; environmental contamination; the emergency preparedness system. (au)

  15. Longtime radionuclide monitoring in the vicinity of Salaspils nuclear reactor

    International Nuclear Information System (INIS)

    Riekstina, D.; Berzins, J.; Krasta, T.; Skrypnik, O.; Alksnis, J.

    2016-01-01

    The research nuclear reactor in Salaspils was decommissioned in 1998. Now reactor is partially dismantled and its territory is used as a temporary storage of radioactivity contaminated materials and water. Environment radioactivity monitoring for presence of artificial radionuclides in the vicinity of Salaspils nuclear reactor is carried out since 1990. Data include Cs-137 concentration in soils, tritium concentration in ground water, as well as H-3, Cs-137, Co-60 concentration and gross beta-activity of reactors sewage and rainwater drainage. The systematic monitoring allowed to detect in December 2014 a leakage from the special wastewater basin and so to prevent a pollution of ground water outside reactors territory.

  16. Study on effect of substituents in α positron of N,N-diethylamides by nuclear magnetic resonance

    International Nuclear Information System (INIS)

    Martins, M.A.P.

    1982-01-01

    The effect of a substituent in the α position of some N,N-diethylamides, through the 1 H and 13 C n.m.r. spectroscopy is studied. Eight N,N-diethylamides having the structure: Y-CH 2 -C(O) - NEt 2 , where Y=H, Me, Cl, Br, I, OMe, SMe, and NMe 2 were prepared by usual procedures; all these compounds were characterized by their 1 H and 13 C n.m.r. and infrared spectra, as well as by their elementary analysis. (M.J.C.) [pt

  17. Halogen–Metal Exchange on Bromoheterocyclics with Substituents Containing an Acidic Proton via Formation of a Magnesium Intermediate

    Directory of Open Access Journals (Sweden)

    Qingqiang Tian

    2017-11-01

    Full Text Available A selective and practical bromine–metal exchange on bromoheterocyclics bearing substituents with an acidic proton under non-cryogenic conditions was developed by a simple modification of an existing protocol. Our protocol of using a combination of i-PrMgCl and n-BuLi has not only solved the problem of intermolecular quenching that often occurred when using alkyl lithium alone as the reagent for halogen–lithium exchange, but also offered a highly selective method for performing bromo–metal exchange on dibrominated arene compounds through chelation effect.

  18. Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

    Directory of Open Access Journals (Sweden)

    Seiya Nagao

    2011-12-01

    Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.

  19. Atmospheric dispersion estimates in the vicinity of buildings

    International Nuclear Information System (INIS)

    Ramsdell, J.V. Jr.; Fosmire, C.J.

    1995-01-01

    A model describing atmospheric dispersion in the vicinity of buildings was developed for the U.S. Nuclear Regulatory Commission (NRC) in the late 1980s. That model has recently undergone additional peer review. The reviewers identified four areas of concern related to the model and its application. This report describes revisions to the model in response to the reviewers concerns. Model revision involved incorporation of explicit treatment of enhanced dispersion at low wind speeds in addition to explicit treatment of enhanced dispersion at high speeds resulting from building wakes. Model parameters are evaluated from turbulence data. Experimental diffusion data from seven reactor sites are used for model evaluation. Compared with models recommended in current NRC guidance to licensees, the revised model is less biased and shows more predictive skill. The revised model is also compared with two non-Gaussian models developed to estimate maximum concentrations in building wakes. The revised model concentration predictions are nearly the same as the predictions of the non-Gaussian models. On the basis of these comparisons of the revised model concentration predictions with experimental data and the predictions of other models, the revised model is found to be an appropriate model for estimating concentrations in the vicinity of buildings

  20. Linewidths and line shapes in the vicinity of graphene

    International Nuclear Information System (INIS)

    Bhattacharyya, Pallavi; Sebastian, K. L.

    2014-01-01

    It is well known that graphene, by virtue of its pi-cloud delocalization, has a continuum of electronic energy states and thus behaves nearly like a metal. Instances involving quenching of electronic energy excitation in fluorophores placed in the proximity of graphene sheets are well documented. In this paper, we perform theoretical investigations on the broadening of vibrational and electronic transitions in the vicinity of graphene. We find that for CO vibrations in the vicinity of undoped graphene, the broadening at a distance of 5 Å is ∼0.008 cm −1 (κ ~ =2, κ ~ being the effective dielectric constant). In comparison, for electronic transitions, the linewidth is much larger, being of the order of several cm −1 . Also, if the transition dipole were parallel to the graphene sheet, the linewidth would be reduced to half the value for the case where it is perpendicular, an observation which should be easy to check experimentally for electronic transitions. This should be observable for the f − f transitions (which are rather narrow) of Lanthanide complexes placed within a distance of a few nanometers from a graphene sheet. Further the linewidth would have a (distance) −4 dependence as one varies the distance from graphene

  1. Substituent-directed structural and physicochemical controls of diruthenium catecholate complexes with ligand-unsupported Ru-Ru bonds.

    Science.gov (United States)

    Chang, Ho-Chol; Mochizuki, Katsunori; Kitagawa, Susumu

    2005-05-30

    A family of diruthenium complexes with ligand-unsupported Ru-Ru bonds has been systematically synthesized, and their crystal structures and physical properties have been examined. A simple, useful reaction between Ru2(OAc)4Cl (OAc- = acetate) and catechol derivatives in the presence of bases afforded a variety of diruthenium complexes, generally formulated as [Na(n){Ru2(R4Cat)4}] (n = 2 or 3; R4 = -F4, -Cl4, -Br4, -H4, -3,5-di-t-Bu, and -3,6-di-t-Bu; Cat(2-) = catecholate). The most characteristic feature of the complexes is the formation of short ligand-unsupported Ru-Ru bonds (2.140-2.273 A). These comprehensive studies were carried out to evaluate the effects of the oxidation states and the substituents governing the molecular structures and physicochemical properties. The Ru-Ru bond distances, rotational conformations, and bending structures of the complexes were successfully varied. The results presented in this manuscript clearly demonstrate that the complexes with ligand-unsupported Ru-Ru bonds can sensitively respond to redox reactions and ligand substituents on the basis of the greater degree of freedom in their molecular structures.

  2. Dual fluorescence of excited state intra-molecular proton transfer of HBFO: mechanistic understanding, substituent and solvent effects.

    Science.gov (United States)

    Yang, Wenjing; Chen, Xuebo

    2014-03-07

    A combined approach of the multiconfigurational perturbation theory with the Rice-Ramsperger-Kassel-Marcus methodology has been employed to calculate the minimum potential energy profiles and the rates of excited state intra-molecular proton transfer (ESIPT) for the WOLED material molecule of HBFO and its four meta- or para-substituted compounds in gas phase, acetonitrile and cyclohexane solvents. The kinetic control for these reactions is quantitatively determined and extensively studied on the basis of the accurate potential energy surfaces when the thermodynamic factor associated with the free energy change becomes negligible in the case of the existence of a significant barrier in the ESIPT process. These computational efforts contribute to a deep understanding of the ESIPT mechanism, dual emission characteristics, kinetic controlling factor, substituent and solvent effects for these material molecules. The white light emission is generated by the establishment of dynamic equilibrium between enol and keto forms in the charge transfer excited SCT((1)ππ*) state. The performance of white light emission is quantitatively demonstrated to be mainly sensitive to the molecular tailoring approach of the electronic properties of meta- or para- substituents by the modulation of the forward/backward ESIPT rate ratio. The quality of white light emission is slightly tunable through its surrounding solvent environment. These computational results will provide a useful strategy for the molecular design of OLED and WOLED materials.

  3. Atomic-Level Organization of Vicinal Acid-Base Pairs through the Chemisorption of Aniline and Derivatives onto Mesoporous SBA15

    KAUST Repository

    Basset, Jean-Marie

    2016-06-09

    The design of novel heterogeneous catalysts with multiple adjacent functionalities is of high interest for heterogeneous catalysis. Herein, we report a method to obtain a majority bifunctional acid-base pairs on SBA15. Aniline reacts with SBA15 by opening siloxane bridges leading to N-phenylsilanamine-silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR: 2D ¹H-¹H double-quantum, ¹H-¹³C HETCOR experiments and dynamic nuclear polarization enhanced ²⁹Si and ¹⁵N spectra demonstrate both the close proximity between the two moieties and the formation of a covalent Si-N surface bond and confirm the design of vicinal acid-base pairs. This approach was successfully applied to the design of a series of aniline derivatives bifunctional SBA15. A correlation of the substituents effects on the aromatic ring (Hammet parameters) on the kinetics of the model reaction of Knoevenagel is observed.

  4. The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents.

    Science.gov (United States)

    Mojica, Martha; Méndez, Francisco; Alonso, Julio A

    2016-02-12

    The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

  5. Relative substituent orientation in the structure of cis-3-chloro-1,3-dimethyl-N-(4-nitrophenyl-2-oxocyclopentane-1-carboxamide

    Directory of Open Access Journals (Sweden)

    Matthias Zeller

    2014-09-01

    Full Text Available The structure of the title compound, C14H15ClN2O4, prepared by reaction of a methacryloyl dimer with nitroaniline, was determined to establish the relative substituent orientation on the cyclopentanone ring. In agreement with an earlier proposed reaction mechanism, the amide group and the methyl group adjacent to the chloro substituent adopt equatorial positions and relative cis orientation, whereas the Cl substituent itself and the methyl group adjacent to the amide have axial orientations relative to the mean plane of the five-membered ring. The conformation of the molecule is stabilized by one classical N—H...O (2.18 Å and one non-classical C—H...O (2.23 Å hydrogen bond, each possessing an S(6 graph-set motif. The crystal packing is defined by several non-classical intramolecular hydrogen bonds, as well as by partial stacking of the aromatic rings.

  6. Stress distribution characteristics in the vicinity of coal seam floor

    Science.gov (United States)

    Cui, Zimo; Chanda, Emmanuel; Zhao, Jingli; Wang, Zhihe

    2018-01-01

    Although longwall top-coal caving (LTCC) has been a popular, more productive and cost-effective method in recent years, roadway floor heave and rock bursts frequently appear when exploiting such coal seams with large dip angle. This paper proposes addressing this problem by adopting three-dimensional roadway layout of stagger arrangement (3-D RLSA). In this study, the first step was to analyse the stress distribution characteristics in the vicinity of coal seam floor based on the stress slip line field theory. In the second step, numerical calculation using FLAC3D was conducted. Finally, an evaluation of the 3-D RLSA for solving this particular issue was given. Results indicate that for this particular mine the proposed 3-D RLSA results in 24% increase in the coal recovery ratio and a modest reduction in excavation and maintenance costs compared to the conventional LTCC method.

  7. Radiolysis of water in the vicinity of passive surfaces

    International Nuclear Information System (INIS)

    Moreau, S.; Fenart, M.; Renault, J.P.

    2014-01-01

    Highlights: • HO° production through water radiolysis is enhanced near metal surfaces. • Hastelloy and Stainless steel surfaces can also produce HO° radicals through hydrogen peroxide activation. • There is a deficit in solvated electron production compared to hydroxyl radicals near metal surfaces. - Abstract: Porous metals were used to describe the water radiolysis in the vicinity of metal surfaces. The hydroxyl radical production under gamma irradiation was measured by benzoate scavenging in water confined in a 200 nm porous Ni base alloy or in Stainless steel. The presence of the metallic surfaces changed drastically the HO° production level and lifetime. The solvated electron production was measured via glycylglycine scavenging for Stainless steel and was found to be significantly smaller than hydroxyl production. These observations imply that interfacial radiolysis may deeply impact the corrosion behavior of the SS and Ni based alloys

  8. M-Area Settling Basin and vicinity: Environmental information document

    International Nuclear Information System (INIS)

    Pickett, J.B.; Colven, W.P.; Bledsoe, H.W.

    1986-12-01

    This document provides environmental information on postulated closure options for the M-Area Settling Basin and vicinity at the Savannah River Plant and was developed as background technical documentation for the Department of Energy's proposed Environmental Impact Statement (EIS) on waste management activities for groundwater protection at the plant. The results of groundwater and atmospheric pathway analyses, accident analysis, and other environmental assessments discussed in this document are based upon a conservative analysis of all foreseeable scenarios as defined by the National Environmental Policy Act (40 CFR 1500-1508). The scenarios do not necessarily represent actual environmental conditions. This document is not meant to be used as a closure plan or other regulatory document to comply with required federal or state environmental regulations

  9. Developing the "Lunar Vicinity" Scenario of the Global Exploration Roadmap

    Science.gov (United States)

    Schmidt, G.; Neal, C. R.; Crawford, I. A.; Ehrenfreund, P.

    2014-04-01

    The Global Exploration Roadmap (GER, [1]) has been developed by the International Space Exploration Coordination Group (ISECG - comprised of 14 space agencies) to define various pathways to getting humans beyond low Earth orbit and eventually to Mars. Such pathways include visiting asteroids or the Moon before going on to Mars. This document has been written at a very high level and many details are still to be determined. However, a number of important papers regarding international space exploration can form a basis for this document (e.g. [2,3]). In this presentation, we focus on developing the "Lunar Vicinity" scenario by adding detail via mapping a number of recent reports/documents into the GER. Precedence for this scenario is given by Szajnfarber et al. [4] who stated "We find that when international partners are considered endogenously, the argument for a "flexible path" approach is weakened substantially. This is because international contributions can make "Moon first" economically feasible". The documents highlighted here are in no way meant to be all encompassing and other documents can and should be added, (e.g., the JAXA Space Exploration Roadmap). This exercise is intended to demonstrate that existing documents can be mapped into the GER despite the major differences in granularity, and that this mapping is a way to promote broader national and international buy-in to the Lunar Vicinity scenario. The documents used here are: the Committee on Space Research (COSPAR) Panel on Exploration report on developing a global space exploration program [5], the Strategic Knowledge Gaps (SKGs) report from the Lunar Exploration Analysis Group (LEAG) [6], the Lunar Exploration Roadmap developed by LEAG [7], the National Research Council report Scientific Context for the Exploration of the Moon (SCEM) [8], the scientific rationale for resuming lunar surface exploration [9], the astrobiological benefits of human space exploration [9,10].

  10. Substituent and structural effects on the kinetics of the reaction of N-(substituted phenylmethylene-m- and -p-aminobenzoic acids with diazodiphenylmethane

    Directory of Open Access Journals (Sweden)

    BRATISLAV Z. JOVANOVIC

    2007-12-01

    Full Text Available The rate constants for the reaction of twenty-two N-(substituted phenyl methylene-m- and -p-aminobenzoic acids with diazodiphenylmethane were determined in absolute ethanol at 30 °C. The effects of substituents on the reactivity of the investigated compounds were interpreted by correlation of the rate constants with LFER equations. The results of quantum mechanical calculations of the mole cular structure together with experimental results gave a better insight into the effects of structure on the transmission of electronic effects of the substituents. New σ constants for substituted benzylideneamino group were calculated.

  11. Catharanthine C16 substituent effects on the biomimetic coupling with vindoline: preparation and evaluation of a key series of vinblastine analogues

    Science.gov (United States)

    Tam, Annie; Gotoh, Hiroaki; Robertson, William M.; Boger, Dale L.

    2010-01-01

    The examination of the catharanthine C16 substituent effects on the Fe(III)-promoted biomimetic coupling reaction with vindoline is detailed, confirming the importance of the presence of a C16 electron-withdrawing substituent, and establishing an unanticipated unique role (>10-fold) that the C16 methyl ester plays in the expression of the natural product properties. Thus, replacement of the vinblastine C16′ methyl ester with an ethyl ester (10-fold), a cyano group (100-fold), an aldehyde (100-fold), a hydroxymethyl group (1000-fold), or a primary carboxamide (>1000-fold) led to surprisingly large reductions in cytotoxic activity. PMID:20932748

  12. Structural dependence of the multi-functionalized carbon nanotubes to the substituents on the grafted diazo compounds

    Science.gov (United States)

    Amiri, Rahebeh; Rasouli, Sousan; Ghasemi, Alireza; Eghbali, Babak; Mohammadi, Soutodeh

    2014-05-01

    Systematic studies on the covalent functionalization of multi-walled carbon nanotubes were performed by a series of azo molecules with different substituents. For this investigation, 4-substituted diazonium reagents have been used in the reaction with the functionalized multi-walled carbon nanotubes. We analyzed the effect of the substituted groups on the diazo component affinity in the grafting. Also, the structural differences of the final products were evaluated by visual dispersion test, UV-Vis absorption. Fourier transforms infrared, Raman, and several complementary techniques (scanning electron microscopy, thermal gravimetric analysis, and colorimetry test). Nuclear magnetic resonance spectroscopy has been used to confirm the allylic protons attached to the surface of carbon nanotubes after functionalization.

  13. Substituent effects in heterogeneous catalysis--4. Adsorption estimations during competitive hydrogenation of cyclohexanone and its 2-alkyl derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Chihara, T; Tanaka, K

    1979-02-01

    Adsorption estimations during competitive hydrogenation of cyclohexanone and its 2-alkyl derivatives alumina-supported ruthenium, rhodium, and platinum catalysts were obtained in a study to determine the relative contributions of the rate constants and the adsorption equilibrium constants to the substituent-dependent constant. The reaction rates obtained during competitive hydrogenation were in the order cyclohexanone (A) Vertical Bar3:Vertical Bar3: 2-methyl cyclohexanone (B) Vertical Bar3: 2-ethyl cyclohexanone (C) Vertical Bar3: 2-propyl cyclohexanone (D) for all catalysts, whereas the rates obtained during individual hydrogenation were in the order A Vertical Bar3: B approx. C approx. D. The adsorption equilibrium constants which were estimated by analyzing the kinetic data agreed well with the theoretical values derived from statistical mechanics by using a model in which the substrate ketones were immobilely adsorbed.

  14. Indolylarylsulfones as HIV-1 non-nucleoside reverse transcriptase inhibitors: new cyclic substituents at indole-2-carboxamide.

    Science.gov (United States)

    La Regina, Giuseppe; Coluccia, Antonio; Brancale, Andrea; Piscitelli, Francesco; Gatti, Valerio; Maga, Giovanni; Samuele, Alberta; Pannecouque, Christophe; Schols, Dominique; Balzarini, Jan; Novellino, Ettore; Silvestri, Romano

    2011-03-24

    New indolylarylsulfone derivatives bearing cyclic substituents at indole-2-carboxamide linked through a methylene/ethylene spacer were potent inhibitors of the WT HIV-1 replication in CEM and PBMC cells with inhibitory concentrations in the low nanomolar range. Against the mutant L100I and K103N RT HIV-1 strains in MT-4 cells, compounds 20, 24-26, 36, and 40 showed antiviral potency superior to that of NVP and EFV. Against these mutant strains, derivatives 20, 24-26, and 40 were equipotent to ETV. Molecular docking experiments on this novel series of IAS analogues have also suggested that the H-bond interaction between the nitrogen atom in the carboxamide chain of IAS and Glu138:B is important in the binding of these compounds. These results are in accordance with the experimental data obtained on the WT and on the mutant HIV-1 strains tested.

  15. Photoinduced electron transfer in covalent ruthenium-anthraquinone dyads: relative importance of driving-force, solvent polarity, and donor-bridge energy gap.

    Science.gov (United States)

    Hankache, Jihane; Wenger, Oliver S

    2012-02-28

    Four rigid rod-like molecules comprised of a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) photosensitizer, a 9,10-anthraquinone electron acceptor, and a molecular bridge connecting the two redox partners were synthesized and investigated by optical spectroscopic and electrochemical means. An attempt was made to assess the relative importance of driving-force, solvent polarity, and bridge variation on the rates of photoinduced electron transfer in these molecules. Expectedly, introduction of tert-butyl substituents in the bipyridine ligands of the ruthenium complex and a change in solvent from dichloromethane to acetonitrile lead to a significant acceleration of charge transfer rates. In dichloromethane, photoinduced electron transfer is not competitive with the inherent excited-state deactivation processes of the photosensitizer. In acetonitrile, an increase in driving-force by 0.2 eV through attachment of tert-butyl substituents to the bpy ancillary ligands causes an increase in electron transfer rates by an order of magnitude. Replacement of a p-xylene bridge by a p-dimethoxybenzene spacer entails an acceleration of charge transfer rates by a factor of 3.5. In the dyads from this study, the relative order of importance of individual influences on electron transfer rates is therefore as follows: solvent polarity ≥ driving-force > donor-bridge energy gap.

  16. Cooperative Magnetism in Crystalline N-Aryl-Substituted Verdazyl Radicals: First-Principles Predictions and Experimental Results.

    Science.gov (United States)

    Eusterwiemann, Steffen; Dresselhaus, Thomas; Doerenkamp, Carsten; Janka, Oliver; Niehaus, Oliver; Massolle, Anja; Daniliuc, Constantin G; Eckert, Hellmut; Pöttgen, Rainer; Neugebauer, Johannes; Studer, Armido

    2017-05-02

    We report on a series of eight diaryl-6-oxo-verdazyl radicals containing a tert-butyl group at the C(3) position with regard to their crystal structure and magnetic properties by means of magnetic susceptibility measurements in combination with quantum chemical calculations using a first-principles bottom-up approach. The latter method allows for a qualitative prediction and detailed analysis of the correlation between the solid-state architecture and magnetic properties. Although the perturbation in the molecular structure by varying the substituent on the N-aryl ring may appear small, the effects upon the structural parameters controlling intermolecular magnetic coupling interactions are strong, resulting in a wide spectrum of cooperative magnetic behavior. The non-substituted 1,5-diphenyl-tert-butyl-6-oxo-verdazyl radical features a ferromagnetic one-dimensional spin ladder type magnetic network-an extremely rarely observed phenomenon for verdazyl radicals. By varying substituents at the phenyl group, different non-isostructural compounds were obtained with widely different magnetic motifs ranging from linear and zigzag one-dimensional chains to potentially two-dimensional networks, from which we predict magnetic susceptibility data that are in qualitative agreement with experiments and reveal a large sensitivity to packing effects of the molecules. The present study advances the fundamental understanding between solid-state structure and magnetism in organically based radical systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Anionic polymerization of acrylates. XII. Polymerization of methyl methacrylate and tert-butyl acrylate initiated with alkyllithiums or methyl 2-lithioisobutyrate in the presence of lithium tert-butoxide

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Otoupalová, Jaroslava; Janata, Miroslav; Látalová, Petra; Masař, Bohumil; Toman, Luděk

    2002-01-01

    Roč. 43, č. 25 (2002), s. 7179-7184 ISSN 0032-3861 R&D Projects: GA ČR GA203/01/0513; GA MŠk OC P1.10 Institutional research plan: CEZ:AV0Z4050913 Keywords : ligated anionic polymerization * (meth)acrylates * lithium tert-butoxide Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.838, year: 2002

  18. Volumetric Behaviour of the Ternary Liquid System Composed of Methyl tert-Butyl Ether, Toluene, and Isooctane at Temperatures from (298.15 to 328.15) K. Experimental Data and Correlation

    Czech Academy of Sciences Publication Activity Database

    Morávková, Lenka; Wagner, Zdeněk; Sedláková, Zuzana; Linek, Jan

    2010-01-01

    Roč. 42, č. 7 (2010), s. 920-925 ISSN 0021-9614 R&D Projects: GA ČR GA104/09/0666 Institutional research plan: CEZ:AV0Z40720504 Keywords : isooctane * ternary mixture * adiabatic compressibility Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.794, year: 2010

  19. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethyl cyclopropene V. 3,3-Dimethyl-1-(trimethylgermyl)cyclopropene

    Science.gov (United States)

    De Maré, G. R.; Panchenko, Yu. N.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2004-02-01

    3,3-Dimethyl-1-(trimethylgermyl)cyclopropene ( I) was synthesised using a standard procedure. The IR and Raman spectra of I in the liquid phase were measured. The molecular geometry of I was optimised completely at the HF/6-31G* level. The HF/6-31G*//HF/6-31G* force field was calculated and scaled using the set of scale factors transferred from those determined previously for scaling the theoretical force fields of 3,3-dimethylbutene-1 and 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene. The assignments of the observed vibrational bands were performed using the theoretical frequencies calculated from the scaled HF/6-31G*//HF/6-31G* force field and the ab initio values of the IR intensities, Raman cross-sections and depolarisation ratios. The theoretical spectra are given. The completely optimised structural parameters of I and its vibrational frequencies are compared with corresponding data of related molecules.

  20. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    Science.gov (United States)

    Arıcı, Mürsel; Zafer Yeşilel, Okan; Büyükgüngör, Orhan

    2017-05-01

    Four coordination polymers including, [Co(μ-Htbip)2(μ-dib)]n (1), [Co(μ-tbip)(μ-dmib)0.5]n (2), [Zn2(μ-tbip)(μ3-tbip)(μ-dmib)1.5]n (3) and [Cd(μ3-tbip)(μ-dib)0.5 (H2O)]n (4) (tbip: 5-tert-butylisophthalate, dib: 1,4-bis(imidazol-1yl)benzene, dmib: 1,4-bis(imidazol-1yl)-2,5-dimethylbenzene), were hydrothermally synthesized and characterized by elemental analysis, IR spectra, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). The structural diversity is observed depending on ligands and coordination number of metal centers in the synthesized complexes. The tbip ligand displayed five different coordination modes in its complexes. In 1 and 2, complex 1 is 3D framework with the dia topology while complex 2 has 2D structure with the sql topology depending on coordination geometries of Co ions. Complex 3 is 3D framework with the fsh 4,6-conn topology and complex 4 has 2D 4-connected sql topology. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in methanol could be used as a fluorescent sensor for the detection of acetone. Moreover, thermal and optical properties of the complexes were also studied.

  1. Large-scale synthesis of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate by a stereoselective carbonyl reductase with high substrate concentration and product yield.

    Science.gov (United States)

    Liu, Zhi-Qiang; Hu, Zhong-Liang; Zhang, Xiao-Jian; Tang, Xiao-Ling; Cheng, Feng; Xue, Ya-Ping; Wang, Ya-Jun; Wu, Lin; Yao, Dan-Kai; Zhou, Yi-Teng; Zheng, Yu-Guo

    2017-05-01

    To biosynthesize the (3R,5S)-CDHH in an industrial scale, a newly synthesized stereoselective short chain carbonyl reductase (SCR) was successfully cloned and expressed in Escherichia coli. The fermentation of recombinant E. coli harboring SCR was carried out in 500 L and 5000 L fermenters, with biomass and specific activity of 9.7 g DCW/L, 15749.95 U/g DCW, and 10.97 g DCW/L, 19210.12 U/g DCW, respectively. The recombinant SCR was successfully applied for efficient production of (3R,5S)-CDHH. The scale-up synthesis of (3R,5S)-CDHH was performed in 5000 L bioreactor with 400 g/L of (S)-CHOH at 30°C, resulting in a space-time yield of 13.7 mM/h/g DCW, which was the highest ever reported. After isolation and purification, the yield and d.e. of (3R,5S)-CDHH reached 97.5% and 99.5%, respectively. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:612-620, 2017. © 2017 American Institute of Chemical Engineers.

  2. Crystal structure of 5,5′-dibromo-3,3′-di-tert-butyl-6,6′-dimethylbiphenyl-2,2′-diol

    Directory of Open Access Journals (Sweden)

    Rika Obata

    2015-05-01

    Full Text Available The whole molecule of the title compound, C22H28Br2O2, is generated by twofold rotation symmetry. The dihedral angle of the biphenyl moiety is 85.05 (11°. The hydroxy groups show intramolecular O—H...π interactions without any other hydrogen-bond acceptors. In the crystal, there are no other significant intermolecular interactions present.

  3. N-(N-[2-(3,5-Difluorophenyl)acetyl]-(S)-alanyl)-(S)-phenylglycine tert-butyl ester (DAPT): an inhibitor of γ-secretase, revealing fine electronic and hydrogen-bonding features

    Energy Technology Data Exchange (ETDEWEB)

    Czerwinski, Andrzej; Valenzuela, Francisco [Peptides International Inc., 11621 Electron Drive, Louisville, KY 40299 (United States); Afonine, Pavel [Lawrence Berkeley National Laboratory, One Cyclotron Road, Building 64R0121, Berkeley, CA 94720 (United States); Dauter, Miroslawa, E-mail: dauter@anl.gov [Basic Research Program, SAIC-Frederick Inc., Synchrotron Radiation Research Section, MCL, NCI, Argonne National Laboratory, Biosciences Division, Building 202, Argonne, IL 60439 (United States); Dauter, Zbigniew [Synchrotron Radiation Research Section, MCL, NCI, Argonne National Laboratory, Biosciences Division, Building 202, Argonne, IL 60439 (United States); Peptides International Inc., 11621 Electron Drive, Louisville, KY 40299 (United States)

    2010-12-01

    The title compound, C{sub 23}H{sub 26}F{sub 2}N{sub 2}O{sub 4}, is a dipeptidic inhibitor of γ-secretase, one of the enzymes involved in Alzheimer’s dis@@ease. The mol@@ecule adopts a compact conformation, without intra@@molecular hydrogen bonds. In the crystal structure, one of the amide N atoms forms the only inter@@molecular N—H⋯O hydrogen bond; the second amide N atom does not form hydrogen bonds. High-resolution synchrotron diffraction data permitted the unequivocal location and refinement without restraints of all H atoms, and the identification of the characteristic shift of the amide H atom engaged in the hydrogen bond from its ideal position, resulting in a more linear hydrogen bond. Significant residual densities for bonding electrons were revealed after the usual SHELXL refinement, and modeling of these features as additional inter@@atomic scatterers (IAS) using the program PHENIX led to a significant decrease in the R factor from 0.0411 to 0.0325 and diminished the r.m.s. deviation level of noise in the final difference Fourier map from 0.063 to 0.037 e Å{sup −3}.

  4. Bis(3,5-di-tert-butyl-4H-1,2,4-triazol-4-amine-κN1(nitrato-κOsilver(I ethanol monosolvate monohydrate

    Directory of Open Access Journals (Sweden)

    Ya-Mei Liu

    2012-06-01

    Full Text Available The AgI atom in the title compound, [Ag(NO3(C10H20N42]·C2H5OH·H2O, is coordinated by the N atoms of two N-heterocycles [N—Ag—N = 151.5 (1°]; the approximately linear coordination geometry is distorted into a T-shaped geometry owing to a long Ag...Onitrate bond [2.717 (4 Å]. The N atoms of the N-heterocycles that are not involved in coordination point towards the lattice water molecule, which functions as a hydrogen-bond donor. The water molecule itself is a hydrogen-bond acceptor towards the ethanol solvent molecule. Hydrogen bonds of the type N–H...O give rise to a layer motif parallel to (001.

  5. tert-Butyl 3-(8-bromo-4H,10H-1,2-oxazolo[4,3-c][1]benzoxepin-10-yl-2-methyl-1H-indole-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Ankur Trigunait

    2010-08-01

    Full Text Available In the title compound, C25H23BrN2O4, the seven-membered ring adopts a twisted-boat conformation. The indole ring system is planar within 0.021 (2 Å and the ester group [–C(=O—O—C–] is almost coplanar with it [dihedral angle = 3.0 (2°]. The conformation of the ester group is influenced by intramolecular C—H...O interactions. In the crystal structure, molecules are linked into chains along the b axis by C—H...N hydrogen bonds.

  6. Study of 2-methyl-2-oxo-3,5-di-tert. -butyl-. delta. /sup 4/-1,3,2-oxazaphospholine interaction with lanthanide shifting reagents. [Lanthanides: Eu, Pr

    Energy Technology Data Exchange (ETDEWEB)

    Turov, A.V.; Povolotskij, M.I.; Balitskij, Yu.V.; Kornilov, M.Yu.; Boldeskul, I.E. (AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii; Kievskij Gosudarstvennyj Univ. (Ukrainian SSR))

    1983-10-01

    2-methyl-2-oxo-3.5-di-tret.-butyl-..delta../sup 4/-1, 3, 2-oxazaphospholine in CDCl/sub 3/ solution reacts with lanthanide shifting reagents-tris (dipivaloylmethanates) of europium (3) and praseodymium (3)-with the formation of adducts of constant composition. At that, in (/sup +/H, /sup 13/C) NMR spectra considerable pseudocontact induced shifts of substratum signals take place. Geometry of the adducts formed is calculated.

  7. Protective effects of flavonoids isolated from Korean milk thistle Cirsium japonicum var. maackii (Maxim.) Matsum on tert-butyl hydroperoxide-induced hepatotoxicity in HepG2 cells.

    Science.gov (United States)

    Jung, Hyun Ah; Abdul, Qudeer Ahmed; Byun, Jeong Su; Joung, Eun-Ji; Gwon, Wi-Gyeong; Lee, Min-Sup; Kim, Hyeung-Rak; Choi, Jae Sue

    2017-09-14

    Milk thistle leaves and flowers have been traditionally used as herbal remedy to alleviate liver diseases for decades. Korean milk thistle, Cirsium japonicum var. maackii (Maxim.) Matsum has been employed in traditional folk medicine as diuretic, antiphlogistic, hemostatic, and detoxifying agents. The aim of current investigation was to evaluate hepatoprotective properties of the MeOH extract of the roots, stems, leaves and flowers of Korean milk thistle as well as four isolated flavonoids, luteolin, luteolin 5-O-glucoside, apigenin and apigenin 7-O-glucuronide during t-BHP-induced oxidative stress in HepG2 cells. Hepatoprotective potential of the MeOH extracts and flavonoids derived from Korean milk thistle against t-BHP-induced oxidative stress in HepG2 cells were evaluated following MTT method. Incubating HepG2 cells with t-BHP markedly decreased the cell viability and increased the intracellular ROS generation accompanied by depleted GSH levels. Protein expression of heme oxygenase (HO-1) and nuclear factor-E2-related factor 2 (Nrf-2) was determined by Western blot. Our findings revealed that pretreating HepG2 cells with MeOH extracts and bioactive flavonoids significantly attenuated the t-BHP-induced oxidative damage, followed by increased cell viability in a dose-dependent manner. The results illustrate that excess ROS generation was reduced and GSH levels increased dose-dependently when HepG2 cells were pretreated with four flavonoids. Moreover, Western blotting analysis demonstrated that protein expressions of Nrf-2 and HO-1 were also up-regulated by flavonoids treatment. These results clearly demonstrate that the MeOH extracts and flavonoids from Korean milk thistle protected HepG2 cells against oxidative damage triggered by t-BHP principally by modulating ROS generation and restoring depleted GSH levels in addition to the increased Nrf-2/HO-1 signaling cascade. These flavonoids are potential natural antioxidative biomarkers against oxidative stress-induced hepatotoxicity. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

  8. Synthesis, antimalarial activity, and preclinical pharmacology of a novel series of 4'-fluoro and 4'-chloro analogues of amodiaquine. Identification of a suitable "back-up" compound for N-tert-butyl isoquine.

    Science.gov (United States)

    O'Neill, Paul M; Shone, Alison E; Stanford, Deborah; Nixon, Gemma; Asadollahy, Eghbaleh; Park, B Kevin; Maggs, James L; Roberts, Phil; Stocks, Paul A; Biagini, Giancarlo; Bray, Patrick G; Davies, Jill; Berry, Neil; Hall, Charlotte; Rimmer, Karen; Winstanley, Peter A; Hindley, Stephen; Bambal, Ramesh B; Davis, Charles B; Bates, Martin; Gresham, Stephanie L; Brigandi, Richard A; Gomez-de-Las-Heras, Federico M; Gargallo, Domingo V; Parapini, Silvia; Vivas, Livia; Lander, Hollie; Taramelli, Donatella; Ward, Stephen A

    2009-04-09

    On the basis of a mechanistic understanding of the toxicity of the 4-aminoquinoline amodiaquine (1b), three series of amodiaquine analogues have been prepared where the 4-aminophenol "metabolic alert" has been modified by replacement of the 4'-hydroxy group with a hydrogen, fluorine, or chlorine atom. Following antimalarial assessment and studies on mechanism of action, two candidates were selected for detailed ADME studies and in vitro and in vivo toxicological assessment. 4'-Fluoro-N-tert-butylamodiaquine (2k) was subsequently identified as a candidate for further development studies based on potent activity versus chloroquine-sensitive and resistant parasites, moderate to excellent oral bioavailability, low toxicity in in vitro studies, and an acceptable safety profile.

  9. Product analyses and kinetic studies on gas phase oxidation of the fuel additive ethyl tert-butyl ether and its products; Produktanalysen und Kinetikuntersuchungen der Gasphasenoxidation des Kraftstoffadditivs Ethyl-tert-butylether und seiner Produkte

    Energy Technology Data Exchange (ETDEWEB)

    Becker, K H; Thuener, L

    1997-04-01

    The widespread use of the additive ETBE in gasoline leads to an increased release of this compound into the atmosphere via evaporation or exhaust fumes. In order to determine the influence of this additive on trace gas cycles it is first necessary to carry out studies on the degradation mechanisms and pertinent kinetic properties of this substance. The aim of the present study was to examine the degradation mechanisms of the fuel additive t-butyl ethyl ether under atmospheric conditions. The reactions of the main degradation products (t-butyl formiate and t-butyl acetate, together ca. 80%) were also studied in order to obtain as complete a picture of the degradation paths as possible. This was to permit an assessment of the influence of ETBE and its products on tropospheric trace gas cycles and ozone formation. [Deutsch] Bei haeufigem Zusatz von ETBE in Benzin wird diese Verbindung durch Verdampfung oder als Abgas verstaerkt in die Atmosphaere abgegeben. Um den Einfluss des Additivs auf die Spurengas-Kreislaeufe zu bestimmen, sind daher Untersuchungen noetig, um die Abbau-Mechanismen und die zugehoerigen kinetischen Daten zu ermitteln. Das Ziel dieser Arbeit ist die Untersuchung der Abbaumechanismen des Kraftstoffadditivs t-Butylethylether unter atmosphaerischen Bedingungen. Fuer eine moeglichst vollstaendige Analyse des Abbauweges werden auch die Reaktionen der Hauptabbauprodukte (t-Butylformiat und t-Butylacetat, zusammen etwa 80%) untersucht. Dadurch soll der Einfluss auf troposphaerische Spurengas-Kreislaeufe und auf die Ozonbildung von ETBE und seinen Produkten abgeschaetzt werden. (orig./SR)

  10. Isothermal Vapour-Liquid Equilibria in the Binary and Ternary Systems Composed of tert-Butyl Methyl Ether, 3,3-Dimethyl-2-butanone and 2,2-Dimethyl-1-propanol

    Czech Academy of Sciences Publication Activity Database

    Bernatová, Svatoslava; Pavlíček, Jan; Wichterle, Ivan

    2009-01-01

    Roč. 278, 1-2 (2009), s. 129-134 ISSN 0378-3812 R&D Projects: GA ČR GA104/07/0444 Institutional research plan: CEZ:AV0Z40720504 Keywords : alcohol * ether * ketone Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.857, year: 2009

  11. 4,4′,6,6′-Tetra-tert-butyl-2,2′-[1,3-diazinane-1,3-diylbis(methylene]diphenol 0.25-hydrate

    Directory of Open Access Journals (Sweden)

    Manman Zhang

    2012-07-01

    Full Text Available The title compound, C34H54N2O2·0.25H2O, the organic molecule, a potential tetradentate ligand with a bulky phenolic donor, has overall mirror symmetry. A partially occupied water molecule of solvation is present in the lattice. The six-membered 1,3-diazinane ring displays a chair conformation. An intramolecular O—H...N hydrogen bond ocurs. In the crystal, molecules are linked by O—H...O interactions.

  12. Gymnaster koraiensis and its major components, 3,5-di-O-caffeoylquinic acid and gymnasterkoreayne B, reduce oxidative damage induced by tert-butyl hydroperoxide or acetaminophen in HepG2 cells

    Directory of Open Access Journals (Sweden)

    Eun Hye Jho

    2013-10-01

    Full Text Available We investigated the protective effects of Gymnaster koraiensisagainst oxidative stress-induced hepatic cell damage. We usedtwo different cytotoxicity models, i.e., the administration oftert-butyl hydroperoxide (t-BHP and acetaminophen, in HepG2cells to evaluate the protective effects of G. koraiensis. The ethylacetate (EA fraction of G. koraiensis and its major compound,3,5-di-O-caffeoylquinic acid (DCQA, exerted protective effectsin the t-BHP-induced liver cytotoxicity model. The EA fractionand DCQA ameliorated t-BHP-induced reductions in GSHlevels and exhibited free radical scavenging activity. The EAfraction and DCQA also significantly reduced t-BHP-inducedDNA damage in HepG2 cells. Furthermore, the hexane fractionof G. koraiensis and its major compound, gymnasterkoreayne B(GKB, exerted strong hepatoprotection in the acetaminopheninducedcytotoxicity model. CYP 3A4 enzyme activity wasstrongly inhibited by the extract, hexane fraction, and GKB. Thehexane fraction and GKB ameliorated acetaminophen-inducedreductions in GSH levels and protected against cell death. [BMBReports 2013; 46(10: 513-518

  13. Biomarkers derived from heterolytic and homolytic cleavage of allylic hydroperoxides resulting from alkenone autoxidation

    Digital Repository Service at National Institute of Oceanography (India)

    Rontania, J.F.; Harji, R.; Volkmanc, J.K.

    Laboratory incubation of alkenone mixtures with tert-butyl hydroperoxide and di-tert-butyl nitroxide (radical initiator) in hexane, as a means to simulate alkenone autoxidation processes, rapidly led to the formation of allylic hydroperoxides, whose...

  14. 13C nuclear magnetic resonance data of lanosterol derivatives—Profiling the steric topology of the steroid skeleton via substituent effects on its 13C NMR

    Science.gov (United States)

    Dias, Jerry Ray; Gao, Hongwu

    2009-12-01

    The 13C NMR spectra of over 24 tetracyclic triterpenoid derivatives have been structurally analyzed. The 13C NMR chemical shifts allow one to probe the steric topology of the rigid steroid skeleton and inductive effects of its substituents. Use of deuterium labeling in chemical shift assignment and B-ring aromatic terpenoids are also featured.

  15. Photochemical generation of highly destabilized vinyl cations: the effects of alpha- and beta-trifluoromethyl versus alpha- and beta-methyl substituents

    NARCIS (Netherlands)

    Alem, van K.; Belder, G.; Lodder, G.; Zuilhof, H.

    2005-01-01

    The photochemical reactions in methanol of the vinylic halides 1-4, halostyrenes with a methyl or a trifluoromethyl substituent at the - or -position, have been investigated quantitatively. Next to E/Z isomerization, the reactions are formation of vinyl radicals, leading to reductive dehalogenation

  16. Acylated 2-(N-arylaminomethylene)benzo[b]thiophene-3(2H)-Ones: Molecular Switches with Varying Migrants and Substituents

    International Nuclear Information System (INIS)

    Dubonosov, A.D.; Rybalkin, V.P.; Tsukanov, A.V.; Minkin, V.I.; Popova, L.L.; Revinsky, Y.V.; Bren, V.A.; Minkin, V.I.

    2009-01-01

    Synthesis and properties of photo chromic acylated 2-(N-arylaminomethylene)benzo[b]thiophene-3(2H)-ones are described. Their structure largely depends on the nature of acyl migrant and in a less degree on N-aryl substituent.

  17. 77 FR 5398 - Safety Zone; Atlantic Intracoastal Waterway, Vicinity of Marine Corps Base, Camp Lejeune, NC

    Science.gov (United States)

    2012-02-03

    ...-AA00 Safety Zone; Atlantic Intracoastal Waterway, Vicinity of Marine Corps Base, Camp Lejeune, NC... zone on the Atlantic Intracoastal Waterway (AICW) adjacent to Marine Corps Base (MCB) Camp Lejeune..., Vicinity of Marine Corps Base, Camp Lejeune, NC in the Federal Register (77 FR 1431). We received no...

  18. On the nature of electromagnetic waves in the vicinity of auroral archs

    International Nuclear Information System (INIS)

    Volokitin, A.S.; Mordovskaya, V.G.

    1988-01-01

    Excitation of kinetic Alfven waves by longitudinal current in the vicinity of auroral arcs is considered in the framework of quasilinear theory. It is shown that experimentally observed low-frequency electromagnetic waves with f<2Hz frequency in the vicinity of uniform auroral arcs represent the Alfven waves, excited at altitudes of three Earth radii and above by longitudinal electric current

  19. Massive binaries in the vicinity of Sgr A*

    Energy Technology Data Exchange (ETDEWEB)

    Pfuhl, O.; Gillessen, S.; Genzel, R.; Eisenhauer, F.; Fritz, T. K.; Ott, T. [Max-Planck-Institut für Extraterrestrische Physik, D-85748 Garching (Germany); Alexander, T. [Faculty of Physics, Weizmann Institute of Science, P.O. Box 26, Rehovot 76100 (Israel); Martins, F., E-mail: pfuhl@mpe.mpg.de [LUPM, Université Montpelier 2, CNRS, Place Eugéne Bataillon, F-34095, Montpellier (France)

    2014-02-20

    A long-term spectroscopic and photometric survey of the most luminous and massive stars in the vicinity of the supermassive black hole Sgr A* revealed two new binaries: a long-period Ofpe/WN9 binary, IRS 16NE, with a modest eccentricity of 0.3 and a period of 224 days, and an eclipsing Wolf-Rayet binary with a period of 2.3 days. Together with the already identified binary IRS 16SW, there are now three confirmed OB/WR binaries in the inner 0.2 pc of the Galactic center. Using radial velocity change upper limits, we were able to constrain the spectroscopic binary fraction in the Galactic center to F{sub SB}=0.30{sub −0.21}{sup +0.34} at a confidence level of 95%, a massive binary fraction close to that observed in dense clusters. The fraction of eclipsing binaries with photometric amplitudes Δm > 0.4 is F{sub EB}{sup GC}=3%±2%, which is consistent with local OB star clusters (F {sub EB} = 1%). Overall, the Galactic center binary fraction seems to be similar to the binary fraction in comparable young clusters.

  20. Organofluorine chemistry: synthesis and conformation of vicinal fluoromethylene motifs.

    Science.gov (United States)

    O'Hagan, David

    2012-04-20

    The C-F bond is the most polar bond in organic chemistry, and thus the bond has a relatively large dipole moment with a significant -ve charge density on the fluorine atom and correspondingly a +ve charge density on carbon. The electrostatic nature of the bond renders it the strongest one in organic chemistry. However, the fluorine atom itself is nonpolarizable, and thus, despite the charge localization on fluorine, it is a poor hydrogen-bonding acceptor. These properties of the C-F bond make it attractive in the design of nonviscous but polar organic compounds, with a polarity limited to influencing the intramolecular nature of the molecule and less so intermolecular interactions with the immediate environment. In this Perspective, the synthesis of aliphatic chains carrying multivicinal fluoromethylene motifs is described. It emerges that the dipoles of adjacent C-F bonds orientate relative to each other, and thus, individual diastereoisomers display different backbone carbon chain conformations. These conformational preferences recognize the influence of the well-known gauche effect associated with 1,2-difluoroethane but extend to considering 1,3-fluorine-fluorine dipolar repulsions. The synthesis of carbon chains carrying two, three, four, five, and six vicinal fluoromethylene motifs is described, with an emphasis on our own research contributions. These motifs obey almost predictable conformational behavior, and they emerge as candidates for inclusion in the design of performance organic molecules. © 2012 American Chemical Society

  1. Noisy coupled logistic maps in the vicinity of chaos threshold.

    Science.gov (United States)

    Tirnakli, Ugur; Tsallis, Constantino

    2016-04-01

    We focus on a linear chain of N first-neighbor-coupled logistic maps in the vicinity of their edge of chaos in the presence of a common noise. This model, characterised by the coupling strength ϵ and the noise width σmax, was recently introduced by Pluchino et al. [Phys. Rev. E 87, 022910 (2013)]. They detected, for the time averaged returns with characteristic return time τ, possible connections with q-Gaussians, the distributions which optimise, under appropriate constraints, the nonadditive entropy, Sq, basis of nonextensive statistics mechanics. Here, we take a closer look on this model, and numerically obtain probability distributions which exhibit a slight asymmetry for some parameter values, in variance with simple q-Gaussians. Nevertheless, along many decades, the fitting with q-Gaussians turns out to be numerically very satisfactory for wide regions of the parameter values, and we illustrate how the index q evolves with (N,τ,ϵ,σmax). It is nevertheless instructive on how careful one must be in such numerical analysis. The overall work shows that physical and/or biological systems that are correctly mimicked by this model are thermostatistically related to nonextensive statistical mechanics when time-averaged relevant quantities are studied.

  2. Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox conditions

    NARCIS (Netherlands)

    Waals, van der Marcelle J.; Pijls, Charles; Sinke, Anja J.C.; Langenhoff, Alette A.M.; Smidt, Hauke; Gerritse, Jan

    2018-01-01

    The increasing use of biobased fuels and fuel additives can potentially change the typical fuel-related contamination in soil and groundwater. Anaerobic biotransformation of the biofuel additive ethyl tert-butyl ether (EtBE), as well as of methyl tert-butyl ether (MtBE), benzene, and tert-butyl

  3. The influence of different cyclometalated ligand substituents and ancillary ligand on the phosphorescent properties of iridium(III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Qing; Li, Yuanyuan; Wang, Xin; Wang, Li, E-mail: chemwangl@henu.edu.cn; Zhang, Jinglai, E-mail: zhangjinglai@henu.edu.cn

    2016-07-01

    Four iridium(III) complexes, (dfpmpy){sub 2}Ir(pic), (1), (dfpmpy){sub 2}Ir(EO{sub 2}-pic) (2), (dfpmpy){sub 2}Ir(pic-N-O) (3), and (dfpmpy){sub 2}Ir(EO{sub 2}-pic-N-O) (4) (dfpmpy = 2-(2,4-difluorophenyl)-4-methylpyridine, pic = picolinic acid, EO{sub 2}-pic = 4-(2-ethoxyethoxy) picolinic acid, pic-N-O = picolinic acid N-oxide, and EO{sub 2}-pic-N-O = 4-(2-ethoxyethoxy) picolinic acid N-oxide) are investigated by means of the density functional theory/time-dependent density functional theory (DFT/TD-DFT) to explore the influence of the ancillary ligand on the electronic structures, phosphorescent properties, and organic light-emitting diode (OLED) performance. Employing pic-N-O and EO{sub 2}-pic-N-O as the ancillary ligands would decrease the vertical energy and result in the red-shifted wavelength. Then, other four iridium(III) complexes (2a-2d) (See Scheme 1) are designed by introduction of the phenyl and −CHO substituents on the pyridine ring and phenyl ring of complex 2, respectively. As compared with complex 2, theoretical results show that newly designed complexes 2a-2c might be potential candidates for blue-emitting phosphors with better/comparable quantum yield and Δλ. Moreover, the performance of complexes 2a and 2c, i.e., introducing phenyl on the para-position of pyridine ring and phenyl ring in dfpmpy ligand, are better than that of 2b. - Highlights: • The structure-property relationship of Ir(III) complexes are investigated. • The effect of different substituents/positions on properties is explored. • Do the emissions follow the Kasha or non-Kasha scenario? • Newly possible blue-emitting Ir(III) complexes are theoretically designed.

  4. Effects of Bulky Substituents of Push-Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Higashino, Tomohiro; Kawamoto, Kyosuke; Sugiura, Kenichi; Fujimori, Yamato; Tsuji, Yukihiro; Kurotobi, Kei; Ito, Seigo; Imahori, Hiroshi

    2016-06-22

    To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.

  5. Effect of the Antibiotic Neomycin on the Toxicity of the Glycoside Vicine in Rats

    Directory of Open Access Journals (Sweden)

    Mahmoud S. Arbid

    2013-01-01

    Full Text Available Vicine is hydrolyzed by microflora to highly reactive free radical generating compound divicine which causes mortality and other adverse effects. This study in the rats established the effect of a broad spectrum and poorly absorbed antibiotic, neomycin sulfate on the toxicity of vicine. The results showed extremely decrease in mortality rate in the group pretreated with neomycin. Hemoglobin (Hb concentration, hematocrit (Hct value, and red blood cells (RBCs count were significantly decreased after injection of vicine and the improvement of these values in the group pretreated with neomycin. The same results were observed in white blood cells (WBCs. The results showed a significant decrease in glucose level and returned to normal in group pretreated with neomycin. Glutathione (GSH was significantly decreased in the vicine group and returned to normal value in the group pretreated with neomycin. Lipid peroxide (TBARs was significantly increased in the group treated with vicine and neomycin pretreated group decreased to the normal level. Glucose-6-phosphate dehydrogenase (G6-PD activity was significantly decreased and returned to normal level in rats pretreated with neomycin. Serum protein and globulin were significantly decreased but serum albumin showed insignificant decrease in vicine and neomycin groups compared to control. Alanine aminotransferase (ALT and aspartate aminotransferase (AST were significantly decreased in the vicine group. The group pretreated with neomycin showed significantly increased activities of AST and ALT compared with vicine group. In conclusion, neomycin pretreatment of rats injected with glycoside vicine decreased to a great extent of its toxic and mortality effects and is useful in favism and hemolytic anemia.

  6. Ge growth on vicinal si(001) surfaces: island's shape and pair interaction versus miscut angle.

    Science.gov (United States)

    Persichetti, L; Sgarlata, A; Fanfoni, M; Balzarotti, A

    2011-10-01

    A complete description of Ge growth on vicinal Si(001) surfaces is provided. The distinctive mechanisms of the epitaxial growth process on vicinal surfaces are clarified from the very early stages of Ge deposition to the nucleation of 3D islands. By interpolating high-resolution scanning tunneling microscopy measurements with continuum elasticity modeling, we assess the dependence of island's shape and elastic interaction on the substrate misorientation. Our results confirm that vicinal surfaces offer an additional degree of control over the shape and symmetry of self-assembled nanostructures.

  7. In vitro phase I metabolism of gamabufotalin and arenobufagin: Reveal the effect of substituent group on metabolic stability.

    Science.gov (United States)

    Feng, Yujie; Wang, Chao; Tian, Xiangge; Huo, Xiaokui; Feng, Lei; Sun, Chengpeng; Ge, Guangbo; Yang, Ling; Ning, Jing; Ma, Xiaochi

    2017-09-01

    Bufadienolides are a major class of bioactive compounds derived from amphibian skin secretion. Gamabufotalin (GB) and arenobufagin (AB) are among the top of the intensively investigated natural bufadienolides for their outstanding biological activities. This study aimed to characterize the phase I metabolism of GB and AB with respect to the metabolic profiles, enzymes involved, and catalytic efficacy, thereafter tried to reveal substituent effects on metabolism. Two mono-hydroxylated products of GB and AB were detected in the incubation mixtures, and they were accurately identified as 1- and 5-hydroxylated bufadienolides by NMR and HPLC-MS techniques. Reaction phenotyping studies demonstrated that CYP3A mediated the metabolism of the two bufadienolides with a high specific selectivity. Further kinetic evaluation demonstrated that the metabolism stability of GB and AB were better than other reported bufadienolides. Additionally, the CYP3A5 preference for hydroxylation of AB was observed, which was different to the selectivity of CYP3As for bufadienolides suggested by our previous report. This study can provide important data for elucidating the phase I metabolism of GB and AB and can lead to a better understanding of the bufadienolide-CYP3A interaction which is helpful for preclinical development and rational use of bufadienolides. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Effects of La-Zn substituent and calcination temperature on the microstructure and magnetic properties of Sr-ferrites

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiangcheng; Zhao, Zhang; Zhu, Boquan [Wuhan Univ. of Science and Technology (China). State Key Lab. of Refractories and Metallurgy

    2015-01-15

    In this study, La-Zn-substituted SrFe{sub 12}O{sub 19} ferrites were synthesized using the traditional ceramic process. The by-products of iron oxide scales from a steel plant were used as the main raw materials. The influence of the La-Zn substituent and the calcination temperature on the microstructure and magnetic properties of Sr{sub 1-x}La{sub x}Fe{sub 12-x}Zn{sub x}O{sub 19} ferrites was investigated. The results showed that with the increase in the x value, the crystalline lattice constant of the a- and c-axes and the cell volume decreased. There was no α-Fe{sub 2}O{sub 3} phase in the ferrites when the value of x was 0.3. The corresponding saturation magnetization (M{sub s}) and remnant magnetization (M{sub r}) values were, respectively, about 65 emu g{sup -1} and 39.5 emu g{sup -1}. Both values of M{sub s} and M{sub r} rise to the maximum value. When the calcination temperature was reduced from 1200 C to 1150 C, the average particle size decreased from 0.9 μm to 0.7 μm and M{sub s} remained at 65 emu g{sup -1}. However, the coercivity increased from 2690 Oe to 3100 Oe.

  9. Reactivity of main components and substituent distribution in esterified sugarcane bagasse prepared by effective solid phase reaction.

    Science.gov (United States)

    Gan, Tao; Zhang, Yanjuan; Chen, Yane; Hu, Huayu; Yang, Mei; Huang, Zuqiang; Chen, Dong; Huang, Aimin

    2018-02-01

    Three main components of lignocellulose (cellulose, hemicellulose, and lignin isolated from sugarcane bagasse (SCB)) as well as holocellulose and SCB were modified with maleic acid by mechanical activation (MA)-assisted solid phase reaction (MASPR) technology. The order of reactivity was found to be lignin>hemicellulose>cellulose. The amorphous structure of lignin and hemicellulose mainly attributed to their better reactivity, and the modified lignin could reach a maximum degree of esterification (DE) of 93.45%. MA improved the accessibility and reactivity of cellulose, as the DE of modified cellulose gradually increased with milling time and reached the maximum value of 57.30% at 120min, which had significant effect on structure changes and DE of modified holocellulose and SCB. MA enhanced the esterification of all three components in lignocellulose with relatively high substituent distribution in them, and maleated SCB with a maximum DE of 64.17% was successfully prepared by this simple, green, and effective MASPR technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Substituent effects on the relaxation dynamics of furan, furfural and β-furfural: a combined theoretical and experimental approach.

    Science.gov (United States)

    Oesterling, Sven; Schalk, Oliver; Geng, Ting; Thomas, Richard D; Hansson, Tony; de Vivie-Riedle, Regina

    2017-01-18

    For the series furan, furfural and β-furfural we investigated the effect of substituents and their positioning on the photoinduced relaxation dynamics in a combined theoretical and experimental approach. Using time resolved photoelectron spectroscopy with a high intensity probe pulse, we can, for the first time, follow the whole deactivation process of furan through a two photon probe signal. Using the extended 2-electron 2-orbital model [Nenov et al., J. Chem. Phys., 2011, 135, 034304] we explain the formation of one central conical intersection and predict the influence of the aldehyde group of the derivatives on its geometry. This, as well as the relaxation mechanisms from photoexcitation to the final outcome was investigated using a variety of theoretical methods. Complete active space self consistent field was used for on-the-fly calculations while complete active space perturbation theory and coupled cluster theory were used to accurately describe critical configurations. Experiment and theory show the relaxation dynamics of furfural and β-furfural to be slowed down, and together they disclose an additional deactivation pathway, which is attributed to the n O lonepair state introduced with the aldehyde group.

  11. A Successful Attempt to Obtain the Linear Dependence Between One-Photon and Two-Photon Spectral Properties and Hammett Parameters of Various Aromatic Substituents in New π-Extended Asymmetric Organic Chromophores.

    Science.gov (United States)

    Hu, Nvdan; Gong, Yulong; Wang, Xinchao; Lu, Yao; Peng, Guangyue; Yang, Long; Zhang, Shengtao; Luo, Ziping; Li, Hongru; Gao, Fang

    2015-11-01

    A series of new asymmetric chromophores containing aromatic substituents and possessing the excellent π-extension in space were prepared through multi-steps routes. One-photon and two-photon spectral properties of these new chromophores could be tuned by these substituents finely and simultaneously. The linear correlation of the wave numbers of the one-photon absorption and emission maxima to Hammett parameters of these substituents was presented. Near infrared two-photon absorption emission integrated areas of the target chromophores were correlated linearly to Hammett constants of these substituted groups.

  12. Basalt microlapilli in deep sea sediments of Indian Ocean in the vicinity of Vityaz fracture zone

    Digital Repository Service at National Institute of Oceanography (India)

    Nath, B.N.; Iyer, S.D.

    Two cores recovered from the flanks of Mid-India oceanic ridge in the vicinity of Vityaz fracture zone consist of discrete pyroclastic layers at various depths. These layers are composed of coarse-grained, angular basaltic microlapilli in which...

  13. Phosphorus-containing podands. 14. Effect of alkyl substituents at phosphorus atom on complexing ability of neutral monopodands. On the nature of abnormal alkyl effect

    International Nuclear Information System (INIS)

    Tsvetkov, E.N.; Evreinov, V.I.; Bondarenko, N.A.; Safronova, Z.V.

    1996-01-01

    The previously revealed unusual effect of alkyl substituents at phosphorus atom in phosphorus-containing monopodands of the general formula o-R 2 P(O)C 6 H 4 (OCH 2 CH 2 ) n OC 6 H 4 P(O)R 2 -o, n=1-5, R = Alk, Ph, OEt on their complexing ability towards alkali metals cations has been interpreted. Alkyl radicals create great spatial obstacles to rotation of R 2 P(O) fragments around the C-P bond as compared with other substituents, which gives rise to the appearance of anomalous alkyl effect. Solvation is an additional factor, which can bring about the anomalous effect appearance or a change in the degree of its pronouncement. 47 refs.; 3 figs.; 7 tabs

  14. Application of the Fenske-Hall molecular orbital method to the calculation of 11B NMR chemical shifts. Antipodal substituent effects in deltahedral clusters

    International Nuclear Information System (INIS)

    Fehlner, T.P.; Czech, P.T.; Fenske, R.F.

    1990-01-01

    Utilizing Fenske-Hall wave functions and eigenvalues combined with the Ramsey sum over states (SOS) approximation, it is demonstrated that the sign and magnitude of the paramagnetic contribution to the shielding correlates well with the observed 11 B chemical shifts of a substantial variety of boron- and metal-containing compounds. Analysis of the molecular orbital (MO) contributions in the SOS approximation leads to an explanation of the large downfield shifts associated with metal-rich metallaboranes. A similar analysis demonstrates the importance of selected cluster occupied and unoccupied MO's in explaining both exo-cage substituent effects in which the antipodal boron resonance is shifted upfield and endo-cage substituent effects (interchange of isolobal fragments within the cage framework) in which the antipodal boron resonance is shifted downfield. Exo- and endo-cage substitution perturbs these MO's in an understandable fashion, leading to an internally consistent explanation of the observed chemical shift changes. 36 refs., 8 figs., 4 tabs

  15. A 3D visualization of the substituent effect : A brief analysis of two components of the operational formula of dual descriptor for open-shell systems.

    Science.gov (United States)

    Martínez-Araya, Jorge I; Yepes, Diana; Jaque, Pablo

    2017-12-27

    Six organometallic compounds coming from a basic Mo-based complex were analyzed from the perspective of the dual descriptor in order to detect subtle influences that a substituent group could exert on the reactive core at a long range. Since the aforementioned complexes are open-shell systems, the used operational formula for the dual descriptor is that one defined for those aforementioned systems, which was then compared with spin density. In addition, dual descriptor was decomposed into two terms, each of which was also applied on every molecular system. The obtained results indicated that components of dual descriptor could become more useful than the operational formula of dual descriptor because differences exerted by the substituents at the para position were better detected by components of dual descriptor rather than the dual descriptor by itself.

  16. Synthesis of some fenchyl-substituted alkenes and enol-ethers containing 3-oxyphenyl substituents by the Barton-Kellogg reaction

    International Nuclear Information System (INIS)

    Ciscato, Luiz Francisco M.L.; Bartoloni, Fernando H.; Baader, Wilhelm Josef; Bastos, Erick L.; Guenther, Wolfgang; Weiss, Dieter; Beckert, Rainer

    2010-01-01

    The synthesis of one fenchyl-substituted alkene and two enol-ethers, containing 3-oxyphenyl substituents by the Barton-Kellogg reaction is described. The tri-substituted aromatic fenchylalkene 1a was prepared in 53% yield from thiofenchone and a diazoanisole; whereas enol-ethers 1b and 1c were obtained (95 and 75% yield, respectively) using an inverse approach based on diazofenchone and aromatic thionoesters. A mixture of Z and E isomers was obtained in all cases; isomer attribution and quantification has been carried out by analysis of NMR spectroscopic data assisted by theoretical calculations (E/Z ratio: 1a = 0.72, 1b = 2.2, 1c = 1.8). Reaction proceeds with low stereoselectivity leading to the preferential formation of diastereoisomeric olefins and enol-ethers where the aromatic substituent resides at the side of the two fenchyl methyl groups. (author)

  17. Synthesis of some fenchyl-substituted alkenes and enol-ethers containing 3-oxyphenyl substituents by the Barton-Kellogg reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ciscato, Luiz Francisco M.L.; Bartoloni, Fernando H.; Baader, Wilhelm Josef, E-mail: wjbaader@iq.usp.b [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental; Bastos, Erick L. [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas; Guenther, Wolfgang; Weiss, Dieter; Beckert, Rainer [Friedrich-Schiller Universitaet Jena (Germany). Institut fuer Organische Chemie und Makromolekulare Chemie

    2010-07-01

    The synthesis of one fenchyl-substituted alkene and two enol-ethers, containing 3-oxyphenyl substituents by the Barton-Kellogg reaction is described. The tri-substituted aromatic fenchylalkene 1a was prepared in 53% yield from thiofenchone and a diazoanisole; whereas enol-ethers 1b and 1c were obtained (95 and 75% yield, respectively) using an inverse approach based on diazofenchone and aromatic thionoesters. A mixture of Z and E isomers was obtained in all cases; isomer attribution and quantification has been carried out by analysis of NMR spectroscopic data assisted by theoretical calculations (E/Z ratio: 1a = 0.72, 1b = 2.2, 1c = 1.8). Reaction proceeds with low stereoselectivity leading to the preferential formation of diastereoisomeric olefins and enol-ethers where the aromatic substituent resides at the side of the two fenchyl methyl groups. (author)

  18. The influence of serum substituents on serum-free Vero cell conditioned culture media manufactured from Dulbecco's modified Eagle medium in mouse embryo culture.

    Science.gov (United States)

    Lee, Jong-Seon; Kim, Ju-Hwan; Seo, Young-Seok; Yang, Jung-Bo; Kim, Yong-Il; Kim, Hye-Jin; Lee, Ki-Hwan

    2013-09-01

    This study was conducted to examine the influences of supplementation of the serum substituents and available period of serum-free Vero cell conditioned media (SF-VCM) manufactured from Dulbecco's modified Eagle medium cultured with Vero cells for in vitro development of mouse preimplantation embryos. A total of 1,099 two-cell embryos collected from imprinting control region mice were cultured in SF-VCM with 10% and 20% human follicular fluid (hFF), serum substitute supplement (SSS), and serum protein substitute (SPS). Development of embryos was observed every 24 hours. Results between different groups were analyzed by chi-square test, and considered statistically significant when P-value was less than 0.05. The rates of embryonic development cultured in SF-VCM supplemented with serum substituents were significantly higher compare with serum-free group (P media up to 4 weeks did not affect on embryonic development.

  19. π-face donation from the aromatic N-substituent of N-heterocyclic carbene ligands to metal and its role in catalysis

    KAUST Repository

    Credendino, Raffaele

    2012-05-16

    In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.

  20. Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag{sup +}/TiO{sub 2}: Influence of electron donating and withdrawing substituents

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Jiadong [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Xie, Yongbing, E-mail: ybxie@ipe.ac.cn [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Han, Qingzhen [State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Cao, Hongbin [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Wang, Yujiao [Department of Chemical and Biomedical Engineering, University of Science and Technology Beijing (China); Nawaz, Faheem; Duan, Feng [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China)

    2016-03-05

    Highlights: • A weak EWG benefited photocatalytic oxidation of phenols the most. • Phenolic compounds were dominantly oxidized by ·O{sub 2}{sup −}, rather than ·OH, {sup 1}O{sub 2} or h{sup +}. • ·O{sub 2}{sup −} preferred to nucleophilically attack EDG substituted phenols. • ·O{sub 2}{sup −} more likely electrophilically attacked EWG substituted phenols. • ·O{sub 2}{sup −} simultaneously nucleophilically and electrophilically assaulted p-chlorophenol. - Abstract: A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag{sup +}/TiO{sub 2} suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (·O{sub 2}{sup −}) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between ·O{sub 2}{sup −} and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of ·O{sub 2}{sup −} and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by ·O{sub 2}{sup −}, while ·O{sub 2}{sup −} preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by ·O{sub 2}{sup −} could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate

  1. Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag"+/TiO_2: Influence of electron donating and withdrawing substituents

    International Nuclear Information System (INIS)

    Xiao, Jiadong; Xie, Yongbing; Han, Qingzhen; Cao, Hongbin; Wang, Yujiao; Nawaz, Faheem; Duan, Feng

    2016-01-01

    Highlights: • A weak EWG benefited photocatalytic oxidation of phenols the most. • Phenolic compounds were dominantly oxidized by ·O_2"−, rather than ·OH, "1O_2 or h"+. • ·O_2"− preferred to nucleophilically attack EDG substituted phenols. • ·O_2"− more likely electrophilically attacked EWG substituted phenols. • ·O_2"− simultaneously nucleophilically and electrophilically assaulted p-chlorophenol. - Abstract: A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag"+/TiO_2 suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (·O_2"−) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between ·O_2"− and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of ·O_2"− and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by ·O_2"−, while ·O_2"− preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by ·O_2"− could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate constant. Possible reactive positions on the phenolic compounds were also detailedly uncovered.

  2. Dark and Photoinduced Cytotoxic Activity of the New Chlorophyll-a Derivatives with Oligoethylene Glycol Substituents on the Periphery of Their Macrocycles

    OpenAIRE

    Yana I. Pylina; Dmitry M. Shadrin; Oksana G. Shevchenko; Olga M. Startseva; Igor O. Velegzhaninov; Dmitry V. Belykh; Ilya O. Velegzhaninov

    2017-01-01

    In the present work, we investigated the dark and photoinduced cytotoxic activity of the new chlorophyll-a derivatives which contain the substituents of oligoethylene glycol on the periphery of their macrocycles. These compounds were tested using human cell lines to estimate their potential as photosensitizers for photodynamic therapy of cancer. It was shown that all the tested compounds have expressed photoinduced cytotoxic activity in vitro. Detailed study of the biological activity of one ...

  3. Influence of different amino substituents in position 1 and 4 on spectroscopic and acid base properties of 9,10-anthraquinone moiety.

    Science.gov (United States)

    Wcisło, Anna; Niedziałkowski, Paweł; Wnuk, Elżbieta; Zarzeczańska, Dorota; Ossowski, Tadeusz

    2013-05-01

    A series of novel 1-amino and 1,4-diamino-9,10-anthraquinones, substituted with different alkyl groups, were synthesized as the result of alkylation with amino substituents. All the obtained aminoanthraquinone derivatives were characterized by NMR, IR spectroscopy and mass spectrometry. The spectroscopic properties of these compounds were determined by using UV-Vis spectroscopy in acetonitrile, and in the mixture of acetonitrile and methanol at different pH ranges. The effects of various substituents present in the newly developed anthraquinone derivatives and their ability to form hydrogen bonds between the carbonyl oxygen atom of anthraquinone moiety and nitrogen atom of N-H group in 1-aminoanthraquinone (1-AAQ) and 1,4-diaminoanthraquinone (1,4-DAAQ) were studied. Additionally, the effects of hydrogen bond formation between O-H group in hydroxyethylamino substituent and the carbonyl oxygen atom of anthraquinone were investigated. The spectroscopic behavior of the studied derivatives strongly depended on the solvent-solute interactions and the nature of solvent. The values of pKa for the new anthraquinones were determined by the combined potentiometric and spectrophotometric titration methods. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Substituent and solvent effects on spectroscopic properties of 2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene derivatives

    International Nuclear Information System (INIS)

    Józefowicz, M.; Bajorek, A.; Pietrzak, M.; Heldt, J.R.; Heldt, J.

    2014-01-01

    In this article, we report the photophysical properties of six, newly synthesized donor-substituted 2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene fluorophores. The steady-state and time-resolved spectroscopic experiments have been used to investigate the substituent and solvent effects on the locally excited (LE) and intramolecular charge transfer (ICT) emission. We demonstrate that the spectroscopic characteristics (fluorescence quantum yields, fluorescence decay times, radiative rate constants, and ground and excited state dipole moments) of the studied D–A dyes, as well as the reorganization energies characterizing the solute–solvent interactions and intramolecular torsion motions greatly depend on different substituents and microenvironment. On the basis of the experimental results and our previous quantum-chemical calculations, it was shown that two emitting charge transfer states: non-relaxed (ICT) NR and relaxed (ICT) R exist in six biphenyl derivatives dissolved in polar solvents (e.g., THF), whereas in non-polar medium (MCH) the existence of two emissive states have been attributed to non-relaxed and relaxed, locally excited state ((LE) NR , (LE) R ). - Highlights: • Spectroscopic properties greatly depend on different substituents and microenvironment. • Investigated dyes form a typically spectrally inhomogeneous system. • Two emitting charge transfer states (ICT) NR and (ICT) R exist in polar solvents. • In non-polar medium locally excited fluorescence is possible from (LE) NR and (LE) R states

  5. Electrical transport in strained silicon quantum wells on vicinal substrates

    International Nuclear Information System (INIS)

    Kaya, S.

    1999-01-01

    This thesis deals with the electrical transport studies of strained Si quantum wells grown on tilted Si substrates. Magnetotransport measurements at very low temperatures are used to investigate the high electron mobility, scattering processes and modified band structure for four different substrate orientations (2, 4, 6 and 10 deg.) and in two different directions of transport. We first discuss the morphology of the tilted system with the aid of, atomic force and optical microscopy. A clear change of surface morphology of tilted layers in comparison with the (001) type surfaces is explained by the degree of tilt in the system. The electron mobility and in-plane effective mass becomes anisotropic, which scale roughly with the tilt angle. The mobility anisotropy is shown to be the result of extra scattering when electrons travel across the steps common to vicinal surfaces. The extra scattering has characteristics similar to interface roughness scattering, as inferred from the trend that the transport (τ t ) and quantum scattering (τ q ) times follow. As the tilt angle grows, it is found that τ t /τ q →1 in the direction perpendicular to the steps. Electrons in tilted channels of multivalley semiconductors can involve a new interband scattering mechanism due to a one dimensional minigap opening in the conduction band. This effect, known from bulk Si MOSFETs, is investigated in strained Si for the first time in this thesis. First, the effect of applied electric fields on electron conduction is considered. Shubnikov-de Haas oscillations in the magnetoresistance data indicate a remarkably different electron scattering behaviour in tilted samples with increasing fields in directions parallel and perpendicular to the tilt direction. An FFT analysis of the data produces extra peaks in the electron density spectra. By clear contrast, flat samples grown under similar conditions do not show any unusual features. The difference is attributed to the existence of a minigap

  6. First Spectroscopic Studies and Detection in SgrB2 of 13C-DOUBLY Substitued Ethyl Cyanide

    Science.gov (United States)

    Margulès, L.; Motiyenko, R. A.; Guillemin, J.-C.; Müller, Holger S. P.; Belloche, Arnaud

    2015-06-01

    Ethyl cyanide (CH_3CH_2CN) is one of the most abundant complex organic molecules in the interstellar medium firstly detected in OMC-1 and Sgr B2 in 1977. The vibrationally excited states are enough populated under ISM conditions and could be detected. Apart from the deuterated ones, all mono-substituted isotopologues of ethyl cyanide (13C and 15N have been detected in the ISM. The detection of isotopologues in the ISM is important: it can give information about the formation process of complex organic molecules, and it is essential to clean the ISM spectra from the lines of known molecules in order to detect new ones. The 12C/13C ratio found in SgrB2: 20-30 suggests that the doubly 13C could be present in the spectral line survey recently obtained with ALMA (EMoCA), but no spectroscopic studies exist up to now. We measured and analyzed the spectra of the 13C-doubly-substitued species up to 1 THz with the Lille solid-state based spectrometer. The spectroscopic results and and the detection of the doubly 13C species in SgrB2 will be presented. This work was supported by the CNES and the Action sur Projets de l'INSU, PCMI. This work was also done under ANR-13-BS05-0008-02 IMOLABS. Support by the Deutsche Forschungsgemeinschaft via SFB 956, project B3 is acknowledged D.~R.~Johnson, et al., Astrophys.~J. 1977, 218, L370 A.~Belloche, et al., A&A 2013, 559, A47 A.M.~Daly, et al., Astrophys.~J. 2013, 768, 81 K.~Demyk, et al. A&A 2007 466, 255 Margulès, et al. A&A 2009, 493, 565 Belloche et al. 2014, Science, 345, 1584

  7. Charge-Shift Corrected Electronegativities and the Effect of Bond Polarity and Substituents on Covalent-Ionic Resonance Energy.

    Science.gov (United States)

    James, Andrew M; Laconsay, Croix J; Galbraith, John Morrison

    2017-07-13

    Bond dissociation energies and resonance energies for H n A-BH m molecules (A, B = H, C, N, O, F, Cl, Li, and Na) have been determined in order to re-evaluate the concept of electronegativity in the context of modern valence bond theory. Following Pauling's original scheme and using the rigorous definition of the covalent-ionic resonance energy provided by the breathing orbital valence bond method, we have derived a charge-shift corrected electronegativity scale for H, C, N, O, F, Cl, Li, and Na. Atomic charge shift character is defined using a similar approach resulting in values of 0.42, 1.06, 1.43, 1.62, 1.64, 1.44, 0.46, and 0.34 for H, C, N, O, F, Cl, Li, and Na, respectively. The charge-shift corrected electronegativity values presented herein follow the same general trends as Pauling's original values with the exception of Li having a smaller value than Na (1.57 and 1.91 for Li and Na respectively). The resonance energy is then broken down into components derived from the atomic charge shift character and polarization effects. It is then shown that most of the resonance energy in the charge-shift bonds H-F, H 3 C-F, and Li-CH 3 and borderline charge-shift H-OH is associated with polarity rather than the intrinsic atomic charge-shift character of the bonding species. This suggests a rebranding of these bonds as "polar charge-shift" rather than simply "charge-shift". Lastly, using a similar breakdown method, it is shown that the small effect the substituents -CH 3 , -NH 2 , -OH, and -F have on the resonance energy (<10%) is mostly due to changes in the charge-shift character of the bonding atom.

  8. Cu(II) bis(thiosemicarbazone) radiopharmaceutical binding to serum albumin: further definition of species dependence and associated substituent effects

    International Nuclear Information System (INIS)

    Basken, Nathan E.; Green, Mark A.

    2009-01-01

    Introduction: The pyruvaldehyde bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-PTSM) and diacetyl bis(N 4 -methylthiosemicarbazonato)copper(II) (Cu-ATSM) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) radiopharmaceutical appears to exhibit only nonspecific binding to HSA and animal serum albumins. Methods: To further probe the structural basis for the species dependence of this albumin binding interaction, we examined protein binding of these three radiopharmaceuticals in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat and elephant). We also evaluated the albumin binding of several copper(II) bis(thiosemicarbazone) chelates offering more diverse substitution of the ligand backbone. Results: Cu-PTSM and Cu-ATSM exhibit a strong interaction with HSA that is not apparent with the albumins of other species, while the binding of Cu-ETS to albumin is much less species dependent. The strong interaction of Cu-PTSM with HSA does not appear to simply correlate with variation, relative to the animal albumins, of a single amino acid lining HSA's IIA site. Those agents that selectively interact with HSA share the common feature of only methyl or hydrogen substitution at the carbon atoms of the diimine fragment of the ligand backbone. Conclusions: The interspecies variations in albumin binding of Cu-PTSM and Cu-ATSM are not simply explained by unique amino acid substitutions in the IIA binding pocket of the serum albumins. However, the specific affinity for this region of HSA is disrupted when substituents bulkier than a methyl group appear on the imine carbons of the copper bis(thiosemicarbazone) chelate.

  9. Cu(II) bis(thiosemicarbazone) radiopharmaceutical binding to serum albumin: further definition of species dependence and associated substituent effects

    Energy Technology Data Exchange (ETDEWEB)

    Basken, Nathan E. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States); Green, Mark A. [Division of Nuclear Pharmacy, Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette, IN 47907 (United States)], E-mail: magreen@purdue.edu

    2009-07-15

    Introduction: The pyruvaldehyde bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-PTSM) and diacetyl bis(N{sup 4}-methylthiosemicarbazonato)copper(II) (Cu-ATSM) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) radiopharmaceutical appears to exhibit only nonspecific binding to HSA and animal serum albumins. Methods: To further probe the structural basis for the species dependence of this albumin binding interaction, we examined protein binding of these three radiopharmaceuticals in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat and elephant). We also evaluated the albumin binding of several copper(II) bis(thiosemicarbazone) chelates offering more diverse substitution of the ligand backbone. Results: Cu-PTSM and Cu-ATSM exhibit a strong interaction with HSA that is not apparent with the albumins of other species, while the binding of Cu-ETS to albumin is much less species dependent. The strong interaction of Cu-PTSM with HSA does not appear to simply correlate with variation, relative to the animal albumins, of a single amino acid lining HSA's IIA site. Those agents that selectively interact with HSA share the common feature of only methyl or hydrogen substitution at the carbon atoms of the diimine fragment of the ligand backbone. Conclusions: The interspecies variations in albumin binding of Cu-PTSM and Cu-ATSM are not simply explained by unique amino acid substitutions in the IIA binding pocket of the serum albumins. However, the specific affinity for this region of HSA is disrupted when substituents bulkier than a methyl group appear on the imine carbons of the copper bis(thiosemicarbazone) chelate.

  10. Synthesis and characterization of new fluorescent styrene-containing carborane derivatives: the singular quenching role of a phenyl substituent.

    Science.gov (United States)

    Ferrer-Ugalde, Albert; Juárez-Pérez, Emilio José; Teixidor, Francesc; Viñas, Clara; Sillanpää, Reijo; Pérez-Inestrosa, Ezequiel; Núñez, Rosario

    2012-01-09

    A set of neutral and anionic carborane derivatives in which the styrenyl fragment is introduced as a fluorophore group has been successfully synthesized and characterized. The reaction of the monolithium salts of 1-Ph-1,2-C(2)B(10)H(11), 1-Me-1,2-C(2)B(10)H(11) and 1,2-C(2)B(10)H(12) with one equivalent of 4-vinylbenzyl chloride leads to the formation of compounds 1-3, whereas the reaction of the dilithium salt of 1,2-C(2)B(10)H(12) with two equivalents of 4-vinylbenzyl chloride gives disubstituted compound 4. The closo clusters were degraded using the classical method, KOH in EtOH, to afford the corresponding nido species, which were isolated as tetramethylammonium salts. The crystal structure of the four closo compounds 1-4 were analyzed by X-ray diffraction. All compounds, except 1, display emission properties, with quantum yields dependent on the nature of the cluster (closo or nido) and the substituent on the second C(cluster) atom. In general, closo compounds 2-4 exhibit high fluorescence emission, whereas the presence of a nido cluster produces a decrease of the emission intensity. The presence of a phenyl group bonded to the C(cluster) results in an excellent electron-acceptor unit that produces a quenching of the fluorescence. DFT calculations have confirmed the charge-separation state in 1 to explain the quenching of the fluorescence and the key role of the carboranyl fragment in this luminescent process. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Enantioselective copper catalysed intramolecular C-H insertion reactions of α-diazo-β-keto sulfones, α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones; the influence of the carbene substituent.

    Science.gov (United States)

    Shiely, Amy E; Slattery, Catherine N; Ford, Alan; Eccles, Kevin S; Lawrence, Simon E; Maguire, Anita R

    2017-03-22

    Enantioselectivities in C-H insertion reactions, employing the copper-bis(oxazoline)-NaBARF catalyst system, leading to cyclopentanones are highest with sulfonyl substituents on the carbene carbon, and furthermore, the impact is enhanced by increased steric demand on the sulfonyl substituent (up to 91%ee). Enantioselective intramolecular C-H insertion reactions of α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones are reported for the first time.

  12. Surface energy and surface stress on vicinals by revisiting the Shuttleworth relation

    Science.gov (United States)

    Hecquet, Pascal

    2018-04-01

    In 1998 [Surf. Sci. 412/413, 639 (1998)], we showed that the step stress on vicinals varies as 1/L, L being the distance between steps, while the inter-step interaction energy primarily follows the law as 1/L2 from the well-known Marchenko-Parshin model. In this paper, we give a better understanding of the interaction term of the step stress. The step stress is calculated with respect to the nominal surface stress. Consequently, we calculate the diagonal surface stresses in both the vicinal system (x, y, z) where z is normal to the vicinal and the projected system (x, b, c) where b is normal to the nominal terrace. Moreover, we calculate the surface stresses by using two methods: the first called the 'Zero' method, from the surface pressure forces and the second called the 'One' method, by homogeneously deforming the vicinal in the parallel direction, x or y, and by calculating the surface energy excess proportional to the deformation. By using the 'One' method on the vicinal Cu(0 1 M), we find that the step deformations, due to the applied deformation, vary as 1/L by the same factor for the tensor directions bb and cb, and by twice the same factor for the parallel direction yy. Due to the vanishing of the surface stress normal to the vicinal, the variation of the step stress in the direction yy is better described by using only the step deformation in the same direction. We revisit the Shuttleworth formula, for while the variation of the step stress in the direction xx is the same between the two methods, the variation in the direction yy is higher by 76% for the 'Zero' method with respect to the 'One' method. In addition to the step energy, we confirm that the variation of the step stress must be taken into account for the understanding of the equilibrium of vicinals when they are not deformed.

  13. Cancer incidence in the vicinity of nuclear power plants in Taiwan: a population-based study.

    Science.gov (United States)

    Wang, Shiow-Ing; Yaung, Chih-Liang; Lee, Long-Teng; Chiou, Shang-Jyh

    2016-01-01

    Numerous antinuclear demonstrations reveal that the public is anxious about the potential health effects caused by nuclear power plants. The purpose of this study is to address the question "Is there a higher cancer incidence rate in the vicinity of nuclear power plants in Taiwan?" The Taiwan Cancer Registry database from 1979 to 2003 was used to compare the standardized incidence rate of the top four cancers with strong evidence for radiation risks between the "plant-vicinity" with those "non-plant-vicinity" groups. All cancer sites, five-leading cancers in Taiwan, and gender-specific cancers were also studied. We also adopted different observation time to compare the incidence rate of cancers between two groups to explore the impact of the observation period. The incidences of leukemia, thyroid, lung, and breast cancer were not significantly different between two groups, but cervix uteri cancer showed higher incidence rates in the plant-vicinity group. The incidence of cervical cancer was not consistently associated with the duration of plant operation, according to a multiyear period comparison. Although there was higher incidence in cervix cancer in the plant-vicinity group, our findings did not provide the crucial evidence that nuclear power plants were the causal factor for some cancers with strong evidence for radiation risks.

  14. Preparation of Different Substitued Polypyridine Ligands, Ruthenium(II)-Bridged Complexes and Spectoscopıc Studies.

    Science.gov (United States)

    Obali, Aslihan Yilmaz; Ucan, Halil Ismet

    2016-09-01

    Novel different substitued polypyridine ligands 4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzaldehyde (BA-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzylidene)-pyrene-4-amine (PR-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10] phenanthroline-2-yl)phenoxy)methyl)benzylidene)-1,10-phenanthroline-5amine (FN-PPY), 2-(4-(bromomethyl)phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (BR-PPY), 2-(4-(azidomethyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (N3-PPY) and triazole containing polypyridine ligand 3,4-bis[(4-(metoxy)-1,2,3-triazole)1-methylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)] benzaldehyde (BA-DIPPY) and Ruthenium(II) complexes were synthesized and characterized. Their photopysical properties were investigated. The complexes RuP(PR-PPY), RuB(PR-PPY, RuP(FN-PPY) and RuB(FN-PPY) exhibited a broad absorption bands at 485, 475, 476, and 453 nm, respectively, assignable to the spin-allowed MLCT (dπ-π*) transition. The emission maxima of the pyrene-appended polypyridine ligand PR-PPY was observed at λems = 616 nm and the phenanthroline-appended polypyridine ligand FN-PPY was observed at λems = 668 nm. And the emission maxima of the complexes RuP(PR-PPY), RuB(PR-PPY), RuP(FN-PPY) and RuB(FN-PPY) were observed at λems = 646, 646, 685 and 685 nm, respectively. As seen in fluorescence spectra, the fluorescence intensities of the ligands are higher than their metal complexes. This is because of quenching effect of Ruthenium(II) metal on chromophore groups.

  15. Geologic history of the Slick Rock district and vicinity, San Miguel and Dolores Counties, Colorado

    International Nuclear Information System (INIS)

    Shawe, D.R.

    1976-01-01

    This report is a narrative summary and interpretation, in the form of a geologic history of the Slick Rock district and vicinity, of four previously published chapters in this series dealing with stratigraphy of the Slick Rock district and vicinity, petrography of sedimentary rocks of the district, structure of the district and vicinity, and altered sedimentary rocks of the district, and of other previously published reports on the district. It forms the background, with the earlier reports, for presentation of a final report in the series describing the uranium-vanadium ore deposits. A review of the origin of sedimentary rocks and geologic history of the region indicates that formation of uranium-vanadium deposits was a natural result of the deposition of th rocks, the occurrence of intrastratal waters therein, and the post-depositional movement of the waters resulting from evolution of the sedimentary rock environment. 31 refs

  16. Some radiation measurements in the vicinity of TV and VDU screens

    International Nuclear Information System (INIS)

    Tuyn, J.W.N.; Roger, P.

    1985-01-01

    The dose rate due to X-rays in the vicinity of TV and VDU screens was determined using a xenon-filled proportional counter. The results confirm that the X-ray dose rate around such devices is extremely low. Of greater impact for the exposure of the population was found to be the influence of the electrostatic field in the vicinity of a TV or VDU screen on the local concentration of radon daughters. Such measurements were performed using air sampling at various distances from the screens on a filter-surface barrier detector unit to identify the radon daughters. The radon concentration in the room was simultaneously measured using TLD in a device based on electrostatic precipitation. It is shown that the presence of an electrostatic field during operation of a TV or VDU screen reduces the radon daughter concentration in its vicinity. (orig./HP)

  17. Temperature and pressure variations of d-d luminescence band maxima of bis(pyridylalkenolato)palladium(II) complexes with different ligand substituents: opposite-signed trends.

    Science.gov (United States)

    Poirier, Stéphanie; Czympiel, Lisa; Bélanger-Desmarais, Nicolas; Mathur, Sanjay; Reber, Christian

    2016-04-21

    Luminescence spectra of two d(8)-configured bis(pyridylalkenolato)palladium(ii) complexes, [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], are presented at variable temperature and pressure. Bands are assigned as d-d transitions. The heptafluoropropyl and methyl substituents on the ligands have different steric demands, influencing luminescence spectra. Broad bands with maxima at approximately 12 700 cm(-1) (790 nm) for ligands with heptafluoropropyl substituents and 12,100 cm(-1) (830 nm) for ligands with methyl substituents and widths of approximately 2100 cm(-1) for both complexes are observed at 80 K. Quenching of the luminescence is observed as temperature increases. The maxima of [Pd{PyCHC(C3F7)O}2] show a shift of -0.9 ± 0.1 cm(-1) K(-1) due to broadening of the spectra to lower energy. The luminescence maxima of [Pd{PyCHC(CH3)O}2] shift in the opposite direction by +7.2 ± 0.7 cm(-1) K(-1). Shifts with different signs are also obtained from variable-pressure luminescence spectra, with values of +13 ± 2 cm(-1) kbar(-1) and -15 ± 7 cm(-1) kbar(-1) for [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], respectively. The pressure-induced decrease is unusual and likely caused by intermolecular interactions involving the palladium(ii) center and a vinylic proton of a neighboring complex.

  18. Population distribution, food production and other aspects in the vicinity of the Embalse Nuclear Power Station

    International Nuclear Information System (INIS)

    Cancio, D.; Ciallella, N.R.; Zunino, R.; Perez, T.; Jordan, O.

    1978-01-01

    The paper presents some of the results of the pre-operational studies carried out in the vicinity of the site of the Embalse Nuclear Power Station, which is being built in the Province of Cordoba, Rio Tercero, next to the lake Embalse. The studies cover population distribution, food production, and other local aspects. The low population in the vicinity of the site increases in summer due to tourism. Main use of the land is grazing and cereal production. Milk production is small, but some is produced near the site. Other aspects of the study are presented in other papers of the Seminar. (author)

  19. Surface Science in an MOCVD Environment: Arsenic on Vicinal Ge(100)

    International Nuclear Information System (INIS)

    Olson, J.M.; McMahon, W.E.

    1998-01-01

    Scanning tunneling microscope (STM) images of arsine-exposed vicinal Ge(100) surfaces show that most As/Ge steps are reconstructed, and that a variety of different step structures exist. The entire family of reconstructed As/Ge steps can be divided into two types, which we have chosen to call ''single-row'' steps and ''double-row'' steps. In this paper we propose a model for a double-row step created by annealing a vicinal Ge(100) substrate under an arsine flux in a metal-organic chemical vapor deposition (MOCVD) chamber

  20. NORM in the vicinity of the thermal power plant 'Nikola Tesla' B - experimental results

    International Nuclear Information System (INIS)

    Kisic, D.; Veselinovic, N.; Tokonami, S.; Celikovic, I.; Stojanovic, Z.; Cuknic, O.; Nemcevic, M.; Simovic, R.; Zunic, Z. S.

    2009-01-01

    The paper deals with the results related to identification of ionizing radiation from natural sources (NORM - Naturally Occurring Radioactive Materials) in the vicinity of the fly ash deposit of Thermal Power Plant 'Nikola Tesla B' (TENT B). The survey included such as follows: determination of distribution of naturally soil occurring gases radon ( 222 Rn) and thoron ( 220 Tn) in the vicinity of TENT B by means of passive discriminative solid state nuclear track detectors (CR 39) at the depth of 80 cm with defining its appropriate GPS coordinates. (author) [sr

  1. Synthesis and Evaluation of Changes Induced by Solvent and Substituent in Electronic Absorption Spectra of New Azo Disperse Dyes Containig Barbiturate Ring

    Directory of Open Access Journals (Sweden)

    Hooshang Hamidian

    2013-01-01

    Full Text Available Six azo disperse dyes were prepared by diazotizing 4-amino hippuric acid and coupled with barbituric acid and 2-thiobarbituric acid. Then, the products were reacted with aromatic aldehyde, sodium acetate, and acetic anhydride, and oxazolone derivatives were formed. Characterization of the dyes was carried out by using UV-Vis, FT-IR, 1H NMR and 13C NMR, and mass spectroscopic techniques. The solvatochromic behavior of azo disperse dyes was evaluated in various solvents. The effects of substituents of aromatic aldehyde, barbiturate, and thiobarbiturate ring on the color of dyes were investigated.

  2. DFT studies for the substituent effect on the diels-alder reaction of 1,4-diaza-1,3-butadienes

    International Nuclear Information System (INIS)

    Lee, Gab Yong

    2001-01-01

    DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular orbital) energies for the optimized 1,4-disubstituted-1,4DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively

  3. Adducts of pyridine with 7,8-dicarbo-nido-undecahydrononaborane and its iodo and bromo substituents: a comparative study of their physicochemical properties

    International Nuclear Information System (INIS)

    Volkov, O.V.; Il'inchik, E.A.; Volkov, V.V.; Voronina, G.S.; Yur'eva, O.P.

    1997-01-01

    The synthesis of bromo- and iodo substituents 7,8-C 2 B 9 H 11 xRu is accomplished and their comparative study is carried out through the methods of NMR 11 B-, PMR-, IR- and UV-spectroscopy. It is established that by introduction of halogen into carborane polyhedron there takes place increase in the acceptor capability of the latter and in the result the adduct stabilization. At the same time the introduction of halogen atom leads to sharp decrease in the intensity of the adduct fluorescence in the crystal state

  4. Conformational equilibrium and effects of some 2-mono substituted cyclohexanone substituents; Equilibrio conformacional e efeitos dos substituintes de algumas cicloexanonas 2-monossubstituidas

    Energy Technology Data Exchange (ETDEWEB)

    Basso, Ernani A [Universidade Estadual de Maringa, PR (Brazil); Trevisan, Paulo S [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica; Lambert, Joseph B [Northwestern Univ. (United States)

    1992-12-31

    This work re-evaluates, using a high-field device (400 MHz) and the Eliel method, the 2-halo substituted cyclohexanone conformational equilibrium, which applies the chemical shift values ({delta}) and the {alpha} proton coupling constants (J). {sup 13} C NMR spectra were also obtained for investigation of the substituent effects on the cyclohexanone ring carbons chemical shift, since the few works treating the subject are at most incomplete. The results are compared with those obtained for the 2-methoxy cyclohexanone previously described, and reproduced in this work 12 refs., 4 figs., 3 tabs.

  5. Model Studies of the Histidine-Tyrosine Cross-Link in Cytochrome c Oxidase Reveal the Flexible Substituent Effect of the Imidazole Moiety

    Science.gov (United States)

    Pratt, Derek A.; Pesavento, Russell P.; van der Donk, Wilfred A.

    2010-01-01

    Experimental and theoretical studies were carried out to interrogate the effect of an imidazole substituent in each of the ortho, meta, and para positions on the pKa, E°, and O–H BDE of phenol. The results reveal that imidazole substitution lowers the pKa of phenol and increases the E° of phenoxide due to its σ-electron withdrawing ability (σp− = +0.21, σm− = +0.45) but decreases the O–H BDE and E° of phenol due to its σ-electron-donating ability (σp+ = −0.45). PMID:15957934

  6. Asthma in the vicinity of power stations: II - outdoor air quality and symptoms

    International Nuclear Information System (INIS)

    Henry, R.L.; Bridgman, H.A.; Wlodarczyk, J.; Abramson, R.; Adler, J.A.; Hensley, M.J.

    1995-01-01

    After a study suggesting that children who live in the vicinity of a coal thermal power plant present a bronchial tubes hyper reactivity, more often than children of an other city far from this power plant, an other study was realized; it is presented here but the way of doing is controversial. (N.C.)

  7. Measuring dose from radiotherapy treatments in the vicinity of a cardiac pacemaker.

    Science.gov (United States)

    Peet, Samuel C; Wilks, Rachael; Kairn, Tanya; Crowe, Scott B

    2016-12-01

    This study investigated the dose absorbed by tissues surrounding artificial cardiac pacemakers during external beam radiotherapy procedures. The usefulness of out-of-field reference data, treatment planning systems, and skin dose measurements to estimate the dose in the vicinity of a pacemaker was also examined. Measurements were performed by installing a pacemaker onto an anthropomorphic phantom, and using radiochromic film and optically stimulated luminescence dosimeters to measure the dose in the vicinity of the device during the delivery of square fields and clinical treatment plans. It was found that the dose delivered in the vicinity of the cardiac device was unevenly distributed both laterally and anteroposteriorly. As the device was moved distally from the square field, the dose dropped exponentially, in line with out-of-field reference data in the literature. Treatment planning systems were found to substantially underestimate the dose for volumetric modulated arc therapy, helical tomotherapy, and 3D conformal treatments. The skin dose was observed to be either greater or lesser than the dose received at the depth of the device, depending on the treatment site, and so care should be if skin dose measurements are to be used to estimate the dose to a pacemaker. Square field reference data may be used as an upper estimate of absorbed dose per monitor unit in the vicinity of a cardiac device for complex treatments involving multiple gantry angles. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  8. In-beam γ-ray spectroscopy in the vicinity of 100Sn

    International Nuclear Information System (INIS)

    Seweryniak, D.

    1998-01-01

    In recent years, in-beam x-ray experiments supplied a vast amount of data on high-spin states in nuclei in the vicinity of 100 Sn. The present contribution reviews spectroscopic information obtained recently for N ≥ 50 nuclei around 100 Sn, with emphasis on isomer studies, and discusses selected results in the frame of the shell model

  9. 33 CFR 110.190 - Tortugas Harbor, in vicinity of Garden Key, Dry Tortugas, Fla.

    Science.gov (United States)

    2010-07-01

    ... Garden Key, Dry Tortugas, Fla. 110.190 Section 110.190 Navigation and Navigable Waters COAST GUARD..., in vicinity of Garden Key, Dry Tortugas, Fla. (a) The anchorage grounds. All of Bird Key Harbor, southwest of Garden Key, bounded by the surrounding reefs and shoals and, on the northeast, by a line...

  10. Assessment of Indoor Radon (222Rn) Concentrations in the Vicinity of

    African Journals Online (AJOL)

    MLAY

    ABSTRACT. This study aimed to assess indoor radon concentrations in the vicinity of the Manyoni Uranium ... risk of lung cancer proportionally to the ... deposit, power plant, industrial radiation, etc. ... in foundations, walls, hollow concrete .... (AlphaGUARD User Manual 2007). ... used as control are presented in Table 4. The.

  11. Properties of Soils and Plants Uptake within the Vicinity of Selected ...

    African Journals Online (AJOL)

    Backyard farming is becoming popular among the auto mechanics near their workshops where spent engine oil and carcass of vehicles are continuously dumped in Nigeria. The properties of soil and maize plants sampled from the vicinity of selected auto mechanic workshops in Ile-Ife, Nigeria were investigated. The results ...

  12. Surface-water quality, Oneida Reservation and vicinity, Wisconsin, 1997-98

    Science.gov (United States)

    Schmidt, Morgan A.; Scudder, Barbara C.; Richards, Kevin D.

    2000-01-01

    Streamwater samples were collected at 19 sites in the vicinity of the Oneida Tribe of Indians of Wisconsin Reservation. Samples were collected during 5 sampling periods in 1997-98. Field measurements were made and samples were analyzed for nutrients, suspended sediment, major ions, and pesticides.

  13. Preliminary assessment of the electromagnetic environment in the immediate vicinity of the ETA accelerator

    International Nuclear Information System (INIS)

    Cabayan, H.S.; Bogdan, E.; Zicker, J.; Wythe, D.; Burke, G.J.

    1980-04-01

    The electromagnetic fields in the immediate vicinity of the Experimental Test Accelerator (ETA) at the Lawrence Livermore Laboratory have been characterized. Various EM sensors that cover the frequency band from the very low frequencies up into the GHz region have been used. The report describes in detail the probes, the test set-up and the data processing techniques

  14. Application of a LEED apparatus provided with a lens to the study of vicinal surfaces

    International Nuclear Information System (INIS)

    Laydevant, Louis; Dupuy, J.C.

    1979-01-01

    Steps presence on vicinal surfaces changes the low energy electron difraction (LEED) pattern: a system of regulary spaced steps is causing some spots to be splitted. Using a high voltage LEED apparatus allows an easy explanation of the patterns: the spot position does not depend about energy and so some cristallographic parameters can be easily measured [fr

  15. High-frequency pressure variations in the vicinity of a surface CO2 flux chamber

    Science.gov (United States)

    Eugene S. Takle; James R. Brandle; R. A. Schmidt; Rick Garcia; Irina V. Litvina; William J. Massman; Xinhua Zhou; Geoffrey Doyle; Charles W. Rice

    2003-01-01

    We report measurements of 2Hz pressure fluctuations at and below the soil surface in the vicinity of a surface-based CO2 flux chamber. These measurements were part of a field experiment to examine the possible role of pressure pumping due to atmospheric pressure fluctuations on measurements of surface fluxes of CO2. Under the moderate wind speeds, warm temperatures,...

  16. Nonradical Zinc-Barbier Reaction for Diastereoselective Synthesis of Vicinal Amino Alcohols

    DEFF Research Database (Denmark)

    Keinicke, Lise Edelmann; Fristrup, Peter; Norrby, Per-Ola

    2005-01-01

    A new protocol for the synthesis of vicinal amino alcohols is described. The method employs a Barbier-type reaction between an imine and 3-benzoyloxyallyl bromide in the presence of zinc metal. The addition products are debenzoylated to afford amino alcohols in good yields and with diastereomeric...

  17. Programmatic Environmental Report for remedial actions at UMTRA [Uranium Mill Tailings Remedial Action] Project vicinity properties

    International Nuclear Information System (INIS)

    1985-03-01

    This Environmental Report (ER) examines the environmental consequences of implementing a remedial action that would remove radioactive uranium mill tailings and associated contaminated materials from 394 vicinity properties near 14 inactive uranium processing sites included in the Uranium Mill Tailings Remedial Action (UMTRA) Project pursuant to Public Law 95--604, the Uranium Mill Tailings Radiation Control Act (UMTRCA) of 1978. Vicinity properties are those properties in the vicinity of the UMTRA Project inactive mill sites, either public or private, that are believed to be contaminated by residual radioactive material originating from one of the 14 inactive uranium processing sites, and which have been designated under Section 102(a)(1) of UMTRCA. The principal hazard associated with the contaminated properties results from the production of radon, a radioactive decay product of the radium contained in the tailings. Radon, a radioactive gas, can diffuse through the contaminated material and be released into the atmosphere where it and its radioactive decay products may be inhaled by humans. A second radiation exposure pathway results from the emission of gamma radiation from uranium decay products contained in the tailings. Gamma radiation emitted from contaminated material delivers an external exposure to the whole body. If the concentration of radon and its decay products is high enough and the exposure time long enough, or if the exposure to direct gamma radiation is long enough, cancers (i.e., excess health effects) may develop in persons living and working at the vicinity properties. 3 refs., 7 tabs

  18. Steric congestion at, and proximity to, a ferrous center leads to hydration of α-nitrile substituents forming coordinated carboxamides.

    Science.gov (United States)

    Thallaj, Nasser K; Orain, Pierre-Yves; Thibon, Aurore; Sandroni, Martina; Welter, Richard; Mandon, Dominique

    2014-08-04

    The question of the conversion of nitrile groups into amides (nitrile hydration) by action of water in mild and eco-compatible conditions and in the presence of iron is addressed in this article. We come back to the only known example of hydration of a nitrile function into carboxamide by a ferrous [Fe(II)] center in particularly mild conditions and very efficiently and demonstrate that these unusual conditions result from the occurrence of steric stress at the reaction site and formation of a more stable end product. Two bis(cyano-substituted) (tris 2-pyridyl methyl amine) ligands have been prepared, and the structures of the corresponding FeCl2 complexes are reported, both in the solid state and in solution. These two ligands only differ by the position of the nitrile group on the tripod in the α and β position, respectively, with respect to the pyridine nitrogen. In any case, intramolecular coordination is impossible. Upon action of water, the nitrile groups are hydrated however only if they are located in the α position. The fact that the β-substituted β-(NC)2TPAFeCl2 complex is not water sensitive suggests that the reaction proceeds in an intramolecular way at the vicinity of the metal center. In the bis α-substituted α-(NC)2TPAFeCl2 complex, both functions are converted in a very clean fashion, pointing out that this complex exhibits ligand flexibility and is not deactivated after the first hydration. At a preparative scale, this reaction allows the one-pot conversion of the bis(cyano-substituted) tripod into a bis(amido-substituted) one in particularly mild conditions with a very good yield. Additionally, the XRD structure of a ferric compound in which the two carboxamido ligands are bound to the metal in a seven-coordinate environment is reported.

  19. Electronic optimization of heteroleptic Ru(II) bipyridine complexes by remote substituents: synthesis, characterization, and application to dye-sensitized solar cells.

    Science.gov (United States)

    Han, Won-Sik; Han, Jung-Kyu; Kim, Hyun-Young; Choi, Mi Jin; Kang, Yong-Soo; Pac, Chyongjin; Kang, Sang Ook

    2011-04-18

    We prepared a series of new heteroleptic ruthenium(II) complexes, Ru(NCS)(2)LL' (3a-3e), where L is 4,4'-di(hydroxycarbonyl)-2,2'-bipyridine and L' is 4,4'-di(p-X-phenyl)-2,2'-pyridine (X = CN (a), F (b), H (c), OMe (d), and NMe(2) (e)), in an attempt to explore the structure-activity relationships in their photophysical and electrochemical behavior and in their performance in dye-sensitized solar cells (DSSCs). When substituent X is changed from electron-donating NMe(2) to electron-withdrawing CN, the absorption and emission maxima reveal systematic bathochromic shifts. The redox potentials of these dyes are also significantly influenced by X. The electronic properties of the dyes were theoretically analyzed using density functional theory calculations; the results show good correlations with the experimental results. The solar-cell performance of DSSCs based on dye-grafted nanocrystalline TiO(2) using 3a-3e and standard N3 (bis[(4,4'-carboxy-2,2'-bipyridine)(thiocyanato)]ruthenium(II)) were compared, revealing substantial dependences on the dye structures, particularly on the remote substituent X. The 3d-based device showed the best performance: η = 8.30%, J(SC) = 16.0 mA·cm(-2), V(OC) = 717 mV, and ff = 0.72. These values are better than N3-based device.

  20. Chameleonic reactivity of vicinal diazonium salt of acetylenyl-9,10-anthraquinones: synthetic application toward two heterocyclic targets.

    Science.gov (United States)

    Stepanov, A A; Gornostaev, L M; Vasilevsky, S F; Arnold, E V; Mamatyuk, V I; Fadeev, D S; Gold, B; Alabugin, I V

    2011-11-04

    The nature of products in the diazotization of 1-amino-2-acetylenyl-9,10-anthraquinones strongly depends on the nature of substituents at both the alkyne and at the anthraquinone core. Donor substitution (NHAr, OH) at the fourth position stabilizes the diazonium salt at C1, decelerating electrophilic cyclization at the arylethynyl substituent at C2. This effect allows the replacement of the diazonium with azide group and subsequent closure into isoxazole ring with preservation of the alkyne. In contrast, electrophilic 5-exo-dig cyclizations to condensed pyrazoles is observed for the combination of donor substituents at the aryl alkyne moiety and an OAc substituent at C4. The latter process provides a new synthetic route to 3-ethynyl-[1,9-cd]isoxazol-6-ones that are difficult to access otherwise. DFT calculations suggest that donor substituents have only a minor effect on alkyne and diazonium polarization in the reactant but provide specific transition state stabilization by stabilizing the incipient vinyl cation. This analysis provides the first computational data on electrophilic 5-exo-dig cyclization in its parent form and the nucleophile-promoted version. This cyclization is a relatively fast but endothermic process that is rendered thermodynamically feasible by the enol-keto tautomerization with concomitant aromatization in the five-membered heteroaromatic ring. Computations suggest that the importance of nucleophilic assistance in the transition state for a relatively weak nucleophile such as water is minor because the energy gain due to the Lewis base coordination to the carbocationic center is more than compensated for by the unfavorable entropic term for the bimolecular proces.