Reinforced poly(propylene oxide): a very soft and extensible dielectric electroactive polymer

International Nuclear Information System (INIS)

Goswami, K; Mazurek, P; Daugaard, A E; Skov, A L; Galantini, F; Gallone, G

2013-01-01

Poly(propylene oxide) (PPO), a novel soft elastomeric material, and its composites were investigated as a new dielectric electroactive polymer (EAP). The PPO networks were obtained from thiol-ene chemistry by photochemical crosslinking of α,ω-diallyl PPO with a tetra-functional thiol. The elastomer was reinforced with hexamethylenedisilazane treated fumed silica to improve the mechanical properties of PPO. The mechanical properties of PPO and composites thereof were investigated by shear rheology and stress–strain measurements. It was found that incorporation of silica particles improved the stability of the otherwise mechanically weak pure PPO network. Dielectric spectroscopy revealed high relative dielectric permittivity of PPO at 10 3 Hz of 5.6. The relative permittivity was decreased slightly upon addition of fillers, but remained higher than the commonly used acrylic EAP material VHB4910. The electromechanical actuation performance of both PPO and its composites showed properties as good as VHB4910 and a lower viscous loss. (paper)

Understanding the effect of postsynthesis ammonium treatment on the catalytic activity of Au/TI-SBA-15 catalysts for the oxidation of propene

NARCIS (Netherlands)

Sacaliuc, E.; Friedrich, H.; Palkovits, R.; Weckhuysen, B.M.; Nijhuis, T.A.

2008-01-01

Postsynthesis ammonium treatment induces a substantial increase in the catalytic activity of Au/Ti-SBA-15 catalysts for the direct vapor-phase epoxidation of propylene using hydrogen and oxygen. The PO formation rate of a calcined Au/Ti-SBA-15 catalyst prepared by this method increased from 4.3 mgPO

Effects of hydrogen and propylene presence on decomposition of hydrogen peroxide over palladium catalysts

NARCIS (Netherlands)

Chen, T.; Kertalli, E.; Nijhuis, T.A.; Podkolzin, S.

2016-01-01

Reaction rates for H2O2 decomposition in a methanol solution were measured over Pd/SiO2 catalysts in the presence of gas-phase N2, H2 and propylene. The H2O2 decomposition rates were higher in the presence of H2 and lower in the presence of propylene compared to those under N2, which acted as an

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

KAUST Repository

Anderson, Carly E.; Vagin, Sergei I.; Hammann, Markus; Zimmermann, Leander; Rieger, Bernhard

2013-01-01

Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

KAUST Repository

Anderson, Carly E.

2013-09-18

Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

MWCNTs-Reinforced Epoxidized Linseed Oil Plasticized Polylactic Acid Nanocomposite and Its Electroactive Shape Memory Behaviour

OpenAIRE

Alam, Javed; Alam, Manawwer; Raja, Mohan; Abduljaleel, Zainularifeen; Dass, Lawrence

2014-01-01

A novel electroactive shape memory polymer nanocomposite of epoxidized linseed oil plasticized polylactic acid and multi-walled carbon nanotubes (MWCNTs) was prepared by a combination of solution blending, solvent cast technique, and hydraulic hot press moulding. In this study, polylactic acid (PLA) was first plasticized by epoxidized linseed oil (ELO) in order to overcome the major limitations of PLA, such as high brittleness, low toughness, and low tensile elongation. Then, MWCNTs were inc...

Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

Science.gov (United States)

Xu, Tiwen; Jia, Zhixin; Luo, Yuanfang; Jia, Demin; Peng, Zheng

2015-02-01

The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress-strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

Science.gov (United States)

Hudson, R. L.; Loeffler, M. J.; Yocum, K. M.

2017-01-01

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

Energy Technology Data Exchange (ETDEWEB)

Hudson, R. L.; Loeffler, M. J. [Astrochemistry Laboratory (Code 691), NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Yocum, K. M., E-mail: Reggie.Hudson@nasa.gov [Department of Chemistry, Kutztown University, Kutztown, PA 19530 (United States)

2017-02-01

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

Microdroplets Accelerate Ring Opening of Epoxides

Science.gov (United States)

Lai, Yin-Hung; Sathyamoorthi, Shyam; Bain, Ryan M.; Zare, Richard N.

2018-05-01

The nucleophilic opening of an epoxide is a classic organic reaction that has widespread utility in both academic and industrial applications. We have studied the reaction of limonene oxide with morpholine to form 1-methyl-2-morpholino-4-(prop-1-en-2-yl) cyclohexan-1-ol in bulk solution and in electrosprayed microdroplets with a 1:1 v/ v water/methanol solvent system. We find that even after 90 min at room temperature, there is no product detected by nuclear magnetic resonance spectroscopy in bulk solution whereas in room-temperature microdroplets (2-3 μm in diameter), the yield is already 0.5% in a flight time of 1 ms as observed by mass spectrometry. This constitutes a rate acceleration of 105 in the microdroplet environment, if we assume that as much as 5% of product is formed in bulk after 90 min of reaction time. We examine how the reaction rate depends on droplet size, solvent composition, sheath gas pressure, and applied voltage. These factors profoundly influence the extent of reaction. This dramatic acceleration is not limited to just one system. We have also found that the nucleophilic opening of cis-stilbene oxide by morpholine is similarly accelerated. Such large acceleration factors in reaction rates suggest the use of microdroplets for ring opening of epoxides in other systems, which may have practical significance if such a procedure could be scaled. [Figure not available: see fulltext.

Microdroplets Accelerate Ring Opening of Epoxides

Science.gov (United States)

Lai, Yin-Hung; Sathyamoorthi, Shyam; Bain, Ryan M.; Zare, Richard N.

2018-03-01

The nucleophilic opening of an epoxide is a classic organic reaction that has widespread utility in both academic and industrial applications. We have studied the reaction of limonene oxide with morpholine to form 1-methyl-2-morpholino-4-(prop-1-en-2-yl) cyclohexan-1-ol in bulk solution and in electrosprayed microdroplets with a 1:1 v/v water/methanol solvent system. We find that even after 90 min at room temperature, there is no product detected by nuclear magnetic resonance spectroscopy in bulk solution whereas in room-temperature microdroplets (2-3 μm in diameter), the yield is already 0.5% in a flight time of 1 ms as observed by mass spectrometry. This constitutes a rate acceleration of 105 in the microdroplet environment, if we assume that as much as 5% of product is formed in bulk after 90 min of reaction time. We examine how the reaction rate depends on droplet size, solvent composition, sheath gas pressure, and applied voltage. These factors profoundly influence the extent of reaction. This dramatic acceleration is not limited to just one system. We have also found that the nucleophilic opening of cis-stilbene oxide by morpholine is similarly accelerated. Such large acceleration factors in reaction rates suggest the use of microdroplets for ring opening of epoxides in other systems, which may have practical significance if such a procedure could be scaled. [Figure not available: see fulltext.

An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15.

Science.gov (United States)

Zhang, Lei; Abbenhuis, Hendrikus C L; Gerritsen, Gijsbert; Bhriain, Nollaig Ní; Magusin, Pieter C M M; Mezari, Brahim; Han, Wei; van Santen, Rutger A; Yang, Qihua; Li, Can

2007-01-01

A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copolymerization on a mesoporous SBA-15-supported polystyrene polymer. The resulting hybrid materials exhibit attractive textural properties (highly ordered mesostructure, large specific surface area (>380 m2 g-1) and pore volume (>or==0.46 cm3 g-1)), and high activity in the epoxidation of alkenes. In the epoxidation of cyclooctene with tert-butyl hydrogen peroxide (TBHP), the hybrid catalysts have rate constants comparable with that of their homogeneous counterpart, and can be recycled at least seven times. They can also catalyze the epoxidation of cyclooctene with aqueous H2O2 as the oxidant. In two-phase reaction media, the catalysts show much higher activity than their homogeneous counterpart due to the hydrophobic environment around the active centers. They behave as interfacial catalysts due to their multifunctionality, that is, the hydrophobicity of polystyrene and the polyhedral oligomeric silsesquioxanes (POSS), and the hydrophilicity of the silica and the mesoporous structure. Combination of the immobilization of homogeneous catalysts on two conventional supports, inorganic solid and organic polymer, is demonstrated to achieve novel heterogeneous catalytic ensembles with the merits of attractive textural properties, tunable surface properties, and optimized environments around the active sites.

Highly efficient epoxidation of alkenes with m-chloroperbenzoic acid ...

Indian Academy of Sciences (India)

on a solid support such as polymer, zeolite and silica have recently been reported as innovation in the cat- alytic properties of such compounds.19 23 ..... the homogeneous phases, the Co(III) complex was used ..... solvent-extraction and catalase-like activity studies J. ... 15 as highly active catalysts for epoxidation of styrene.

Polymeric membranes containing silver salts for propylene/propane separation

Directory of Open Access Journals (Sweden)

L. D. Pollo

2012-06-01

Full Text Available The separation of olefin/paraffin mixtures is one of the most important processes of the chemical industry. This separation is typically carried out by distillation, which is an energy and capital intensive process. One promising alternative is the use of facilitated transport membranes, which contain specific carrier agents in the polymer matrix that interact reversibly with the double bond in the olefin molecule, promoting the simultaneous increase of its permeability and selectivity. In this study, polyurethane (PU membranes were prepared using two different silver salts (triflate and hexafluorantimonate. The membranes were structurally characterized and their performance for the separation of propylene/propane mixtures was evaluated. The results of the characterization analyses indicated that the triflate salt was the most efficient carrier agent. The membranes containing this salt showed the best performance, reaching an ideal selectivity of 10 and propylene permeability of 188 Barrer.

Suppressing propylene carbonate decomposition by coating graphite electrode foil with silver

International Nuclear Information System (INIS)

Gao, J.; Zhang, H.P.; Fu, L.J.; Zhang, T.; Wu, Y.P.; Takamura, T.; Wu, H.Q.; Holze, R.

2007-01-01

A method has been developed to suppress the decomposition of propylene carbonate (PC) by coating graphite electrode foil with a layer of silver. Results from electrochemical impedance measurements show that the Ag-coated graphite electrode presents lower charge transfer resistance and faster diffusion of lithium ions in comparison with the virginal one. Cyclic voltammograms and discharge-charge measurements suggest that the decomposition of propylene carbonate and co-intercalation of solvated lithium ions are prevented, and lithium ions can reversibly intercalate into and deintercalate from the Ag-coated graphite electrode. These results indicate that Ag-coating is a good way to improve the electrochemical performance of graphitic carbon in PC-based electrolyte solutions

Lysophosphatidic acids are new substrates for the phosphatase domain of soluble epoxide hydrolase.

Science.gov (United States)

Oguro, Ami; Imaoka, Susumu

2012-03-01

Soluble epoxide hydrolase (sEH) is a bifunctional enzyme that has a C-terminus epoxide hydrolase domain and an N-terminus phosphatase domain. The endogenous substrates of epoxide hydrolase are known to be epoxyeicosatrienoic acids, but the endogenous substrates of the phosphatase activity are not well understood. In this study, to explore the substrates of sEH, we investigated the inhibition of the phosphatase activity of sEH toward 4-methylumbelliferyl phosphate by using lecithin and its hydrolyzed products. Although lecithin itself did not inhibit the phosphatase activity, the hydrolyzed lecithin significantly inhibited it, suggesting that lysophospholipid or fatty acid can inhibit it. Next, we investigated the inhibition of phosphatase activity by lysophosphatidyl choline, palmitoyl lysophosphatidic acid, monopalmitoyl glycerol, and palmitic acid. Palmitoyl lysophosphatidic acid and fatty acid efficiently inhibited phosphatase activity, suggesting that lysophosphatidic acids (LPAs) are substrates for the phosphatase activity of sEH. As expected, palmitoyl, stearoyl, oleoyl, and arachidonoyl LPAs were efficiently dephosphorylated by sEH (Km, 3-7 μM; Vmax, 150-193 nmol/min/mg). These results suggest that LPAs are substrates of sEH, which may regulate physiological functions of cells via their metabolism.

Cooperative properties of single phases of complex oxide catalyst for oxidation of propylene to acrolein

International Nuclear Information System (INIS)

Orel, L.I.; Udalova, O.V.; Korchak, V.N.; Isaev, O.V.; Krylov, O.V.; Gershenzon, Yu.M.; Aptekar', E.L.

1992-01-01

Synergetic effect of increase of acrolein yield during propylene oxidation on mechanical mixture of (α + β)CoMoO 4 and MoO 3 , as well as CO and CO 2 yield on mixture of CoMoO 4 and Bi 2 O 3 ·2MoO 3 was revealed. It is shown that CoMoO 4 generates allyl radicals, desorption of these radicals to gaseous phase is not practically observed with MoO 3 , bismuth molybdates and Fe 2 O 3 · Fe 2 O 3 ·3MoO 3

Evaluation of some antioxidants in radiation vulcanized ethylene-propylene diene (EPDM) rubber

Energy Technology Data Exchange (ETDEWEB)

Abdel-Aziz, M.M.; Basfar, A.A. E-mail: abasfar@kacst.edu.sa

2001-12-01

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been used to study the oxidation of {gamma}-ray vulcanized ethylene-propylene diene rubber (EPDM) stabilized with various types of antioxidants. The antioxidants used were pentaerythrityl tetrakis(3,5-di-tert-butyl(-4-hydroxyphenyl))propionate (Irganox 1010), Irganox 1035, Irganox 1520D, as primary antioxidants; Irganox B561 and Irganox B900, as synergistic blends; hindered amine light stabilizer (HALS), i.e. Tinuvin 622 LD; N-isopropyl-N-phenyl-p-phenylene diamine (IPPD) and trimethyl quinoline (TMQ) and their mixtures. The measurements were carried out under atmospheric conditions. The effects of antioxidant type and its selected concentration were determined and mechanism of reaction proposed.

Studying the iodine leaching from the compositions based on epoxide resin and lead iodide

International Nuclear Information System (INIS)

Kalinin, N.N.; Elizarova, A.N.

1988-01-01

When studying iodine leaching, the possibility to use solid compositions, produced by incorporation of dry powdered lead iodide and its aqueous suspension into epoxide resin for long-term immobilization of iodine-129 under conditions of monitored storage, is evaluated. Analysis of the results obtained has shown that leaching rate in the first 4 days has the maximum value and constitutes (4.2 - 2700.0) x 10 -6 cm/day. Then the process of leaching is determined by diffusion mechanism. For samples, prepared by wet lead iodide incorporation the rate of leaching is higher than that of the corresponding samples prepared by dry compound incorporation

76 FR 79146 - Propylene Oxide; Proposed Tolerance Actions

Science.gov (United States)

2011-12-21

...: EPA is proposing to establish the tree nut crop group tolerance and separate tolerances on pistachio... (pistachios, pine nuts) in 40 CFR 180.491(a)(1) for residues of propylene oxide in or on pistachio at 300 ppm... pistachio at 10.0 ppm and nut, pine at 10.0 ppm. Establishment of tolerances for pistachios, pine nuts, and...

Salphen-Co(III) complexes catalyzed copolymerization of epoxides with CO2

Czech Academy of Sciences Publication Activity Database

Hošťálek, Z.; Mundil, R.; Císařová, I.; Trhlíková, Olga; Grau, E.; Peruch, F.; Cramail, H.; Merna, J.

2015-01-01

Roč. 63, 20 April (2015), s. 52-61 ISSN 0032-3861 Institutional support: RVO:61389013 Keywords : cobalt salphen catalyst * CO2 epoxide copolymerization * MALDI-TOF Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.586, year: 2015

Kinetic study of the hydration of propylene oxide in the presence of heterogeneous catalyst

Directory of Open Access Journals (Sweden)

Akyalcin Sema

2017-01-01

Full Text Available The kinetics of the hydration of propylene oxide was studied using a pressurized batch reactor for both uncatalyzed and heterogeneously catalyzed reactions. Lewatit MonoPlus M500/HCO3 - was used as heterogeneous catalyst, which showed better performance than Dowex Marathon A/HCO3 -. The effects of the parameters, namely internal and external diffusion resistances, temperature, catalyst loading and mole ratios of reactants, on the reaction rate were studied. The uncatalyzed and heterogeneously catalyzed reactions were proven to follow a series-parallel irreversible homogeneous mechanism. The temperature dependencies of the rate constants appearing in the rate expressions were determined.

Synthesis of a highly dispersed CuO catalyst on CoAl-HT for the epoxidation of styrene.

Science.gov (United States)

Hu, Rui; Yang, Pengfei; Pan, Yongning; Li, Yunpeng; He, Yufei; Feng, Junting; Li, Dianqing

2017-10-10

A highly dispersed CuO catalyst was prepared by the deposition-precipitation method and evaluated for the catalytic epoxidation of styrene with tert-butyl hydroperoxide (TBHP) as the oxidant under solvent acetonitrile conditions. Compared with MgAl hydrotalcite (MgAl-HT)-, MgO-, TiO 2 -, C-, and MCM-22-supported catalysts, CuO/CoAl-HT exhibited preferable activity and selectivity towards styrene oxide (72% selectivity at 99.5% styrene conversion) due to its high dispersion of CuO and surface area of Cu. The improved dispersion of CuO/CoAl-HT could be ascribed to the nature of HT support, especially the synergistic effect of acidic and basic sites on the surface, which facilitated the formation of highly dispersed CuO species. A structure-performance relationship study indicated that copper(ii) in CuO was the active site for the epoxidation and oxidation of styrene, and that Cu II of rich electronic density favored the improvement of selectivity of styrene oxide. Based on these results, a reaction mechanism was proposed. Moreover, the preferred catalytic performance of CuO/CoAl-HT could be maintained in five reused cycles.

Photochemical epoxidation of olefins by visible light in a redox system involving Sb(V) tetraphenylporphyrin and water

Energy Technology Data Exchange (ETDEWEB)

Inoue, Haruo; Hida, Mitsuhiko (Tokyo Metropolitan Univ. (Japan))

1989-03-25

The authors explore electron donors from the viewpoint of solar energy storage. Much attention has been focused on how a water molecule can be incorporated into electron donor system. In this paper, the authors describe a photochemical epoxidation of alkene sensitized by Sb(V)-, P(V)-, Sn(IV)-, Ge(IV)- tetraphenylporphyrin (TPP) with higher oxidation potential than 1.0 Volts vs. NHE in redox systems with a water molecule as an electron donor. The water molecule acts as an electron donor, and alkene acts as an oxygen atom acceptor in this photoredox system. Epoxidation of alkenes usually requires strong oxidizing agents either by the thermal or photochemical method. This is the first example of the photochemical epoxide formation from alkene and water without any strong oxidizing agent. 1 fig.

Effects of organoclay to miscibility, mechanical and thermal properties of poly(lactic acid) and propylene-ethylene copolymer blends

Science.gov (United States)

Wacharawichanant, S.; Ounyai, C.; Rassamee, P.

2017-07-01

The effects of propylene-ethylene copolymer (PEC or PEC3300) and clay surface modified with 25-30 wt% of trimethylstearyl ammonium (Clay-TSA) on morphology, thermal and mechanical properties of poly(lactic acid) (PLA) were investigated. The morphology analysis showed PLA/PEC3300 blends clearly demonstrated a two-phase separation of dispersed phase and the matrix phase and the addition of Clay-TSA could improve the miscibility of PLA and PEC3300 blends due to the decreased of the domain sizes of dispersed PEC3300 phase in the polymer matrix. From X-ray diffraction analysis showed the intercalation of PLA chains inside the Clay-TSA and this result implied that Clay-TSA platelets acted as an effective compatibilizer. The tensile properties showed the strain at break of PLA was improved after adding PEC3300 while Young’s modulus, tensile strength and storage modulus decreased. The addition of Clay-TSA could improve Young’s modulus of PLA/PEC3300 blends. The addition of Clay-TSA 7 phr showed the maximum of Young’s modulus of PLA/PEC3300/Clay-TSA composites. The thermal properties found that the addition of PEC3300 and Clay-TSA did not change significantly on the glass transition temperature and melting point temperature of PLA. The percent of crystallinity of PLA decreased with increasing PEC content. The thermal stability of PLA improved after adding PEC3300.

Rotational dynamics of propylene inside Na-Y zeolite cages

Indian Academy of Sciences (India)

We report here the quasielastic neutron scattering (QENS) studies on the dynamics of propylene inside Na-Y zeolite using triple axis spectrometer (TAS) at Dhruva reactor, Trombay. Molecular dynamics (MD) simulations performed on the system had shown that the rotational motion involves energy larger than that involved ...

Persistence and changes in bioavailability of dieldrin, DDE and heptachlor epoxide in earthworms over 45 years

Science.gov (United States)

Beyer, W. Nelson; Gale, Robert W.

2013-01-01

The finding of dieldrin (88 ng/g), DDE (52 ng/g), and heptachlor epoxide (19 ng/g) in earthworms from experimental plots after a single moderate application (9 kg/ha) 45 years earlier attests to the remarkable persistence of these compounds in soil and their continued uptake by soil organisms. Half-lives (with 95 % confidence intervals) in earthworms, estimated from exponential decay equations, were as follows: dieldrin 4.9 (4.3-5.7) years, DDE 5.3 (4.7-6.1) years, and heptachlor epoxide 4.3 (3.8-4.9) years. These half-lives were not significantly different from those estimated after 20 years. Concentration factors (dry weight earthworm tissue/dry weight soil) were initially high and decreased mainly during the first 11 years after application. By the end of the study, average concentration factors were 1.5 (dieldrin), 4.0 (DDE), and 1.8 (heptachlor epoxide), respectively.

Dysregulation of soluble epoxide hydrolase and lipidomic profiles in anorexia nervosa

KAUST Repository

Shih, P. B.; Yang, J.; Morisseau, C.; German, J. B.; Scott-Van Zeeland, A. A.; Armando, A. M.; Quehenberger, O.; Bergen, A. W.; Magistretti, Pierre J.; Berrettini, W.; Halmi, K. A.; Schork, N.; Hammock, B. D.; Kaye, W.

2015-01-01

Individuals with anorexia nervosa (AN) restrict eating and become emaciated. They tend to have an aversion to foods rich in fat. Because epoxide hydrolase 2 (EPHX2) was identified as a novel AN susceptibility gene, and because its protein product

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei

2015-02-05

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei; Salmeia, Khalifah A.; Vagin, Sergei I.; Rieger, Bernhard

2015-01-01

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

A Review of the Environmental Degradation, Ecotoxicity, and Bioaccumulation Potential of the Low Molecular Weight Polyether Polyol Substances.

Science.gov (United States)

Schupp, Thomas; Austin, Tom; Eadsforth, Charles V; Bossuyt, Bart; Shen, Summer M; West, Robert J

"Polyalkylene glycol" is the name given to a broad class of synthetic organic chemicals which are produced by polymerization of one or more alkylene oxide (epoxide) monomers, such as ethylene oxide (EO) and propylene oxide (PO), with various initiator substances which possess amine or alcohol groups. A generalization of this polymerization reaction is illustrated in Fig. 1.

Ethylene glycol and propylene glycol ethers – Reproductive and developmental toxicity

Directory of Open Access Journals (Sweden)

Beata Starek-Świechowicz

2015-10-01

Full Text Available Both ethylene and propylene glycol alkyl ethers (EGAEs and PGAEs, respectively are widely used, mainly as solvents, in industrial and household products. Some EGAEs demonstrate gonadotoxic, embriotoxic, fetotoxic and teratogenic effects in both humans and experimental animals. Due to the noxious impact of these ethers on reproduction and development of organisms EGAEs are replaced for considerably less toxic PGAEs. The data on the mechanisms of testicular, embriotoxic, fetotoxic and teratogenic effects of EGAEs are presented in this paper. Our particular attention was focused on the metabolism of some EGAEs and their organ-specific toxicities, apoptosis of spermatocytes associated with changes in the expression of various genes that code for oxidative stress factors, protein kinases and nuclear hormone receptors. Med Pr 2015;66(5:725–737

Insights into the deactivation mechanism of supported tungsten hydride on alumina (W-H/Al2O3) catalyst for the direct conversion of ethylene to propylene

KAUST Repository

Mazoyer, Etienne; Szeto, Kaï Chung; Merle, Nicolas; Thivolle-Cazat, Jean; Boyron, Olivier; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2014-01-01

Tungsten hydride supported on alumina prepared by the surface organometallic chemistry method is an active precursor for the direct conversion of ethylene to propylene at low temperature and pressure. An extensive contact time study revealed

Mechanical and thermal properties of eco-friendly poly(propylene carbonate)/cellulose acetate butyrate blends.

Science.gov (United States)

Xing, Chenyang; Wang, Hengti; Hu, Qiaoqiao; Xu, Fenfen; Cao, Xiaojun; You, Jichun; Li, Yongjin

2013-02-15

The eco-friendly poly(propylene carbonate) (PPC)/cellulose acetate butyrate (CAB) blends were prepared by melt-blending in a batch mixer for the first time. PPC and CAB were partially miscible because of the drastically shifted glass transition temperatures of both PPC and CAB, which originated from the specific interactions between carbonyl groups and hydroxyl groups. The incorporation of CAB into PPC matrix enhanced not only tensile strength and modulus of PPC dramatically, but also improved heat resistance and thermal stability of PPC significantly. The tensile strength and the modulus of PPC/CAB=50/50 blend are 27.7 MPa and 1.24 GPa, which are 21 times and 28 times higher than those of the unmodified PPC, respectively. Moreover, the elongation at break of PPC/CAB=50/50 blend is as high as 117%. In addition, the obtained blends exhibited good transparency, which is very important for the package materials. The results in this work pave new possibility for the massive application of eco-friendly polymer materials. Copyright © 2012 Elsevier Ltd. All rights reserved.

Poly(ethylene oxide)–Poly(propylene oxide)-Based Copolymers for ...

African Journals Online (AJOL)

Amphiphilic poly(ethylene oxide)–poly(propylene oxide) (PEO–PPO)-based copolymers are thermoresponsive materials having aggregation properties in aqueous medium. As hydrosolubilizers of poorly water-soluble drugs and improved stability of sensitive agents, these materials have been investigated for improvement ...

Thermoreversible covalent crosslinking of maleated ethylene/propylene copolymers with diols

NARCIS (Netherlands)

Mee, van der M.A.J.; Goossens, J.G.P.; Duin, van M.

2008-01-01

Maleated ethylene/propylene copolymer (MAn-g-EPM) was thermoreversibly cross-linked using different routes, i.e. ionic interactions (ionomers), hydrogen bonding and a combination thereof. Microphase separation into polar MAn-rich aggregates occurs for MAn-g-EPM and all cross-linked materials, which

Lysophosphatidic acids are new substrates for the phosphatase domain of soluble epoxide hydrolase[S

Science.gov (United States)

Oguro, Ami; Imaoka, Susumu

2012-01-01

Soluble epoxide hydrolase (sEH) is a bifunctional enzyme that has a C-terminus epoxide hydrolase domain and an N-terminus phosphatase domain. The endogenous substrates of epoxide hydrolase are known to be epoxyeicosatrienoic acids, but the endogenous substrates of the phosphatase activity are not well understood. In this study, to explore the substrates of sEH, we investigated the inhibition of the phosphatase activity of sEH toward 4-methylumbelliferyl phosphate by using lecithin and its hydrolyzed products. Although lecithin itself did not inhibit the phosphatase activity, the hydrolyzed lecithin significantly inhibited it, suggesting that lysophospholipid or fatty acid can inhibit it. Next, we investigated the inhibition of phosphatase activity by lysophosphatidyl choline, palmitoyl lysophosphatidic acid, monopalmitoyl glycerol, and palmitic acid. Palmitoyl lysophosphatidic acid and fatty acid efficiently inhibited phosphatase activity, suggesting that lysophosphatidic acids (LPAs) are substrates for the phosphatase activity of sEH. As expected, palmitoyl, stearoyl, oleoyl, and arachidonoyl LPAs were efficiently dephosphorylated by sEH (Km, 3–7 μM; Vmax, 150–193 nmol/min/mg). These results suggest that LPAs are substrates of sEH, which may regulate physiological functions of cells via their metabolism. PMID:22217705

Interspecies differences in the enantioselectivity of epoxide hydrolases in Cryptococcus laurentii (Kufferath) C.E. Skinner and Cryptococcus podzolicus (Bab'jeva & Reshetova) Golubev

CSIR Research Space (South Africa)

Botes, AL

2005-01-01

Full Text Available Isolates representing Cryptococcus laurentii and Cryptococcus podzolicus, originating from soil of a heath land indigenous to South Africa, were screened for the presence of enantioselective epoxide hydrolases for 2, 2-disubstituted epoxides...

Optimization of the In Situ Epoxidation of Linoleic Acid of Jatropha Curcas Oil With Performic Acid

International Nuclear Information System (INIS)

Hong, L.K.; Rahimi Mohd Yusop; Nadia Salih; Jumat Salimon

2015-01-01

The aim of this study is to optimise the epoxidation of linoleic acid of Jatropha curcas oil. This experiment was carried out with performic acid generated in situ by using hydrogen peroxide and formic acid. The method was evaluated on different parameters such as reaction temperature, mole ratios of formic acid to ethylenic unsaturation and hydrogen peroxide to ethylenic unsaturation. The optimum relative conversion into oxirane (80.4 %) and conversion of iodine (94.7 %) was achieved with ∼70 % yield at the condition of 45 degree Celsius reaction temperature, formic acid to ethylenic unsaturation mole ratio of 2.0, hydrogen peroxide to ethylenic unsaturation mole ratio of 12.0 for 2 hours of reaction time. The epoxidized linoleic acid was characterized by using Fourier transform infrared (FTIR) spectroscopy and NMR analysis. The result was also found that the formations of an epoxide and oxirane ring cleavage were both occurred at the same time if low amount of hydrogen peroxide was used. (author)

Nanomechanical properties of hydroxyapatite (HAP) with DAB dendrimers (poly-propylene imine) coatings onto titanium surfaces

International Nuclear Information System (INIS)

Charitidis, Costas A.; Skarmoutsou, Amalia; Tsetsekou, Athena; Brasinika, Despina; Tsiourvas, Dimitris

2013-01-01

Highlights: ► The synthesis of hydroxyapatite (HAP) nanoparticles in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB). ► The nanomechanical properties of different HAP-DAB coatings onto titanium surfaces. ► Wear resistance and adhesion properties of the synthesized coatings quantified by nanoindentation data analysis. -- Abstract: Coatings of hydroxyapatite (HAP) nanorods onto titanium surfaces were synthesized with the aim to improve coatings’ mechanical properties and adhesion to the substrate. The coatings are consisting of HAP nanorods synthesized in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB) bearing 32 amine end groups employing varying calcium: dendrimer ratios and varying hydrothermal treatments. The quality, surface morphology and structure of the coatings were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy dispersive microanalysis. Wear resistance and adhesion properties of the coatings onto titanium substrates were studied through nanoindentation analysis. The experimental conditions, namely the calcium: dendrimer molar ratio and the hydrothermal treatment temperature were carefully selected; thus, it was possible to produce coatings of high hardness and elastic modulus values (ranging between 1–4.5 GPa and 40–150 GPa, respectively) and/or high wear resistance and plastic deformation values

Nanomechanical properties of hydroxyapatite (HAP) with DAB dendrimers (poly-propylene imine) coatings onto titanium surfaces

Energy Technology Data Exchange (ETDEWEB)

Charitidis, Costas A., E-mail: charitidis@chemeng.ntua.gr [School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Skarmoutsou, Amalia [School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Tsetsekou, Athena; Brasinika, Despina [School of Mining Engineering and Metallurgy, National Technical University of Athens, Iroon Polytechniou, Zografou, 15780 Athens (Greece); Tsiourvas, Dimitris [National Centre for Scientific Research “Demokritos”, Institute of Physical Chemistry, Agia Paraskevi, 15310 Athens (Greece)

2013-04-20

Highlights: ► The synthesis of hydroxyapatite (HAP) nanoparticles in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB). ► The nanomechanical properties of different HAP-DAB coatings onto titanium surfaces. ► Wear resistance and adhesion properties of the synthesized coatings quantified by nanoindentation data analysis. -- Abstract: Coatings of hydroxyapatite (HAP) nanorods onto titanium surfaces were synthesized with the aim to improve coatings’ mechanical properties and adhesion to the substrate. The coatings are consisting of HAP nanorods synthesized in the presence of a cationic fourth generation diaminobutane poly(propylene imine) dendrimer (DAB) bearing 32 amine end groups employing varying calcium: dendrimer ratios and varying hydrothermal treatments. The quality, surface morphology and structure of the coatings were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy dispersive microanalysis. Wear resistance and adhesion properties of the coatings onto titanium substrates were studied through nanoindentation analysis. The experimental conditions, namely the calcium: dendrimer molar ratio and the hydrothermal treatment temperature were carefully selected; thus, it was possible to produce coatings of high hardness and elastic modulus values (ranging between 1–4.5 GPa and 40–150 GPa, respectively) and/or high wear resistance and plastic deformation values.

Selective Propene Epoxidation on Immobilized Au_6-10 Clusters: The Effect of Hydrogen and Water on Activity and Selectivity

DEFF Research Database (Denmark)

Lee, Sungsik; Molina, Luis M.; López, María J.

2009-01-01

Epoxidation made easy: Subnanometer gold clusters immobilized on amorphous alumina result in a highly active and selective catalyst for propene epoxidation. The highest selectivity is found for gas mixtures involving oxygen and water, thus avoiding the use of hydrogen. Ab initio DFT calculations ...

Surface compounds and the routes of formation of the reaction products in the interaction of propylene with zinc oxide

Energy Technology Data Exchange (ETDEWEB)

Davydov, A.A.; Yefremov, A.A.; Mikhalchenko, V.G.; Sokolovskii, V.D.

1979-06-15

Temperature programed desorption of propylene and allyl bromide from zinc oxide in the absence and presence of oxygen and an IR spectroscopic study of the adsorbed allyl bromide showed that propylene chemisorbed reversibly as a m-allyl species which may undergo dimerization at higher pressures or temperatures but does not form acrolein because the necessary electron transfer does not proceed on the n-type zinc oxide; that propylene also forms carbon dioxide and water via carbonate/carboxylate intermediates; and that the allyl bromide, which forms cations on the zinc oxide surface, is oxidized to acrolein.

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

Crack resistance increasing in epoxide-rubber coatings of NPP room floors

International Nuclear Information System (INIS)

Khorenzhenko, V.I.

1986-01-01

Problems of crack resistance increasing in epoxide-rubber coatings for the floors are considered. Exploitation experience of the floors in the special rooms of NPP is given. Perspectivity of application of the compositions described as the building materials for nuclear power stations is pointed out

High octane gasoline components from catalytic cracking gasoline, propylene, and isobutane by disproportionation, clevage and alkylation

Energy Technology Data Exchange (ETDEWEB)

Banks, R.

1980-07-08

A process is described for producing high octane value gasoline which comprises in a disproportionation zone subjecting propylene and a mixture of propylene and ethylene obtained as hereinafter delineated to disproportionation conditions to produce a stream containing ethylene and a stream containing butenes, passing the ethylene-containing stream from said disproportionation zone together with a catalytic cracking gasoline to a cleavage zone under disproportionation conditions and subjecting the mixture of hydrocarbons therin to cleavage to produce said mixture of propylene and ethylene, a C/sub 5//sup +/ gasoline-containing product and butenes and wherein the butenes obtained in the overall operation of the disproportionation zone and the cleavage zone are passed to an alkylation zone wherein said butenes are used to alkylate an isoparaffin to produce additional high octane value product.

Aerobic methylcyclohexane-promoted epoxidation of stilbene over gold nanoparticles supported on Gd-doped titania

KAUST Repository

Mendez, Violaine; Guillois, Kevin; Daniè le, Sté phane; Tuel, Alain; Caps, Valerie

2010-01-01

Aerobic partial oxidations of alkanes and alkenes are important processes of the petrochemical industry. The radical mechanisms involved can be catalyzed by soluble salts of transition metals (Co, Cu, Mn...). We show here that the model methylcyclohexane/stilbene co-oxidation reaction can be efficiently catalyzed at lower temperature by supported gold nanoparticles. The support has little influence on gold intrinsic activity but more on the apparent reaction rates which are a combination of catalytic activity and diffusion limitations. These are here minimized by using gadolinium-doped titania nanocrystallites as support for gold nanoparticles. This material is obtained by mild hydrolysis of a new Gd4TiO(OiPr)14 bimetallic oxoalkoxide. It leads to enhanced wettability of the < 3 nm gold particles in the tert-butyl hydroperoxide (TBHP)-initiated epoxidation of stilbene in methylcyclohexane; Au/TiO2:Gd3+ is in turn as active as the state-of-the-art hydrophobic Au/SiO2 catalyst. The rate-determining step of this reaction is identified as the gold-catalyzed homolytic decomposition of TBHP generating radicals and initiating the methylcyclohexane-mediated epoxidation of stilbene, yielding a methylcyclohexan-1-ol/trans-stilbene oxide mixture. Methylcyclohexan-1-ol can also be obtained in the absence of the alkene in the gold-catalyzed solvent-free autoxidation of methylcyclohexane, evidencing the catalytic potential of gold nanoparticles for low temperature C-H activation. © 2010 The Royal Society of Chemistry.

Effects of experimental variables on the degree of epoxidation of ...

African Journals Online (AJOL)

Results show that the acid treatment of the bentonite clay improved its support characteristics by achieving some increase in surface area and optimum treatment condition was found to be 10g bentonite clay treated with 30cm3 sulphuric acid for 6 hours. It was found that higher epoxidation was achieved with treated ...

Discovery of the First Interstellar Chiral Molecule: Propylene Oxide

Science.gov (United States)

Carroll, Brandon; McGuire, Brett A.; Loomis, Ryan; Finneran, Ian A.; Jewell, Philip; Remijan, Anthony; Blake, Geoffrey

2016-06-01

Life on Earth relies on chiral molecules, that is, species not superimposable on their mirror images. This manifests itself as a reliance on a single molecular handedness, or homochirality that is characteristic of life and perhaps most readily apparent in the large enhancement in biological activity of particular amino acid and sugar enantiomers. Yet, the ancestral origin of biological homochirality remains a mystery. The non-racemic ratios in some organics isolated from primitive meteorites hint at a primordial chiral seed but even these samples have experienced substantial processing during planetary assembly, obscuring their complete histories. To determine the underlying origin of any enantiomeric excess, it is critical to understand the molecular gas from which these molecules originated. Here, we present the first extra-solar, astronomical detection of a chiral molecule, propylene oxide (CH_3CHCH_2O), in absorption toward the Galactic Center. With the detection of propylene oxide, we at last have a target for broad-ranging searches for the possible cosmic origin of the homochirality of life.

Effective separation of propylene/propane binary mixtures by ZIF-8 membranes

KAUST Repository

Pan, Yichang; Li, Tao; Lestari, Gabriella; Lai, Zhiping

2012-01-01

The separation of propylene/propane mixtures is one of the most important but challenging processes in the petrochemical industry. A novel zeolitic imidazole framework (ZIF-8) membrane prepared by a facile hydrothermal seeded growth method showed

Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide

NARCIS (Netherlands)

Wang, Y.M.; Magusin, P.C.M.M.; Santen, van R.A.; Abbenhuis, H.C.L.

2007-01-01

Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide were synthesized through the acid-catalyzed hydrolysis and co-condensation of organotrialkoxysilane monomers and a,¿-bis(trialkoxysilyl) alkane cross-linkers in ethanol–water solution, with

Molecular weight and its distribution of tetrafluoroethylene and propylene copolymer

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Okamoto, Jiro; Yamaguchi, Koichi.

1978-04-01

In comparison of molecular structure of tetrafluoroethylene and propylene copolymer produced by radiation and chemical initiators respectively, both were fractionated by elution method and fine structure was examined. For the fractionated sample by radiation, the relation between molecular weight anti Mn and intrinsic viscosity ( eta] is ( eta] = 3.97 x 10 -4 anti Mnsup(0.630) The result is not in agreement with that of the unfractionated sample by radiation, and similar to those of samples by chemical initiators. There is no difference, however, in the elution method of GPC between both these copolymers; the elution behavior agrees with that of standard polystyrene. Long chain branching thus exists little in the copolymer of tetrafluoroethylene and propylene. To reveal the relations between reaction conditions and molecular weight and its distribution of the copolymer produced by flow apparatus, the molecular weight distribution was measured by GPC. The method of analysis could evaluate molecular weight distribution changing constantly. (auth.)

Mechanical and morphological characterization of novel vinyl plastisols with epoxidized linseed oil as natural-based plasticizer

International Nuclear Information System (INIS)

Fenollar, O.; Balart, R.; Sanchez-Nacher, L.; Garcia-Sanoguera, D.; Boronat, T.

2010-01-01

Poly(vinyl chloride)(PVC) is one of the most commonly used plastics in the current market due to its low cost and versatility in processing, combined with its satisfactory physical and chemical properties. However, there is an important problem associated to the use of plasticized PVC. This problem is regarding to the toxicity of the most common plasticized used like DOP, DEHP, DINP, due to its possible migration. This problem limits the use of the plasticized PVC in the industry. In this work we have used epoxidized linseed oil (ELO) as a non toxic plasticizer for PVC. This type of natural oil is characterized by acting as both plasticizer and stabilizer of PVC. With this purpose, ELO have been added to PVC. The processing conditions (temperature and time of curing) are vital to determine the final properties of the material. A study of the processing conditions shows the adequate temperature and time to achieve the optimum properties.

Improvement of enantioselectivity by immobilized imprinting of epoxide hydrolase from Rhodotorula glutinis

NARCIS (Netherlands)

Kronenburg, N.A.E.; Bont, de J.A.M.; Fischer, L.

2001-01-01

The yeast Rhodotorula glutinis contains an enantioselective, membrane-associated epoxide hydrolase (EH). Partially purified EH was immobilized in a two-step procedure. In the first step, the proteins were derivatized with itaconic anhydride. In the second step, the derivatized proteins were

Thermodynamic and electrochemical properties of some rare earth cryptates and related complexes in propylene carbonate

International Nuclear Information System (INIS)

Loufouilou, E.L.

1986-03-01

The stability of trivalent lanthanide complexes with [1]-cryptand 22 and [2]-cryptands 222 and 211 and also tris (3.6- dioxa heptyl) amine (TDHA) is studied in propylene carbonate solution by potentiometry with Ag + as an auxiliary cation. Complexation enthalpies and entropies are determined for other complexes of some trivalent lanthanides (La, Er, Pr and Eu) with ligands 222, 221, 211, 22, 21, 18C6 and TDHA. [1]- and [2]- crytands are complexing agents more powerful than TDHA and crown-ethers 15C6 and 18C6. For ligands containing nitrogen complexe stability increase with RE atomic number but decrease for crown-ethers. In propylene carbonate complexes are stabilized by enthalpic effects, entropic contribution is variable. Polarographic reduction of samarium cryptate with ligand 222, 221 and 22 in propylene carbonate is reversible as in more solvating solvents water and methanol. Mixed complexes are formed with chlorides and this cryptate system is more difficult to reduce [fr

A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

KAUST Repository

Bahri-Laleh, Naeimeh

2012-11-01

Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. © 2012 Elsevier B.V.

A combined experimental and theoretical study on ethanol conversion to propylene over Y/ZrO2 catalyst

Science.gov (United States)

Wang, Fangfang; Xia, Wei; Mu, Xichuan; Chen, Kun; Si, Huimin; Li, Zhihao

2018-05-01

ZrO2-based catalysts doped with Y were prepared by co-precipitation method. The effect of yttrium modification on the selective conversion of bio-ethanol to propylene over ZrO2 catalysts was investigated. The physical and chemical properties of the catalysts were characterized by N2 adsorption-desorption method, temperature programmed desorption and X-ray diffraction. The maximum yield of propylene reached 44.0% over 0.03Y/ZrO2 catalyst. A coordination of acid-base properties accounts for the remarkable improvement of reaction activities over Y-doped ZrO2 catalysts in this investigation. On the basis of calculation results, it can be concluded that significant charge transfer occurs as a result of introduction of Y or O-vacancy. The adsorption of ethanol and propylene on perfect t-ZrO2 (1 0 1), defect t-ZrO2 (1 0 1) and Y/ZrO2 (1 0 1) surfaces were investigated with density functional theory (DFT). The adsorption for ethanol on Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces are more stable than that on perfect t-ZrO2 (1 0 1). On the defect t-ZrO2 (1 0 1) surface, ethanol dominantly absorbs at the O-vacancy site, indicating that O-vacancy becomes the favorable adsorption site. On the Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces, the adsorption energy of propylene decreases, which makes propylene desorb quickly after formation.

Stabilizing effect of epoxidized sunflower oil as a secondary stabilizer for Ca/Hg stabilized PVC

Directory of Open Access Journals (Sweden)

2008-01-01

Full Text Available Unsaturated triglyceride oil sunflower was epoxidized and characterized by chemical and spectroscopic methods. Epoxidized sunflower oil (ESO was used as an organic thermal co-stabilizer for rigid poly(vinyl chloride (PVC in the presence of tricalcium dicitrate (Ca3(C6H5O72 and mercury (II acetate (Hg(CH3COO2. The thermo-oxidative degradation of PVC was studied in the presence of these ternary stabilizer systems at 170, 180, 190 and 200°C in N2 atmosphere. The effects of metal carboxylate combination Ca/Hg in the absence and in the presence of epoxidized sunflower oil on static heat treatment of PVC have been studied. The formation of polyene sequences was investigated by UV-visible and FT-IR spectroscopy and by comparing viscosity data obtained in the presence and in the absence of the additives. It was found that the additives retard the rate of degradation and reduce the extent of polymer chain scission associated with the thermal degradation of poly(vinyl chloride. Synergistic effects were found when stabilizer was blended in 50:50 weight ratios with either. It was found that ESO exerted a stabilizing effect on the degradation of PVC. The activation energy for degraded PVC in absence of stabilizers was 38.6 kJ•mol–1 and in the presence of Ca/Hg and Ca/Hg/ESO were 53.3 and 64.7 kJ•mol–1 respectively. In order of compare the efficiency of the epoxidized sunflower oil with these metal soap stabilizers, thermal stabilities were evaluated on the basis of evolved hydrogen chloride determined by conductometry technique and degree of discoloration are discussed.

Irradiation of isotactic polypropylene and polypropylene/ethylene-propylene (diene-monomer) blends

NARCIS (Netherlands)

Gisbergen, van J.G.M.; Meijerink, J.I.; Overbergh, N.; Kleintjes, L.; Lemstra, P.J.

1989-01-01

The influence of electron beam irradiation on rheological properties and morphology of polypropylene and polypropylene/ethylene-propylene rubber blends was studied. Electron beam irradiation of isotactic PP causes pronounced chain scission (degradation) at dosis = 100 kGy. Melt viscosity can be

EVALUATION OF PROPYLENE CARBONATE IN AIR LOGISTICS CENTER (ALC) DEPAINTING OPERATIONS

Science.gov (United States)

This report summarizes a two-phase, laboratory-scale screening study that evaluated solvent blends containing propylene carbonate (PC) as a potential replacement for methyl ethyl ketone (MEK) in aircraft radome depainting operations. The study was conducted at Oklahoma City Air L...

Rapid epoxidation of palm acid oil with lipase action under microwave irradiation

International Nuclear Information System (INIS)

Saifuddin, N.; Wei Zhan Lee; Koh, X.N.; Ramesh, S.; Abdullah, S.F.

2010-01-01

In view of growing environmental concerns and tightened regulations over contaminants and pollution in the environment in recent years, calls for biodegradable and nontoxic vegetable oil-based lubricants are abound. They have very low volatility due to the higher molecular weight of the triacylglycerol molecule and a narrow range of viscosity changes with temperature. Polar ester groups in the molecule are able to adhere to metal surfaces, and therefore, possess good boundary lubrication properties. In addition, vegetable oils have high solubilising power for polar contaminants and additive molecules. However, vegetable oils show poor oxidative and thermal stability primarily due to the presence of unsaturation. The presence of ester functionality also renders these oils susceptible to hydrolytic breakdown. The proposed modification of the vegetable oils is an important manner to obtain potentially useful products using a renewable feedstock. In designing a green process to effectively carry out the epoxidation reaction, we report herein, an inexpensive, practical, safe and environmentally friendly method to epoxidize palm acid oil under extremely mild conditions. This work highlights the increased reaction rate of the epoxidation process when microwave irradiation is introduced. The starting material used is Palm Acid Oil, a by-product of the alkali refining process of palm oil. Acid oil can serve as an inexpensive raw materials and are very good substitute for neat vegetable oil such as palm oil for the production of bio lubricant. It is high in Free Fatty Acids (FFA) and is the ideal material for the epoxidation process due to the importance of FFAs in producing peroxy-acids as an oxygen carrier. The double bonds the triglycerides are reacted with a per acid, generated for safety reasons in situ using hydrogen peroxide. Novozym 435 acts as the catalyst in the process and with its good selectivity, the occurrence of by-products is controlled. The method and

Synthesis and characterization of new magnetically recoverable molybdenum nanocatalyst for epoxidation of olefins

Energy Technology Data Exchange (ETDEWEB)

Masteri-Farahani, M., E-mail: mfarahany@yahoo.com [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of); Kashef, Z. [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of)

2012-04-15

New heterogeneous molybdenum catalyst was prepared through covalent attachment of a Schiff base ligand on the surface of silica coated magnetite nanoparticles via aminopropyl spacer and subsequent complexation with MoO{sub 2}(acac){sub 2}. The prepared nanocatalyst was characterized with Fourier transform infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopies and vibrating sample magnetometry. Catalytic epoxidation of some olefins and allylic alcohols by prepared nanocatalyst using tert-butyl hydroperoxide and cumene hydroperoxide as oxidants was achieved with good activities and selectivities. - Highlights: Black-Right-Pointing-Pointer Silica coated magnetite nanoparticles were modified with a Schiff base ligand. Black-Right-Pointing-Pointer Next reaction with MoO{sub 2}(acac){sub 2} afforded magnetically recoverable nanocatalyst. Black-Right-Pointing-Pointer The prepared nanocatalyst catalyzed the epoxidation of olefins with TBHP.

Epoxidation of Alkenes with Aqueous Hydrogen Peroxide and Quaternary Ammonium Bicarbonate Catalysts

DEFF Research Database (Denmark)

Mielby, Jerrik Jørgen; Kegnæs, Søren

2013-01-01

A range of solid and liquid catalysts containing bicarbonate anions were synthesised and tested for the epoxidation of alkenes with aqueous hydrogen peroxide. The combination of bicarbonate anions and quaternary ammonium cations opens up for new catalytic systems that can help to overcome...

Purification and characterisation of a novel enantioselective epoxide hydrolase from Aspergillus niger M200

Czech Academy of Sciences Publication Activity Database

Kotík, Michael; Kyslík, Pavel

2006-01-01

Roč. 1760, - (2006), s. 245-252 ISSN 0006-3002 Institutional research plan: CEZ:AV0Z50200510 Keywords : epoxide hydrolase * enantioselectivity * aspergillus niger Subject RIV: EE - Microbiology, Virology

Evaluation of fish models of soluble epoxide hydrolase inhibition.

OpenAIRE

Newman, J W; Denton, D L; Morisseau, C; Koger, C S; Wheelock, C E; Hinton, D E; Hammock, B D

2001-01-01

Substituted ureas and carbamates are mechanistic inhibitors of the soluble epoxide hydrolase (sEH). We screened a set of chemicals containing these functionalities in larval fathead minnow (Pimphales promelas) and embryo/larval golden medaka (Oryzias latipes) models to evaluate the utility of these systems for investigating sEH inhibition in vivo. Both fathead minnow and medaka sEHs were functionally similar to the tested mammalian orthologs (murine and human) with respect to substrate hydrol...

Increase of propylene production and recovery in a PETROBRAS FCC units; Aumento da producao e recuperacao de propeno em uma Unidade de FCC da PETROBRAS

Energy Technology Data Exchange (ETDEWEB)

Penna, Elisangela Melo; Pinho, Andrea de Rezende; Wolff, Marcelo Straubel [Petroleo Brasileiro S.A (PETROBRAS), Rio de Janeiro, RJ (Brazil)

2012-07-01

Propylene is one of the major petrochemical raw materials and its demand has been growing rapidly in recent years. Projections for future years indicate that the growth in propylene production via pyrolysis tends to be lower than the growth in the demand for ethylene, creating a supply deficit of this product. The FCC units are in a unique position to meet this increase in propylene demand due to its operational flexibility. Although their primary function in recent decades has been the gasoline production, FCC units are often operated for maximizing other products, such as LPG or distillates. At the FCC conversion section, the increase of propylene yield requires some increase in reaction severity, which can be obtained by increasing reactor riser temperature, and the use of catalyst additives based on ZSM-5. However, besides maximizing the propylene production in the reactor, a second objective should be pursued: the propylene recovery increase in the gas recovery section. In this section, the yield is affected by the gas compressor performance, the equipment design and process scheme. Eventually, new equipment may be installed, such as chillers, aimed at improving the absorption system. Predicting a real increase in propylene demand in the Brazilian market, this study aims to evaluate the adequacy of the gas recovery section of a PETROBRAS FCC unit, analyzing the impacts that a new products yields profile, which bend the propylene production compared to a conventional operation, would cause on this unit. In this paper, the main limitations and modifications that would be needed for an operation were identified, aiming at maximizing the propylene production, as well as proposed changes in the hardware of the unit. (author)

FY 2000 report on the results of the development of the next generation chemical process technology/development of the non-halogen chemical process technology; 2000 nendo jisedai kagaku process gijutsu kaihatsu non halogen kagaku process gijutsu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-03-01

For the purpose of conserving energy and reducing environmental loads, the R and D were conducted of a new chemical process (non-halogen chemical process) using new catalytic reaction, etc., and the FY 2000 results were summed up. As to the development of a new method to synthesize isocyanate, the development was proceeded with of a method to synthesize diisocyanate by the dicarbamate reaction and pyrolysis of the carbamate, and the effect of catalyst on the yield of carbamate reaction was grasped. Concerning the development of a new synthetic method of epoxides, the development was proceeded with of the catalyst for synthesizing propylene oxides from propylene and hydrogen/oxygen, and conditions were obtained for preparation of a catalyst of the basic catalytic system and with reproducibility. Moreover, the development was proceeded with of a new catalyst used in doing epoxidation of 1-butene using the organic system hydroperoxide. Concerning the development of a new method to synthesize phenol, a promising system was found out by finding out the basic catalytic system of oxidation acetoxyl reaction and proceeding with the search for co-catalyst, carrier, etc. (NEDO)

Differential effects of low-temperature inhibition on the propylene induced autocatalysis of ethylene production, respiration and ripening of 'Hayward' kiwifruit

DEFF Research Database (Denmark)

Antunes, M. D C; Pateraki, I.; Kanellis, A. K.

2000-01-01

production and the respiration rise appeared earlier with increased propylene concentrations. Ripening proceeded immediately after propylene treatment, while ethylene autocatalysis needed a lag period of 24-72 h. The latter event was attributed to the delay found in the induction of 1-aminocyclopropane-1....... It is concluded that kiwifruit stored at 20°C behaves as a typical climacteric fruit, while at 10°C behaves like a non-climacteric fruit. We propose that the main reasons for the inhibition of the propylene induced (autocatalytic) ethylene production in kiwifruit at low temperature (≤ IO°C), are primarily...

Biobased composites from thermoplastic polyurethane elastomer and cross-linked acrylated-epoxidized soybean oil

Science.gov (United States)

Soybean oil is an important sustainable material. Crosslinked acrylated epoxidized soybean oil (AESO) is brittle without flexibility and the incorporation of thermoplastic polyurethane improves its toughness for industrial applications. The hydrophilic functional groups from both oil and polyurethan...

Gamma-induced reactions of bromo-ethane with olefines. Addition of ethyl radicals to hexene-1 and propylene

International Nuclear Information System (INIS)

Myshkin, V.E.; Shostenko, A.G.; Zagorets, P.A.; Pchelkin, A.I.; Markova, K.G.

1978-01-01

Radiation interaction of bromo-ethane with propylene and 1-hexene has been studied with the aim to investigate the action of γ-radiation on bromalkanes. The absorbed dose rate is 50 rad/s. The reaction products separated by preparative chromatography have been identified with infrared spectroscopy, elemental, chromatographic, and other physico-chemical methods of analysis. It has been established that the reaction with propylene gives rise to telomers whereas interaction of bromo-ethane with 1-hexene yields only the addition product (4-bromoctane). The activation energy of the reactions of adding ethyl radicals to 1-hexene and propylene has been found equal to (3.8+-0.4 kcal/mol) and (2.2+-0.2 kcal/mol), respectively. The activation energy of the reaction of chain transfer through bromo-ethane is (3.7+-0.3 kcal/mol.)

UTL titanosilicate: An extra-large pore epoxidation catalyst with tunable textural properties

Czech Academy of Sciences Publication Activity Database

Přech, Jan; Čejka, Jiří

2016-01-01

Roč. 277, č. 1 (2016), s. 2-8 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : titanosilicate UTL * top-down synthesis * epoxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.636, year: 2016

Ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with propylene carbonate

Directory of Open Access Journals (Sweden)

S. Das

2015-02-01

Full Text Available We have studied ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of free ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.

Controlled synthesis of multi-arm star polyether-polycarbonate polyols based on propylene oxide and CO2.

Science.gov (United States)

Hilf, Jeannette; Schulze, Patricia; Seiwert, Jan; Frey, Holger

2014-01-01

Multi-arm star copolymers based on a hyperbranched poly(propylene oxide) polyether-polyol (hbPPO) as a core and poly(propylene carbonate) (PPC) arms are synthesized in two steps from propylene oxide (PO), a small amount of glycidol and CO2 . The PPC arms are prepared via carbon dioxide (CO2 )/PO copolymerization, using hbPPO as a multifunctional macroinitiator and the (R,R)-(salcy)CoOBzF5 catalyst. Star copolymers with 14 and 28 PPC arms, respectively, and controlled molecular weights in the range of 2700-8800 g mol(-1) are prepared (Mw /Mn = 1.23-1.61). Thermal analysis reveals lowered glass transition temperatures in the range of -8 to 10 °C for the PPC star polymers compared with linear PPC, which is due to the influence of the flexible polyether core. Successful conversion of the terminal hydroxyl groups with phenylisocyanate demonstrates the potential of the polycarbonate polyols for polyurethane synthesis. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies on chemically crosslinkable carboxy terminated-poly(propylene fumarate-co-ethylene glycol)-acrylamide hydrogel as an injectable biomaterial

International Nuclear Information System (INIS)

Kallukalam, B C; Jayabalan, M; Sankar, V

2009-01-01

Carboxy terminated-poly(propylene fumarate)-co-ethylene glycol) (CT-PPF-co-PEG) was prepared and set into crosslinked hydrogel material with acrylamide. The setting studies reveal that this copolymer system can be used as an injectable material. The hydrogel material exhibits a higher degree of swelling, good mechanical strength and flexibility. The hydrogel favours adhesion of L929 fibroblast cells without proliferation on the surface. However, cardiac fibroblast cells (isolated from new born rat (Wistar) hearts) adhere and proliferate on the hydrogel due to the formation of synergistic hydrophilic-hydrophobic surface-by-surface reorganization.

Studies on chemically crosslinkable carboxy terminated-poly(propylene fumarate-co-ethylene glycol)-acrylamide hydrogel as an injectable biomaterial

Energy Technology Data Exchange (ETDEWEB)

Kallukalam, B C; Jayabalan, M [Polymer Division, Biomedical Technology Wing, Sree Chitra Tirunal Institute for Medical Sciences and Technology, Thiruvananthapuram 695 012 (India); Sankar, V, E-mail: muthujayabalan@rediffmail.co [Division of Cellular and Molecular Cardiology, Sree Chitra Tirunal Institute for Medical Sciences and Technology, Thiruvananthapuram 695 012 (India)

2009-02-15

Carboxy terminated-poly(propylene fumarate)-co-ethylene glycol) (CT-PPF-co-PEG) was prepared and set into crosslinked hydrogel material with acrylamide. The setting studies reveal that this copolymer system can be used as an injectable material. The hydrogel material exhibits a higher degree of swelling, good mechanical strength and flexibility. The hydrogel favours adhesion of L929 fibroblast cells without proliferation on the surface. However, cardiac fibroblast cells (isolated from new born rat (Wistar) hearts) adhere and proliferate on the hydrogel due to the formation of synergistic hydrophilic-hydrophobic surface-by-surface reorganization.

Epoxidation of polybutadiene rubber in non polar solvent

International Nuclear Information System (INIS)

Schneider, Luciane K. de A.; Jacobi, Marly A.M.

2005-01-01

The epoxidation of polybutadiene rubber in cyclohexane, at 50 deg C, by the method of performic acid generated in situ, at different reagent concentration was investigated. The epoxy degree was determined by 1 H-RMN, and because of the gelation and coagulation of modified rubber during the reaction, only a maximum of 30 mol % of epoxy degree could be achieved. The reaction followed a first order kinetic in relation to hydrogen peroxide and acid concentration showing a rate constant of 4,0 (± 0,5) x 10 -5 L.mol-1.seg -1 . (author)

Effect of Molecular Weight on the Properties of Liquid Epoxidized Natural Rubber Acrylate (LENRA)/ Silica Hybrid Composites

International Nuclear Information System (INIS)

Eda Yuhana Ariffin; Azizan Ahmad; Dahlan Mohd; Mahathir Mohamed

2011-01-01

This paper reports on the effect of molecular weight on the morphological and mechanical properties of liquid epoxidized natural rubber acrylate (LENRA)/ silica hybrid composites prepared by sol-gel technique. The sol-gel reaction was conducted at different concentration of tetraethyl orthosilicate (TEOS), used as a precursor of silica. TEOS were introduced in 10, 20, 30, 40 and 50 parts per hundred rubber (phr) in the composites. Two different molecular weights of ENR were used to study the effect of molecular weight on the mechanical and morphological properties of the compounds. These compounds were cured by ultraviolet (UV) irradiation. The mechanical properties were studied through pendulum hardness and scratch tests. Higher molecular weight of ENR showed better mechanical properties than lower molecular weight. Transmission electron microscope was used to determine the silica size and to study the distribution and dispersion of the silica particles. High molecular weight showed greater distribution and dispersion of silica particles with diameter of 13 - 256 nm. Morphological and mechanical properties of LENRA/ silica hybrid composites were improved by using high molecular weight of ENR. (author)

Performance of 6FDA–6FpDA polyimide for propylene/propane separations

KAUST Repository

Das, Mita; Koros, William J.

2010-01-01

This work addresses the challenges faced by previous researchers with 6FDA-6FpDA polyimide for propylene/propane separations due to plasticization. A study of film annealing temperature is reported to optimize plasticization suppression in elevated

Engineering characterisation of epoxidized natural rubber-modified hot-mix asphalt.

Directory of Open Access Journals (Sweden)

Ramez A Al-Mansob

Full Text Available Road distress results in high maintenance costs. However, increased understandings of asphalt behaviour and properties coupled with technological developments have allowed paving technologists to examine the benefits of introducing additives and modifiers. As a result, polymers have become extremely popular as modifiers to improve the performance of the asphalt mix. This study investigates the performance characteristics of epoxidized natural rubber (ENR-modified hot-mix asphalt. Tests were conducted using ENR-asphalt mixes prepared using the wet process. Mechanical testing on the ENR-asphalt mixes showed that the resilient modulus of the mixes was greatly affected by testing temperature and frequency. On the other hand, although rutting performance decreased at high temperatures because of the increased elasticity of the ENR-asphalt mixes, fatigue performance improved at intermediate temperatures as compared to the base mix. However, durability tests indicated that the ENR-asphalt mixes were slightly susceptible to the presence of moisture. In conclusion, the performance of asphalt pavement can be enhanced by incorporating ENR as a modifier to counter major road distress.

Effect of Organo-Modified Nanoclay on the Thermal and Bulk Structural Properties of Poly(3-hydroxybutyrate-Epoxidized Natural Rubber Blends: Formation of Multi-Components Biobased Nanohybrids

Directory of Open Access Journals (Sweden)

Ali Salehabadi

2014-06-01

Full Text Available Multi-component nanohybrids comprising of organo-modified montmorillonite (MMT and immiscible biopolymer blends of poly(3-hydroxybutyrate (PHB and epoxidized natural rubber (ENR-50 were prepared by solvent casting technique. The one and three dimensional morphology of PHB/ENR-50/MMT systems were studied using Polarizing Optical Microscopy (POM and Scanning Electron Microscopy (SEM. Differential scanning calorimetry (DSC technique was used to evaluate the thermal properties of the nanohybrids. The melting temperature (Tm and enthalpy of melting (ΔHm of PHB decrease with respect to the increase in ENR-50 as well as MMT content. The non-isothermal decomposition of the nanohybrids was studied using thermogravimetric (TG-DTG analysis. FTIR-ATR spectra supported ring opening of the epoxide group via reaction with carboxyl group of PHB and amines of organic modifier. The reaction mechanism towards the formation of the nanohybrids is proposed.

Metal–organic framework-based catalysts: Chemical fixation of CO2 with epoxides leading to cyclic organic carbonates

Directory of Open Access Journals (Sweden)

M. Hassan eBeyzavi

2015-01-01

Full Text Available As a C1 feedstock, CO2 has the potential to be uniquely highly economical in both a chemical and a financial sense. In particular, the highly atom-economical acid-catalyzed cycloaddition of CO2 to epoxides to yield cyclic organic carbonates (OCs, a functionality having many important industrial applications, is an attractive reaction for the utilization of CO2 as a chemical feedstock. Metal–organic frameworks (MOFs are promising candidates in catalysis as they are a class of crystalline, porous and functional materials with remarkable properties including great surface area, high stability, open channels and permanent porosity. MOFs structure tunability and their affinity for CO2, makes them great catalysts for the formation of OCs using CO2 and epoxides. In this review, we examine MOF-based catalytic materials for the cycloaddition of carbon dioxide to epoxides. Catalysts are grouped based on the location of catalytic sites, i.e., at the struts, nodes, defect sites, or some combination thereof. Additionally, important features of each catalyst system are critically discussed.

Hybrid thermosets from vinyl ester resin and acrylated epoxidized soybean oil (AESO

Directory of Open Access Journals (Sweden)

2011-01-01

Full Text Available A series of hybrids composed of styrene crosslinkable vinyl ester (VE and acrylated epoxidized soybean oil (AESO were produced via free radical-induced crosslinking. The VE/AESO ratio was changed between 75/25 and 25/75 wt%. Moreover, to support phase grafting the VE/AESO = 50/50 wt% hybrid was modified with phthalic anhydride in various amounts (1, 5 and 10 wt%. The structure of the hybrid systems was investigated by dynamic mechanical thermal analysis (DMTA, differential scanning calorimetry (DSC, and atomic force microscopy (AFM. The properties of the systems were assessed by static flexural and fracture mechanical tests. The resistance to thermal degradation was inspected by thermogravimetric analysis (TGA. The results suggested that the hybrids have an interpenetrating network (IPN structure. With increasing AESO content the stiffness (modulus, strength and glass transition temperature (Tg of the hybrids decreased, whereas their ductility increased. Phthalic anhydride caused an adverse trend. Both the fracture toughness and fracture energy increased with increasing AESO content. They were less affected by adding phthalic anhydride phase couplant. Interestingly, the hybrids outperformed the parent VE and AESO in respect to resistance to thermal degradation.

Metabolism of polyunsaturated (n-3) fatty acids by monkey seminal vesicles: isolation and biosynthesis of omega-3 epoxides.

Science.gov (United States)

Oliw, E H; Sprecher, H W

1991-11-27

Monooxygenases of monkey seminal vesicles can metabolize arachidonic acid (20:4(n-6)) by w3-hydroxylation to 18(R)-hydroxyeicosatetraenoic acid (18(R)-HETE) and eicosapentaenoic acid (20:5(n-3)) to 17,18-dihydroxyeicosatetraenoic acid (Oliw, E.H. (1989) J. Biol. Chem. 264, 17845-17853). The present study aimed to further characterize the oxygenation of (n-3) polyunsaturated fatty acids. 14C-Labelled 22:6(n-3), 20:5(n-3), 20:4-(n-3) and 18:3(n-3) were incubated with microsomes of seminal vesicles of the cynomolgus monkey, NADPH and a cyclooxygenase inhibitor, diclofenac, and the main metabolites were identified by capillary gas chromatography-mass spectrometry. 22:6(n-3) was slowly metabolized to 19,20-dihydroxy-4,7,10,13,16-docosapentaenoic acid, while 20:5(n-3), 20:4(n-3) and 18:3(n-3) were metabolized more efficiently to the corresponding w4,w3-diols. The w3 epoxides, which were obtained from 20:5(n-3) and 18:3(n-3), were isolated in the presence of an epoxide hydrolase inhibitor, 1(2)epoxy-3,3,3-trichloropropane, and the geometry of the epoxides was determined to be 17S, 18R and 15S, 16R, respectively. While 20:5(n-3) was metabolized almost exclusively to the epoxide and diol pair of metabolites, 18:3(n-3) was metabolized not only to the w3 epoxide and the corresponding diol, but also to the w2 alcohol, 17(R)-hydroxy-9,12,15-octadecatrienoic acid. 22:6(n-3) and 5,8,11,14-eicosatetraynoic acid inhibited the biosynthesis of 18(R)-HETE from arachidonic acid (IC50 0.16 and 0.14 mM, respectively). In comparison with 20:4 or 18:3(n-3), 18:1(n-9) and 22:5(n-6) appeared to be slowly metabolized by seminal monooxygenases, while 18:2(n-6) was converted to the w3 alcohol and to smaller amounts of the w2 alcohol (4:1). Together, the results indicate that the w3-hydroxylase and w3-epoxygenase enzyme(s) metabolize 20:4(n-6) and 20:5(n-3) almost exclusively to the w3(R) alcohol and the w3(R, S) epoxide, respectively, while longer and shorter fatty acids either are poor

Quantifying Residues from Postharvest Propylene Oxide Fumigation of Almonds and Walnuts.

Science.gov (United States)

Jimenez, Leonel R; Hall, Wiley A; Rodriquez, Matthew S; Cooper, William J; Muhareb, Jeanette; Jones, Tom; Walse, Spencer S

2015-01-01

A novel analytical approach involving solvent extraction with methyl tert-butyl ether (MTBE) followed by GC was developed to quantify residues that result from the postharvest fumigation of almonds and walnuts with propylene oxide (PPO). Verification and quantification of PPO, propylene chlorohydrin (PCH) [1-chloropropan-2-ol (PCH-1) and 2-chloropropan-1-ol (PCH-2)], and propylene bromohydrin (PBH) [1-bromopropan-2-ol (PBH-1) and 2-bromopropan-1-ol (PBH-2)] was accomplished with a combination of electron impact ionization MS (EIMS), negative ion chemical ionization MS (NCIMS), and electron capture detection (ECD). Respective GC/EIMS LOQs for PPO, PCH-1, PCH-2, PBH-1, and PBH-2 in MTBE extracts were [ppm (μg/g nut)] 0.9, 2.1, 2.5, 30.3, and 50.0 for almonds and 0.8, 2.2, 2.02, 41.6, and 45.7 for walnuts. Relative to GC/EIMS, GC-ECD analyses resulted in no detection of PPO, similar detector responses for PCH isomers, and >100-fold more sensitive detection of PBH isomers. NCIMS did not enhance detection of PBH isomers relative to EIMS and was, respectively, approximately 20-, 5-, and 10-fold less sensitive to PPO, PCH-1, and PCH-2. MTBE extraction efficiencies were >90% for all analytes. The 10-fold concentration of MTBE extracts yielded recoveries of 85-105% for the PBH isomers and a concomitant decrease in LODs and LOQs across detector types. The recoveries of PCH isomers and PPO in the MTBE concentrate were relatively low (approximately 50 to 75%), which confound improvements in LODs and LOQs regardless of detector type.

An investigation into the Ti-grafting structure on MCM-41 and epoxidation catalysis

DEFF Research Database (Denmark)

Yuan, Q.C.; Hagen, A.; Roessner, F.

2006-01-01

The structure of titanium species grafted on a purely siliceous MCM-41 and their catalysis in the epoxidation of cyclohexene with tert-butyl hydroperoxide (TBHP) were investigated. FT-IR, XANES and UV-vis were used for the examination of the Ti-grafted MCM-41. The results indicated...... that the titanium atoms are grafted on the wall surface of the MCM-41 by four-fold coordination. The four-fold coordinated titanium species are mainly grafted by two or one -O-Si-O- bridges on the MCM-41, resulting in so-called bipodal or monopodal titanium centres in partially polymerised states. The ratio...... of monopodal to bipodal titanium increases with the increase in Ti-content. These partially polymerised titanium species considered as catalytic active centres have high activity and selectivity in the epoxidation reaction. The used Ti-grafted MCM-41 samples were regenerated by heating in nitrogen or air...

Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

KAUST Repository

Widger, Peter C. B.; Ahmed, Syud M.; Coates, Geoffrey W.

2011-01-01

Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

KAUST Repository

Widger, Peter C. B.

2011-07-26

Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

Systematic study on the influence of the morphology of α-MoO3 in the selective oxidation of propylene

DEFF Research Database (Denmark)

Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin

2015-01-01

A variety of morphologically different α-MoO3 samples were prepared by hydrothermal synthesis and applied in the selective oxidation of propylene. Their catalytic performance was compared to α-MoO3 prepared by flame spray pyrolysis (FSP) and a classical synthesis route. Hydrothermal synthesis from...... with nitric acid at 180°C. Particularly, if nitric acid was used during synthesis, the rod-like morphology of the samples could be stabilized during calcination at 550°C and the following catalytic activity tests, which was beneficial for the catalytic performance in propylene oxidation. Characterization...... studies using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy showed that those samples, which retained their rod-like morphology during the activity tests, yielded the highest propylene conversion....

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.

A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

KAUST Repository

Bahri-Laleh, Naeimeh; Nekoomanesh-Haghighi, Mehdi; Mirmohammadi, Seyed Amin

2012-01-01

-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene

Electrochemical reduction of CO2 to CO over Zn in propylene carbonate/tetrabutylammonium perchlorate

Science.gov (United States)

Shen, Feng-xia; Shi, Jin; Chen, Tian-you; Shi, Feng; Li, Qing-yuan; Zhen, Jian-zheng; Li, Yun-fei; Dai, Yong-nian; Yang, Bin; Qu, Tao

2018-02-01

Developing low cost and high efficient electrode for carbon dioxide (CO2) reduction in organic media is essential for practical application. Zn is a cheap metal and has high catalytic effects on CO2 reduction to carbon monoxide (CO) in aqueous solution. However, little attention has been given to investigate the performance of Zn in organic media for CO2 reduction. In present work, we have conducted CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate on Zn due to that propylene carbonate is a widely used industrial absorber, and tetrabutylammonium perchlorate is a commonly used organic supporting electrolyte. In addition, because electrochemical reduction of CO2 to CO naturally produces H2O, we have discussed water effects on CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate+6.8 wt % H2O. Our experiment results reveal that the faradaic efficiency for CO formation reaches to 83%, and the current density remains stable at 6.72 mA/cm2 at voltage -2.3 V for 4 h. Interestingly, Zn presents higher catalytic activity than Ag, and slightly lower than Au. X-ray photoelectron spectroscopy results confirm that no poisonous species is formed and absorbed on the cathode, which is an important advantage in practical application.

The epoxide-diol pathway in the metabolism of vinylbital in rat and man

NARCIS (Netherlands)

Vermeulen, N P; Bakker, B H; Eylers, D; Breimer, D D

1. In urine of rats given vinylbital (5-vinyl-5-(1'-methylbutyl)barbituric acid) i.p., unchanged vinylbital and its devinylated metabolite, 5-(1'-methylbutyl)barbituric acid, were identified. Rats synthetic 1',2'-epoxyvinylbital excreted the same compound as a major metabolite. No unchanged epoxide,

The role of epoxide hydrolase Y113H gene variant in pancreatic diseases.

NARCIS (Netherlands)

Ockenga, J.; Strunck, S.; Post, C.; Schulz, H.U.; Halangk, J.; Pfutzer, R.H.; Lohr, M.; Oettle, H.; Kage, A.; Rosendahl, J.; Keim, V.; Drenth, J.P.H.; Jansen, J.B.M.J.; Lochs, H.; Witt, H.

2009-01-01

OBJECTIVES: Chronic pancreatitis (CP) and pancreatic adenocarcinoma (pCA) are associated with risk factors such as alcohol intake and tobacco smoking. Microsomal epoxide hydrolase (EPHX1) is a phase II detoxifying enzyme capable of tobacco-borne toxicant inactivation. We studied the role of the

Polyethers for biomedical applications. Polymerization of propylene oxide by organozinc/organotin catalysts

NARCIS (Netherlands)

Bots, Jan Gert; van der Does, L.; Bantjes, Adriaan; Broersma, Jaap

1987-01-01

The polymerization of propylene oxide to obtain a high-molecular-weight polymer with an atactic structure required for the application as artificial blood vessels was investigated using combinations of organozinc and organotin compounds as catalyst. The composition of the most active catalyst,

Quantifying residues from postharvest fumigation of almonds and walnuts with propylene oxide

Science.gov (United States)

A novel analytical approach, involving solvent extraction with methyl tert-butyl ether (MTBE) followed by gas chromatography (GC), was developed to quantify residues that result from the postharvest fumigation of almonds and walnuts with propylene oxide (PPO). Verification and quantification of PPO,...

Ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate

Energy Technology Data Exchange (ETDEWEB)

Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in [Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

2015-02-15

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of free ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.

La consommation de propylène en Europe occidentale Propylene Consumption in Western Europe

Directory of Open Access Journals (Sweden)

Barraqué M.

2006-11-01

'éthylène; - le craquage du méthanol. The needs of Western Europe for propylene used in petrochemistry are currently 7. 4 x 10 to the power of 6 metric tons per year. In the coming years, the average rate of increase should be about 1. 8 % per year. Hence in 1995 European petrochemicals should use about 8. 7 x 10 to the power of 6 tons of propylene,Most of this increase in consumption will be due to the sharp rise in polypropylene production and to a lesser extent in propylene oxide, isopropanol and 2-ethyl hexanol production. However, uses for acrylonitrile and cumene will remain fairly stable. Propylene consumption for butanol production should decrease. The share of propylene needs met by European steam crackers, which was 82% in 1986, should be less than 75% in 1995. It will be more and more necessary to turn to other sources of supply. In 1986 European refineries produced 1. 05 x 10 to the power of 6 tons of propylene used for petrochemicals, and imports amounted to 0. 3 x 10 to the power of 6 tons. In 1995 the difference between consumption and production by steam crackers could be beyond 2. 0 x 10 to the power of 6 tons. It seems improbable that catalytic cracking plants can make up for the deficit except if propylene yields were to increase a great deal. The construction of propylene/propane splitters can be expected along with an increase in imports. Likewise, due to the tension that risks could appear in propylene prices, the advantage of some synthesis routes now considered not to be profitable might increase. These new routes are :(a dehydrogenation of propane as is already being considered in other regions (Mexico, Indonesia, Malaysia;(b metathesis between ethylene and butenes-2, which themselves can be produced from ethylene;(c methanol cracking.

Molecular Mechanisms and New Treatment Paradigm for Atrial Fibrillation.

Science.gov (United States)

Sirish, Padmini; Li, Ning; Timofeyev, Valeriy; Zhang, Xiao-Dong; Wang, Lianguo; Yang, Jun; Lee, Kin Sing Stephen; Bettaieb, Ahmed; Ma, Sin Mei; Lee, Jeong Han; Su, Demetria; Lau, Victor C; Myers, Richard E; Lieu, Deborah K; López, Javier E; Young, J Nilas; Yamoah, Ebenezer N; Haj, Fawaz; Ripplinger, Crystal M; Hammock, Bruce D; Chiamvimonvat, Nipavan

2016-05-01

Atrial fibrillation represents the most common arrhythmia leading to increased morbidity and mortality, yet, current treatment strategies have proven inadequate. Conventional treatment with antiarrhythmic drugs carries a high risk for proarrhythmias. The soluble epoxide hydrolase enzyme catalyzes the hydrolysis of anti-inflammatory epoxy fatty acids, including epoxyeicosatrienoic acids from arachidonic acid to the corresponding proinflammatory diols. Therefore, the goal of the study is to directly test the hypotheses that inhibition of the soluble epoxide hydrolase enzyme can result in an increase in the levels of epoxyeicosatrienoic acids, leading to the attenuation of atrial structural and electric remodeling and the prevention of atrial fibrillation. For the first time, we report findings that inhibition of soluble epoxide hydrolase reduces inflammation, oxidative stress, atrial structural, and electric remodeling. Treatment with soluble epoxide hydrolase inhibitor significantly reduces the activation of key inflammatory signaling molecules, including the transcription factor nuclear factor κ-light-chain-enhancer, mitogen-activated protein kinase, and transforming growth factor-β. This study provides insights into the underlying molecular mechanisms leading to atrial fibrillation by inflammation and represents a paradigm shift from conventional antiarrhythmic drugs, which block downstream events to a novel upstream therapeutic target by counteracting the inflammatory processes in atrial fibrillation. © 2016 American Heart Association, Inc.

Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

Science.gov (United States)

Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

2018-04-11

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

Effect of irradiation on poly(vinyl chloride)/epoxidized natural rubber blend in the presence of additives: FTIR analysis

International Nuclear Information System (INIS)

Chantara Thevy Ratnam; Khairul Zaman Dahlan; Baharin, A.; Nasir, M.

2001-01-01

The effect of irradiation on the structure of 50/50 poly(vinyl chloride)/epoxidized natural rubber blend (PVC/ENR) was studied using the Fourier Transform Spectroscopy (FTIR). The 50/50 PVC/ENR blend was irradiated by using 3.0 MeV electron beam machine at 0 and 200 kGy irradiation doses. The influence of several additives such as TMPTA, Irganox 1010, and tribasic lead sulfate on the irradiation induced changes of the blend was investigated. It was found that upon irradiation, ring opening of the epoxide groups, oxidation as well crosslinking at residual double bonds occurred, leading to decreases in the intensities of the epoxide and cis double bond bands and an increases in ether and furan bands. The addition of Irganox 1010 and tribasic lead sulfate were found to inhibit the irradiation-induced reaction in the blend to a considerable extent. The importance of TMPTA in preventing the intramolecular ring opening side chain reaction was also discussed. However, studies did not reveal the exact nature of the irradiation-induced reactions involved in the blend. (Author)

"Green" composites from renewable resources: preparation of epoxidized soybean oil and flax fiber composites.

Science.gov (United States)

Liu, Zengshe; Erhan, Sevim Z; Akin, Danny E; Barton, Franklin E

2006-03-22

In recent years there has been considerable interest in using natural plant fibers as reinforcements for plastics. The motivation includes cost, performance enhancement, weight reduction, and environment concerns. High performance flax fiber could potentially substitute for glass or carbon fibers as reinforcements for plastics. This study reports the "green" composites obtained from a mixture of epoxidized soybean oil and epoxy resin, 1,1,1-tris(p-hydroxyphenyl)ethane triglycidyl ether (THPE-GE), reinforced with flax fiber. The compression molding method is used for making the composites. Curing agents triethylenetetramine and diethylenetriamine provide better physical properties of the composites than Jeffamine agents D-230 and EDR-148. Both the flexural modulus and the tensile modulus of the composites increase as the amount of THPE-GE increases. The flexural modulus increased at a fiber content of fiber content until a maximum at 13.5 wt %, and then it decreases. The flax fiber length affected the mechanical properties of the composites: the longer the fiber length, the better are the mechanical properties observed.

Synthesis and Absolute Configuration of Enantiomerically Pure Vitamin K3 2,3-Epoxide

NARCIS (Netherlands)

Snatzke, Günther; Wijnberg, Hans; Feringa, Bernard; Marsman, Bea G.; Greydanus, Ben; Pluim, Henk

1980-01-01

The 2,3-epoxide of vitamin K3 (menadione, 1) has been prepared in enantiomerically pure form, and the absolute configuration has been deduced from the CD spectrum. The compound with the negative Cotton effect between 340 and 400 nm has the 2R,3S configuration.

Synthesis of epoxidized cardanol and its antioxidative properties for vegetable oils and biodiesel

Science.gov (United States)

A novel antioxidant epoxidized cardanol (ECD), derived from cardanol, was synthesized and characterized by FT-IR, 1H-NMR and 13C-NMR. Oxidative stability of ECD used in vegetable oils and biodiesel was evaluated by pressurized differential scanning calorimetry (PDSC) and the Rancimat method, respect...

Cloning and characterization of an epoxide hydrolase-encoding gene from Rhodotorula glutinis

NARCIS (Netherlands)

Visser, H.; Vreugdenhil, S.; Bont, de J.A.M.; Verdoes, J.C.

2000-01-01

We cloned and characterized the epoxide hydrolase gene, EPH1, from Rhodotorula glutinis. The EPH1 open reading frame of 1230 bp was interrupted by nine introns and encoded a polypeptide of 409 amino acids with a calculated molecular mass of 46.3 kDa. The amino acid sequence was similar to that of

Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

Science.gov (United States)

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

Effects of partial hydrogenation, epoxidation, and hydroxylation on the fuel properties of fatty acid methyl esters

Energy Technology Data Exchange (ETDEWEB)

Wadumesthrige, Kapila; Salley, Steven O.; Ng, K.Y. Simon [Department of Chemical Engineering and Materials Science, Wayne State University, 5050 Anthony Wayne Drive, Detroit, MI 48202 (United States)

2009-10-15

The properties of biodiesel depend on the chemical structure of individual fatty acid methyl esters (FAME). In this work the chemical structure of fatty acid chains was modified by catalytic hydrogenation, epoxidation and hydroxylation under controlled conditions. Hydrolysis of ester functionality or oxidation of fatty acid chain was not observed during these reactions. The properties of hydrogenated FAME strongly depend on the hydrogenation time. The total saturated fatty acid (SFA) percentage increased from 29.3% to 76.2% after 2 h of hydrogenation. This hydrogenated FAME showed higher oxidation stability and higher cetane number but poor cold flow properties. Formation of trans FAME was observed during hydrogenation. Both hydroxylation and epoxidation resulted in a decrease of unsaturated fatty acid methyl ester (UFA) fraction. The percentages of total unsaturated FAME decreased 39% in the epoxidation reaction and 44% in the hydroxylation reaction. The addition of hydroxyl groups to the unsaturated regions of the fatty acid chain yields biodiesel with better cold flow properties, increased lubricity and slightly increased oxidative stability. However, epoxy FAME shows some interesting properties such as higher oxidation stability, higher cetane number and acceptable cold flow properties, which met the limits of ASTM D6751 biodiesel specifications. (author)

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.

Si-Imidazole-HSO4 Functionalized Magnetic Fe3O4 Nanoparticles as an Efficient and Reusable Catalyst for the Regioselective Ring Opening of Epoxides in Water

Directory of Open Access Journals (Sweden)

Eshagh Rezaee Nezhad

2016-01-01

Full Text Available An efficient and simple method for the preparation of Si-Imidazole-HSO4 functionalized magnetic Fe3O4 nanoparticles (Si-Im-HSO4 MNPs and used as an efficient and reusable magnetic catalysts for the regioselective ring opening of epoxides under green conditions in water. This catalyst was used for the ring opening of epoxide corresponding to the thiocyanohydrins and azidohydrines. Compared to the classical ring opening of epoxides, this new method consistently has the advantage of excellent yields, short reaction times, and methodological simplicity.

Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

Science.gov (United States)

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.

Performance of 6FDA–6FpDA polyimide for propylene/propane separations

KAUST Repository

Das, Mita

2010-12-01

This work addresses the challenges faced by previous researchers with 6FDA-6FpDA polyimide for propylene/propane separations due to plasticization. A study of film annealing temperature is reported to optimize plasticization suppression in elevated temperature permeation on properly annealed dense films made with high molecular weight polymer. A detailed analysis of pure and mixed gas results using different permeability models is shown in this work. The annealing effects in terms of plasticization suppression and permeability and selectivity changes are discussed in detail. According to our best knowledge, this is for the first time plasticization suppression for propylene/propane has been reported with any polyimide dense film membrane. Results of pure gas sorption experiments using a pressure decay method with un-annealed and annealed films are discussed and used to analyze the permeation data using the dual-mode model. Mixed gas permeation results also are explained with dual mode and bulk flow transport models. © 2010 Elsevier B.V.

An efficient hybrid, nanostructured, epoxidation catalyst: titanium silsesquioxane-polystyrene copolymer supported on SBA-15

NARCIS (Netherlands)

Santen, van R.A.; Zhang, Lei; Abbenhuis, H.C.L.; Gerritsen, G.; Ní Bhriain, N.M.; Magusin, P.C.M.M.; Mezari, B.; Han, W.; Yang, Q.; Li, Can

2007-01-01

A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active

Selective oxidation of propylene to acrolein by silica-supported bismuth molybdate catalysts

DEFF Research Database (Denmark)

Duc, Duc Truong; Ha, Hanh Nguyen; Fehrmann, Rasmus

2011-01-01

Silica-supported bismuth molybdate catalysts have been prepared by impregnation, structurally characterized and examined as improved catalysts for the selective oxidation of propylene to acrolein. Catalysts with a wide range of loadings (from 10 to 90 wt%) of beta bismuth molybdate (β-Bi2Mo2O9) w...

Zinc-substituted ZIF-67 nanocrystals and polycrystalline membranes for propylene/propane separation

KAUST Repository

Wang, Chongqing

2016-09-09

Continuous ZIF-67 polycrystalline membranes with effective propylene/propane separation performances were successfully fabricated through the incorporation of zinc ions into the ZIF-67 framework. The separation factor increases from 1.4 for the pure ZIF-67 membrane to 50.5 for the 90% zinc-substituted ZIF-67 membrane.

Epoxide hydrolase affects estrogen production in the human ovary.

Science.gov (United States)

Hattori, N; Fujiwara, H; Maeda, M; Fujii, S; Ueda, M

2000-09-01

To investigate the mechanisms of ovarian cell differentiation, we raised a new monoclonal antibody, HCL-3, which reacted with human luteal cells. It also reacted with human and porcine hepatocytes. The immunoaffinity-purified HCL-3 antigen from human corpora lutea (CL) was shown to be a 46-kDa protein. The N-terminal 22 amino acids of the 46-kDa protein from porcine liver exhibited high homology (82%) to human microsomal epoxide hydrolase (mEH). The purified HCL-3 antigen from human CL or porcine liver showed EH enzyme activity, confirming that HCL-3 antigen is identical to mEH, which is reported to detoxify the toxic substrates in the liver. In human follicles, mEH was immunohistochemically detected on granulosa and theca interna cells. In the menstrual and pregnant CL, mEH was also expressed on large and small luteal cells. A competitive inhibitor of EH, 1,2-epoxy-3,3,3-trichloropropane, inhibited the conversion of estradiol from testosterone by granulosa cells cultured in vitro, indicating the involvement of mEH in ovarian estrogen production. Because anticonvulsant sodium valproate and its analogues were reported to inhibit EH enzyme activity, these findings provide a new insight into the etiology of endocrine disorders that are frequently observed among epileptic patients taking anticonvulsant drugs.

Infrared cross-sections and integrated band intensities of propylene: Temperature-dependent studies

KAUST Repository

Es-sebbar, Et-touhami

2014-01-01

Propylene, a by-product of biomass burning, thermal cracking of hydrocarbons and incomplete combustion of fossil fuels, is a ubiquitous molecule found in the environment and atmosphere. Accurate infrared (IR) cross-sections and integrated band intensities of propylene are essential for quantitative measurements and atmospheric modeling. We measured absolute IR cross-sections of propylene using Fourier Transform Infrared (FTIR) Spectroscopy over the wavenumber range of 400-6500cm-1 and at gas temperatures between 296 and 460K. We recorded these spectra at spectral resolutions ranging from 0.08 to 0.5cm-1 and measured the integrated band intensities for a number of vibrational bands in certain spectral regions. We then compared the integrated band intensities measured at room temperature with values derived from the National Institute of Standards and Technology (NIST) and the Pacific Northwest National Laboratory (PNNL) databases. Our results agreed well with the results reported in the two databases with a maximum deviation of about 4%. The peak cross-sections for the primary bands decreased by about 20-54% when the temperature increased from 296 to 460K. Moreover, we determined the integrated band intensities as a function of temperature for certain features in various spectral regions; we found no significant temperature dependence over the range of temperatures considered here. We also studied the effect of temperature on absorption cross-section using a Difference Frequency Generation (DFG) laser system. We compared the DFG results with those obtained from the FTIR study at certain wavenumbers over the 2850-2975cm-1 range and found a reasonable agreement with less than 10% discrepancy. © 2013 Elsevier Ltd.

The influence of propylene glycol ethers on base diesel properties and emissions from a diesel engine

International Nuclear Information System (INIS)

Gómez-Cuenca, F.; Gómez-Marín, M.; Folgueras-Díaz, M.B.

2013-01-01

Highlights: • Effect of propylene glycol ethers on diesel fuel properties. • Effect of these compounds on diesel engine performance and emissions. • Blends with ⩽4 wt.% of oxygen do not change substantially diesel fuel quality. • Blends with ⩽2.5 wt.% of oxygen reduce CO, HC and NOx emissions, but not smoke. • These compounds are helpful to reach a cleaner combustion in a diesel engine. - Abstract: The oxygenated additives propylene glycol methyl ether (PGME), propylene glycol ethyl ether (PGEE), dipropylene glycol methyl ether (DPGME) were studied to determine their influence on both the base diesel fuel properties and the exhaust emissions from a diesel engine (CO, NOx, unburnt hydrocarbons and smoke). For diesel blends with low oxygen content (⩽4.0 wt.%), the addition of these compounds to base diesel fuel decreases aromatic content, kinematic viscosity, cold filter plugging point and Conradson carbon residue. Also, each compound modifies the distillation curve at temperatures below the corresponding oxygenated compound boiling point, the distillate percentage being increased. The blend cetane number depends on the type of propylene glycol ether added, its molecular weight, and the oxygen content of the fuel. The addition of PGME decreased slightly diesel fuel cetane number, while PGEE and DPGME increased it. Base diesel fuel-propylene glycol ether blends with 1.0 and 2.5 wt.% oxygen contents were used in order to determine the performance of the diesel engine and its emissions at both full and medium loads and different engine speeds (1000, 2500 and 4000 rpm). In general, at full load and in comparison with base diesel fuel, the blends show a slight reduction of oxygen-free specific fuel consumption. CO emissions are reduced appreciably for 2.5 wt.% of oxygen blends, mainly for PGEE and DPGME. NOx emissions are reduced slightly, but not the smoke. Unburnt hydrocarbon emissions decrease at 1000 and 2500 rpm, but not at 4000 rpm. At medium load

Solid-state drawing of post-consumer isotactic poly(propylene): Effect of melt filtration and carbon black on structural and mechanical properties.

Science.gov (United States)

Luijsterburg, B J; Jobse, P S; Spoelstra, A B; Goossens, J G P

2016-08-01

Post-consumer plastic waste obtained via mechanical recycling is usually applied in thick-walled products, because of the low mechanical strength due to the presence of contaminants. In fact, sorted post-consumer isotactic poly(propylene) (i-PP) can be considered as a blend of 95% i-PP and 5% poly(ethylene), with traces of poly(ethylene terephthalate) (PET). By applying a treatment such as solid-state drawing (SSD) after melt extrusion, the polymer chains can be oriented in one direction, thereby improving the stiffness and tensile strength. In this research, molecular processes such as crystal break-up and chain orientation of these complex blends were monitored as a function of draw ratio. The melt filter mesh size - used to exclude rigid PET particles - and the addition of carbon black (CB) - often added for coloration in the recycling industry - were varied to investigate their influence on the SSD process. This research shows that despite the blend complexity, the molecular processes during SSD compare to virgin i-PP and that similar draw ratios can be obtained (λmax=20), albeit at reduced stiffness and strength as a result of the foreign polymers present in post-consumer i-PP. It is observed that the process stability improves with decreasing mesh size and that higher draw ratios can be obtained. The addition of carbon black, which resides in the dispersed PE phase, also stabilizes the SSD process. Compared to isotropic post-consumer i-PP, the stiffness can be improved by a factor 10 to over 11GPa, while the tensile strength can be improved by a factor 15-385MPa, which is approx. 70% of the maximum tensile strength achieved for virgin i-PP. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermoreversible cross-linking of maleated ethylene/propylene copolymers with diamines and amino-alcohols

NARCIS (Netherlands)

Mee, van der M.A.J.; Goossens, J.G.P.; Duin, van M.

2008-01-01

Maleated ethylene/propylene copolymers (MAn-g-EPM) were thermoreversibly cross-linked using diamines and amino-alcohols. Covalent cross-links are formed via the equilibrium reaction of the grafted anhydride groups with di-functional cross-linkers containing combinations of primary (1°) and secondary

High-temperature epoxidation of soybean oil in flow : speeding up elemental reactions wanted and unwanted

NARCIS (Netherlands)

Cortese, B.; Croon, de M.H.J.M.; Hessel, V.

2012-01-01

The soybean oil epoxidation reaction is investigated theoretically through kinetic modeling of temperature effects enabled through flow processing under superheated conditions. Different from previous studies on such processing, here a complex reaction network superimposed by multiphase transport is

Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

Energy Technology Data Exchange (ETDEWEB)

Xu, Tiwen [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Jia, Zhixin, E-mail: zxjia@scut.edu.cn [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Luo, Yuanfang; Jia, Demin [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Peng, Zheng [Agricultural Product Processing Research Institute, Chinese Academy of Tropical Agriculture Sciences, Zhanjiang 524001 (China)

2015-02-15

Highlights: • Substantiate the ring open reaction between Si-OH of silica and epoxy groups of ENR. • ENR can act as a bridge between NR and silica to enhance the interfacial interaction. • As a modifier, ENR gets the potential to be used in the tread of green tire for improving the wet skid resistance apparently. - Abstract: The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress–strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

Heteropolytungstate nanoparticles: Microemulsion-mediated preparation and investigation of their catalytic activity in the epoxidation of olefins

Energy Technology Data Exchange (ETDEWEB)

Masteri-Farahani, M., E-mail: mfarahany@yahoo.com; Ghorbani, M.

2016-04-15

Highlights: • Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles were synthesized by using microemulsion system. • The nanoparticles have uniform size of about 25 nm and spherical morphologies. • The prepared nanoparticles act as reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}. - Abstract: Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles (Q = cetyltrimethylammonium cation) were synthesized in water-in-oil (w/o) microemulsion consisted of water/cetyltrimethylammonium bromide/n-butanol/isooctane. Reaction of Na{sub 2}WO{sub 4}, Na{sub 2}HPO{sub 4} and hydrochloric acid within water containing nanoreactors of reverse micelles resulted in the preparation of Q{sub 3}PW{sub 12}O{sub 40} nanoparticles. The resultant nanoparticles were analyzed by physicochemical methods such as FT-IR spectroscopy, X-ray diffraction, energy-dispersive X-ray analysis, thermogravimetric analyses (TGA-DTA), scanning and transmission electron microscopy and atomic force microscopy which show nearly uniform spherical nanoparticles with size of about 15 nm. Finally, catalytic activity of the Q{sub 3}PW{sub 12}O{sub 40} nanoparticles was examined in the epoxidation of olefins with H{sub 2}O{sub 2}. The prepared nanoparticles acted as recoverable and reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}.

Enhancement of catalyst performance in the direct propene epoxidation: a study into gold-titanium synergy

NARCIS (Netherlands)

Chen, J.; Halin, S.J.A.; Pidko, E.A.; Verhoeven, M.W.G.M.; Perez Ferrandez, D.M.; Hensen, E.J.M.; Schouten, J.C.; Nijhuis, T.A.

2013-01-01

Enhanced productivity toward propene oxide in the direct propene epoxidation with hydrogen and oxygen over gold nanoparticles supported on titanium-grafted silica was achieved by adjusting the gold–titanium synergy. Highly isolated titanium sites were obtained by lowering the titanium loading

Mechanistic aspects of the metal catalyzed alternating copolymerization of epoxides and carbon monoxide.

Science.gov (United States)

Allmendinger, Markus; Molnar, Ferenc; Zintl, Manuela; Luinstra, Gerrit A; Preishuber-Pflügl, Peter; Rieger, Bernhard

2005-09-05

The cobalt-catalyzed alternating copolymerization of epoxides and CO is a novel, direct approach to aliphatic polyesters, such as poly(hydroxybutyrate) (PHB). This reaction was found to be catalyzed by Ph3Si[Co(CO)4] (4) and pyridine affording in a first step the stable mono-insertion product Ph3Si-O-CH(CH3)-CH2-CO-Co(CO)4 (5). However, a profound mechanistic understanding, especially of the role of pyridine as the key component for the polymerization reaction was missing. ATR-IR online monitoring under catalytic conditions and DFT calculations were used to show that an acylpyridinium cation is formed by cleavage of the cobalt-acyl bond of 5 in the presence of pyridine. The Lewis acid thus generated activates the next incoming epoxide monomer for ring opening through [Co(CO)4]-. The catalytic cycle is completed by a subsequent CO insertion in the new cobalt-alkyl bond. The calculations are used to explore the energetic hypersurface of the polymerization reaction and are complemented by extended experimental investigations that also support the mechanistic hypotheses.

Atofina participates to a negotiation for two vapo-cracking units in Qatar. Investment in propylene at Singapore. PP: start-up for Formosa...; Atofina participe a une negociation pour deux vapocraqueurs au Qatar. Investissement dans le propylene a Singapour. PP: demarrage pour Formosa...

Energy Technology Data Exchange (ETDEWEB)

Anon.

2002-03-01

Atofina company is finalizing an important negotiation with Qatar General Petroleum Co (QGPC) and Chevron Phillips Chemical for the building of two vapo-cracking units at Ras Laffan, named Q-Chem and Qatofin, which aim at producing about 2 millions of tons of ethylene per year (short paper). Petrochemical Corp. of Singapore (PCS) has decided to increase the propylene capacity of its two vapo-cracking units of Jurong Island. The aim is to add-up 200000 to 300000 t/year of propylene using the metathesis process of ABB Lummus Global and/or the Superflex technology of Halliburton KBR. These processes convert ethylene and C4 olefins into propylene (short paper). Formosa Plastics, which launched a first polypropylene line of 120000 t/year at its Point Comfort site (Texas) in April 2001, has just put into service a second line with the same capacity which raises the total capacity of the unit to 320000 t/year. (short paper). (J.S.)

First results from electron-photon damage equivalence studies on a generic ethylene-propylene rubber

International Nuclear Information System (INIS)

Buckalew, W.H.

1986-04-01

As part of a simulator adequacy assessment program, the relative effectiveness of electrons and photons to produce damage in a generic ethylene propylene rubber (EPR) has been investigated. The investigation was limited in extent in that a single EPR material, in three thickness, was exposed to Cobalt-60 photons and three electron beam energies. Basing material damage on changes in the EPR mechanical properties elongation and tensile strength, we observed that EPR damage was a smoothly varying function of absorbed energy and independent of irradiating particle type. EPR damage tracked equally well as a function of both incident particle energy and material front surface dose. Based on these preliminary data, we tentatively concluded that a correlation between particle, particle energy, and material damage (as measured by changes in material elongation and/or tensile strength) has been demonstrated. 14 figs

One pot 'click' reactions : tandem enantioselective biocatalytic epoxide ring opening and [3+2] azide alkyne cycloaddition

NARCIS (Netherlands)

Campbell-Verduyn, Lachlan S.; Szymanski, Wiktor; Postema, Christiaan P.; Dierckx, Rudi A.; Elsinga, Philip H.; Janssen, Dick B.; Feringa, Ben L.

2010-01-01

Halohydrin dehalogenase (HheC) can perform enantioselective azidolysis of aromatic epoxides to 1,2-azido alcohols which are subsequently ligated to alkynes producing chiral hydroxy triazoles in a one-pot procedure with excellent enantiomeric excess.

Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

Directory of Open Access Journals (Sweden)

Xiao Wu

2016-01-01

Full Text Available The catalytic synthesis of cyclic carbonates using carbon dioxide as a C1-building block is a highly active area of research. Here, we review the catalytic production of enantiomerically enriched cyclic carbonates via kinetic resolution of racemic epoxides catalysed by metal-containing catalyst systems.

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, 7

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Machi, Sueo; Okamoto, Jiro.

1982-02-01

In order to avoid the effects of number of polymer particles on polymerization and bubbles generated by mixing of gaseous monomer and emulsifier-water solution at the early stage of emulsion polymerization, seeded copolymerization of tetrafluoroethylene with propylene by radiation was studied in flow apparatus equipped with tank and pipe type reactors under a pressure of 30 kg/cm 2 and a temperature of 40 0 C. The polymerization rate increases with dose rate and its dose rate exponent changes from 1.0 to 0.5 with increase of dose rate from 10 5 to 10 6 rad/h. In the series of investigation, it was found that the polymer concentration in latex tended to increase accelerately with reaction time. The effects of mean residence time of latex in the reactor and recycle rate of gaseous monomer on the polymerization could not be elucidated because of the acceleration of polymer concentration in latex. The acceleration is assumed to be due to repression of termination reaction by decreases of propylene concentration and mobility of polymer radical in particles with proceeding the polymerization. (author)

Extraction mechanism of sulfamethoxazole in water samples using aqueous two-phase systems of poly(propylene glycol) and salt

Energy Technology Data Exchange (ETDEWEB)

Xie Xueqiao; Wang Yun; Han Juan [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Yan Yongsheng, E-mail: yys@ujs.edu.cn [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China)

2011-02-14

Based on the poly(propylene glycol){sub 400} (PPG{sub 400})-salt aqueous two-phase system (ATPS), a green, economical and effective sample pretreatment technique coupled with high performance liquid chromatography was proposed for the separation and determination of sulfamethoxazole (SMX). The extraction yield of SMX in PPG{sub 400}-salt ATPS is influenced by various factors, including the salt species, the amount of salt, pH, and the temperature. Under the optimum conditions, most of SMX was partitioning into the polymer-rich phase with the average extraction efficiency of 99.2%, which may be attributed to the hydrophobic interaction and salting-out effect. This extraction technique has been successfully applied to the analysis of SMX in real water samples with the recoveries of 96.0-100.6%, the detection limits of 0.1 {mu}g L{sup -1}, and the linear ranges of 2.5-250.0 {mu}g L{sup -1}.

Characteristics of polyaniline electrosynthesized in propylene carbonate medium in the presence of di- and trichloroacetic acids

Directory of Open Access Journals (Sweden)

Venancio Everaldo C.

2001-01-01

Full Text Available In the present work the characterization of polyaniline electrosynthesized in propylene carbonate medium in the presence of di- and trichloroacetic acids was performed using different techniques. The electrochemical response by cyclic voltammetry showed redox processes due to the formation of polaron and bipolaron and polymer degradation. The characterization by infrared and UV-visible spectroscopies indicated that the polymers are in the emeraldine salt form with perchlorate anions incorporated. The films produced with both acids in propylene carbonate media presented a compact morphology as observed by scanning electron microscopy. By testing the polyaniline film produced in selected conditions in a lithium battery environment it was found that it presents a high coulombic efficiency, promising for battery applications.

Exploiting epoxidized natural rubber latex (ENRL) as a starting raw material for latex-based products

Science.gov (United States)

Siti Nor Qamarina, M.; Fatimah Rubaizah, M. R.; Nurul Suhaira, A.; Norhanifah, M. Y.

2017-12-01

Epoxidized natural rubber latex (ENRL) is a chemically modified natural rubber latex produced from epoxidation process that involves usage of organic peracids. Conversion of the ENRL into dry rubber products has been known to exhibit many beneficial properties, however limited published works were found on diversifiying the ENRL latex-based products applications. In this preliminary work, different source of raw materials and neutralization systems were investigated. The objective was to explore possibilities in producing distinctive ENRL. Findings have demonstrated that different source of raw materials and neutralization systems influenced the typical ENRL specifications, stability behavior and particle size distribution. Morphological observations performed on these ENRL systems appeared to agree with the ENRL characteristics achieved. Since experimenting these two main factors resulted in encouraging ENRL findings, detailed work shall be further scrutinized to search for an optimum condition in producing marketable ENRL specifically for latex-based products applications.

Synthesis and properties of cross-linked polymers from epoxidized rubber seed oil and triethylenetetramine

NARCIS (Netherlands)

Abduh, Muhammad Yusuf; Iqbal, Muhammad; Picchioni, Francesco; Manurung, Robert; Heeres, Hero J.

2015-01-01

A series of epoxidized oils were prepared from rubber seed, soybean, jatropha, palm, and coconut oils. The epoxy content varied from 0.03 to 7.4 wt %, in accordance with the degree of unsaturation of the oils (lowest for coconut, highest for rubber seed oil). Bulk polymerization/curing of the

Organic carbonates as solvents in macrocyclic Mn(III) salen catalyzed asymmetric epoxidation of non-functionalized olefins

Czech Academy of Sciences Publication Activity Database

Maity, N. Ch.; Rao, G. V. S.; Prathap, Kaniraj Jeya; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Bajaj, H. C.

2013-01-01

Roč. 366, January (2013), s. 380-389 ISSN 1381-1169 Institutional support: RVO:61388963 Keywords : asymmetric epoxidation * organic carbonate * macrocyclic Mn(III) salen complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.679, year: 2013

Effect of liquid epoxidized natural rubber (LENR) on mechanical properties and morphology of natural rubber/high density polyethylene/mengkuang fiber (NR/HDPE/MK) bio-composite

Science.gov (United States)

Piah, Mohd Razi Mat; Baharum, Azizah

2016-11-01

The use of mengkuang fiber (MK) fibers in NR/HDPE (40/60) blend was studied via surface modification of fiber. The MK fiber was pre-washed with 5%wt/v sodium hydroxide solution prior to treatment with liquid epoxidized natural rubber (LENR). The concentration of LENR were varied from 5%-20%wt in toluene. The effects of LENR concentrations were studied in terms of mechanical properties and morphology formed. Melt-blending was performed using an internal mixer (Haake Rheomix 600). The processing parameters identified were 135°C temperature, 45 rpm rotor speed, 12 minutes processing time and at 20%wt MK fiber loading. The optimum LENR treatment concentration was obtained at 5%wt with tensile strength, tensile modulus, and impact strength of 10.3 MPa, 414.2 MPa and 14.4 kJ/m2 respectively. The tensile modulus of LENR-treated MK fiber filled NR/HDPE bio-composite has shown enhancement up to 16.7% higher than untreated MK fiber. The tensile and impact strength were decreased with increasing LENR concentration due to the broken of MK fibers to smaller particles and adhered to each other. FESEM micrographs confirmed the formation of fiber-fiber agglomeration in NR/HDPE blends. The optical microscope analysis shows MK fibers is shorter than original fiber lengths after NaOH-LENR surface modification. The internal bonding forces of MK fiber seems to be weaker than external force exerted on it, therefore, the MK fiber has broken to smaller particles and reduced the mechanical properties of NR/HDPE/MK(20%) bio-composite.

Natural Optical Activity of Chiral Epoxides: the Influence of Structure and Environment on the Intrinsic Chiroptical Response

Science.gov (United States)

Lemler, Paul M.; Craft, Clayton L.; Vaccaro, Patrick

2017-06-01

Chiral epoxides built upon nominally rigid frameworks that incorporate aryl substituents have been shown to provide versatile backbones for asymmetric syntheses designed to generate novel pharmaceutical and catalytic agents. The ubiquity of these species has motivated the present studies of their intrinsic (solvent-free) circular birefringence (CB), the measurement of which serves as a benchmark for quantum-chemical predictions of non-resonant chiroptical behavior and as a beachhead for understanding the often-pronounced mediation of such properties by environmental perturbations (e.g., solvation). The optical rotatory dispersion (or wavelength-resolved CB) of (R)-styrene oxide (R-SO) and (S,S)-phenylpropylene oxide (S-PPO) have been interrogated under ambient solvated and isolated conditions, where the latter efforts exploited the ultrasensitive techniques of cavity ring-down polarimetry. Both of the targeted systems display marked solvation effects as evinced by changes the magnitude and (in the case of R-SO) the sign of the extracted specific optical rotation, with the anomalously large response evoked from S-PPO distinguishing it from other members of the epoxide family. Linear-response calculations of dispersive optical activity have been performed at both density-functional and coupled-cluster levels of theory to unravel the structural and electronic origins of experimental findings, thereby suggesting the possible involvement of hindered torsional motion along dihedral coordinates adjoining phenyl and epoxide moieties.

Functionalized Poly(propylene imine) Dendrimers as Novel Phase Transfer Catalyst in Supercritical Cabon Dioxide

NARCIS (Netherlands)

Goetheer, E.L.V.; Baars, M.W.P.L.; Broeke, van den L.J.P.; Meijer, E.W.; Keurentjes, J.T.F.

2000-01-01

Perfluoro-functionalized poly(propylene imine) dendrimers have been used as reactive extractants for anionic species and as phase transfer catalysts for two types of reactions. Different generations of dendrimers have been used for applications in carbon dioxide. First, the reactive extraction of

Physicochemical properties of binary solutions of propylene carbonate-acetonitrile in the range of 253.15-313.15 K

Science.gov (United States)

Tyunina, E. Yu.; Chekunova, M. D.

2017-05-01

The density, dynamic viscosity, and dielectric constant of propylene carbonate solutions with acetonitrile are measured over the composition of a mixed solvent at temperatures of 253.15, 273.15, 293.15, and 313.15 K. The molar volume, molar viscosity, and molar capacity of a mixture of propylene carbonate-acetonitrile and an excess amount of it are calculated. The effect the temperature and composition of the mixture have on the excess molar properties is discussed. A linear correlation is observed between the values of the molar fluidity, capacity, polarization, and molar volume of the studied system.

Determination of Mechanical and Surface Properties of Semicrystalline Polyhedral Oligomeric Silsequioxane (POSS) Nanocomposites

National Research Council Canada - National Science Library

Moody, Laura E; Marchant, Darrell; Grabow, Wade W; Lee, Andre Y; Mabry, Joseph M

2005-01-01

.... This study examines the ability of POSS to improve the mechanical and surface properties of three semicrystalline polymers, fluorinated ethylene-propylene (FEP), poly(vinylidene fluoride) (PVDF...

Study of Propylene Glycol, Dimethylformamide and Formaldehyde Vapors Sensors Based on MWCNTs/SnO2 Nanocomposites

Directory of Open Access Journals (Sweden)

Zaven Adamyan

2017-06-01

Full Text Available We present results of our research works related to the study of thick-film multiwall carbon nanotube/tin oxide nanocomposite sensors of propylene glycol (PG, dimethylformamide (DMF and formaldehyde (FA vapors derived using hydrothermal synthesis and sol-gel methods. Investigations of response/recovery characteristics in the 50-300 oC operating temperature range reveal that the optimal operating temperature for PG, DMF and FA vapor sensors, taking into account both high response and acceptable response and recovery times, are about 200 and 220 oC, respectively. A sensor response dependence on gas concentration in all cases is linear. The minimal propylene glycol and dimethylformamide gas concentrations at which the perceptible signal was registered by us were 13 ppm and 5 ppm, respectively.

Thermoreversible cross-linking of maleated ethylene/propylene copolymers using hydrogen-bonding and ionic interactions

NARCIS (Netherlands)

Sun, C.; Mee, van der M.A.J.; Goossens, J.G.P.; Duin, van M.

2006-01-01

Maleated ethylene/propylene copolymers (MAn-g-EPM) were thermoreversibly cross-linked via a reaction with primary alkylamines of different length, either with an equimolar amount to obtain the amideacid or with an excess to obtain the amide-salt, which was confirmed using Fourier transform infrared

Experimental and theoretical study on the reactivity of the R-CN/H2O2 system in the epoxidation of unfunctionalized olefins

Directory of Open Access Journals (Sweden)

von Holleben Maria Luiza A.

2001-01-01

Full Text Available A study on the reactivity of peroxycarboximidic acids in situ generated from acetonitrile, trichloroacetonitrile, benzonitrile, m-chlorobenzonitrile, 3-cyanopyridine, 1-naphthonitrile and 9-anthracenenitrile was performed by semiempirical AM1 method and experimentally in the epoxidation of cyclohexene and R-(+-limonene. Experimental results showed that the reactivity of Cl3CCN/H2O2 was quite similar to MCPBA in the epoxidation of unfunctionalized olefins when a biphasic mixture CH2Cl2/H2O was employed as solvent.

Microstructure study of ethylene, propylene and 1-decene terpolymers by 13C-NMR

International Nuclear Information System (INIS)

Ferreira, Marcio; Escher, Fernanda Nunes; Galland, Griselda Barrera

2001-01-01

Terpolymers of ethylene-propylene-1-decene with different composition of monomers were obtained using the metallocenes catalyst rac-EtInd 2 ZrCl 2 . The complete 13 C-NMR characterization of these terpolymers was done qualitatively and quantitatively. Chemical shifts, carbon assignments and corresponding integrals for each triad sequence are presented. (author)

Direct characterization of cotton fabrics treated with di-epoxide by nuclear magnetic resonance.

Science.gov (United States)

Xiao, Min; Chéry, Joronia; Keresztes, Ivan; Zax, David B; Frey, Margaret W

2017-10-15

A non-acid-based, di-functional epoxide, neopentyl glycol diglycidyl ether (NPGDGE), was used to modify cotton fabrics. Direct characterization of the modified cotton was conducted by Nuclear Magnetic Resonance (NMR) without grinding the fabric into a fine powder. NaOH and MgBr 2 were compared in catalyzing the reaction between the epoxide groups of NPGDGE and the hydroxyl groups of cellulose. Possible reaction routes were discussed. Scanning electron microscopy (SEM) images showed that while the MgBr 2 -catalyzed reaction resulted in self-polymerization of NPGDGE, the NaOH-catalyzed reaction did not. Fourier transform infrared spectroscopy (FTIR) showed that at high NaOH concentration cellulose restructures from allomorph I to II. NMR studies verified the incorporation of NPGDGE into cotton fabrics with a clear NMR signal, and confirmed that at higher NaOH concentration the efficiency of grafting of NPGDGE was increased. This demonstrates that use of solid state NMR directly on woven fabric samples can simultaneously characterize chemical modification and crystalline polymorph of cotton. No loss of tensile strength was observed for cotton fabrics modified with NPGDGE. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preformulation study and influence of DMSO and propylene glycol on the antioxidant action of isocoumarin paepalantine isolated from Paepalanthus bromelioides

Directory of Open Access Journals (Sweden)

João Paulo Loureiro Damasceno

Full Text Available AbstractCoumarins are phenolic compounds and have various biological properties, including antioxidant activity. The isocoumarin paepalantine, isolated from of Paepalanthus bromelioides Silveira, Eriocaulaceae, exhibits a wide range of biological activities, including antimicrobial, anti-inflammatory, antioxidant and cytotoxic properties. Studies on paepalantine often use dimethylsulfoxide as a solvent. However the dimethylsulfoxide interferes with antimicrobial, cytotoxic and antioxidant assays. Thus, this study aims to evaluate alternative solvents for paepalantine and evaluate their potential to interfere with antioxidant assays (ABTS•+, O2•-, HOCl. Of the selected solvents, propylene glycol had good solubility and remained stable throughout the study period. The results suggested that there is no interference from propylene glycol in antioxidant assays, while dimethylsulfoxide significantly interfered with the HOCl assay. The antioxidant assays showed that paepalantine demonstrated similar or even better antioxidant activity than Trolox. Thus, propylene glycol may be the solvent of choice for paepalantine, a compound that has significant biological potential.

In vivo imaging of vesicular monoamine transporter 2 in pancreas using an {sup 18}F epoxide derivative of tetrabenazine

Energy Technology Data Exchange (ETDEWEB)

Kung, Hank F. [Department of Radiology, University of Pennsylvania, Philadelphia, PA 19104 (United States); Department of Pharmacology, University of Pennsylvania, Philadelphia, PA 19104 (United States)], E-mail: kunghf@sunmac.spect.upenn.edu; Lieberman, Brian P. [Department of Radiology, University of Pennsylvania, Philadelphia, PA 19104 (United States); Zhuang Zhiping [Avid Radiopharmaceuticals, Inc., Philadelphia, PA 19104 (United States); Oya, Shunichi; Kung Meiping [Department of Radiology, University of Pennsylvania, Philadelphia, PA 19104 (United States); Choi, Seok Rye [Avid Radiopharmaceuticals, Inc., Philadelphia, PA 19104 (United States); Poessl, Karl; Blankemeyer, Eric; Hou, Catherine [Department of Radiology, University of Pennsylvania, Philadelphia, PA 19104 (United States); Skovronsky, Daniel [Avid Radiopharmaceuticals, Inc., Philadelphia, PA 19104 (United States); Kilbourn, Michael [Department of Radiology, University of Michigan, Ann Arbor, MI 48109 (United States)

2008-11-15

Objectives: Development of imaging agents for pancreatic beta cell mass may provide tools for studying insulin-secreting beta cells and their relationship with diabetes mellitus. In this paper, a new imaging agent, [{sup 18}F](+)-2-oxiranyl-3-isobutyl-9-(3-fluoropropoxy)-10-methoxy-2,3,4,6,7, 11b-hexahydro-1H-pyrido[2,1-a]isoquinoline [{sup 18}F](+)4, which displays properties targeting vesicular monoamine transporter 2 (VMAT2) binding sites of beta cells in the pancreas, was evaluated as a positron emission tomography (PET) agent for estimating beta cell mass in vivo. The hydrolyzable epoxide group of (+)4 may provide a mechanism for shifting biodistribution from liver to kidney, thus reducing the background signal. Methods: Both {sup 18}F- and {sup 19}F-labeled (+) and (-) isomers of 4 were synthesized and evaluated. Organ distribution was carried out in normal rats. Uptake of [{sup 18}F](+)4 in pancreas of normal rats was measured and correlated with blocking studies using competing drugs, (+)dihydrotetrabenazine [(+)-DTBZ] or 9-fluoropropyl-(+)dihydro tetrabenazine [FP-(+)-DTBZ, (+)2]. Results: In vitro binding study of VMAT2 using rat brain striatum showed a K{sub i} value of 0.08 and 0.15 nM for the (+)4 and ({+-})4, respectively. The in vivo biodistribution of [{sup 18}F](+)4 in rats showed the highest uptake in the pancreas (2.68 %ID/g at 60 min postinjection). In vivo competition experiments with cold FP-(+)-DTBZ, (+)2, (3.5 mg/kg, 5 min iv pretreatment) led to a significant reduction of pancreas uptake (85% blockade at 60 min). The inactive isomer [{sup 18}F](-)4 showed significantly lower pancreas uptake (0.22 %ID/g at 30 min postinjection). Animal PET imaging studies of [{sup 18}F](+)4 in normal rats demonstrated an avid pancreatic uptake in rats. Conclusion: The preliminary results suggest that the epoxide, [{sup 18}F](+)4, is highly selective in binding to VMAT2 and it has an excellent uptake in the pancreas of rats. The liver uptake was significantly

Aerobic Epoxidation of Olefins Catalyzed by the Cobalt‐Based Metal–Organic Framework STA‐12(Co)

DEFF Research Database (Denmark)

Beier, Matthias Josef; Kleist, Wolfgang; Wharmby, Michael T.

2012-01-01

, (E)‐stilbene was converted with high selectivities between 80 and 90 %. Leaching of Co was low and the reaction was found to proceed mainly heterogeneously. The catalyst was reusable with only a small loss of activity. The catalytic epoxidation of stilbene with the MOF featured an induction period...

Interpenetrating Polymer Network (IPN with Epoxidized and Acrylated Bioresins and their Composites with Glass and Jute Fibres

Directory of Open Access Journals (Sweden)

Francisco Cardona

2016-02-01

Full Text Available Epoxidized (EHO and acrylated (AEHO bio-resins from hemp oil were synthesized, and their interpenetrating networks (IPNs were investigated in reinforced bio-composites with natural jute fibres and glass fibres. The mechanical properties (tensile, flexural, Charpy impact, and inter-laminar shear and viscoelastic properties (glass transition temperature, storage modulus, and crosslink density of the bio-resins and their hybrid IPNs EHO/AEHO system were investigated as a function of the level of bio-resin hybridization. The hybrid bio-resins exhibited interpenetrating network (IPN behaviour. Composites prepared with the synthetic vinyl ester (VE and epoxy resins showed superior mechanical and viscoelastic properties compared with their bio-resins and IPNs-based counterparts. With glass fibre (GF reinforcement, increases in the EHO content of the IPNs resulted in increased stiffness of the composites, while the strength, inter-laminar shear strength (ILSS, and impact resistance decreased. However, in the jute fibre reinforced bio-composites, increases in AEHO content generated increased tensile modulus, ILSS, and mechanical strength of the bio-materials. Crosslink density and glass transition temperature (Tg were also higher for the synthetic resins than for the bio-resins. Increased AEHO content of the IPNs resulted in improved viscoelastic properties.

Ac-electrical conductivity of poly(propylene) before and after X-ray irradiation

International Nuclear Information System (INIS)

Gaafar, M.

2001-01-01

Study on the ac-electrical conductivity of poly(propylene), before and after X-ray irradiation within the temperature range 300-360 K are reported. The measurements have been performed in a wide range of frequencies (from 0 to 10 5 Hz) and under the effect of different X-ray irradiation doses (from 0 to 15 Gy). Cole-Cole diagrams have been used to show the frequency dependence of the complex impedance at different temperatures. The results exhibit semicircles which are consistent with existing equivalent circuit model. Analysis of the results reveal semiconducting features based mainly on a hopping mechanism. The study shows a pronounced effect of X-ray irradiation on the electrical conductivity at zero frequency σ DC . At the early stage of irradiation, σ DC increased as a result of free radical formation. As the irradiation progressed, it decreased as a result of crosslinking, then it increased again due to irradiation induced degradation, which motivates the generation of mobile free radicals. The study shows that this polymer is one among other polymers which its electrical conductivity is modified by irradiation

Ac-electrical conductivity of poly(propylene) before and after X-ray irradiation

Science.gov (United States)

Gaafar, M.

2001-05-01

Study on the ac-electrical conductivity of poly(propylene), before and after X-ray irradiation within the temperature range 300-360 K are reported. The measurements have been performed in a wide range of frequencies (from 0 to 10 5 Hz) and under the effect of different X-ray irradiation doses (from 0 to 15 Gy). Cole-Cole diagrams have been used to show the frequency dependence of the complex impedance at different temperatures. The results exhibit semicircles which are consistent with existing equivalent circuit model. Analysis of the results reveal semiconducting features based mainly on a hopping mechanism. The study shows a pronounced effect of X-ray irradiation on the electrical conductivity at zero frequency σDC. At the early stage of irradiation, σDC increased as a result of free radical formation. As the irradiation progressed, it decreased as a result of crosslinking, then it increased again due to irradiation induced degradation, which motivates the generation of mobile free radicals. The study shows that this polymer is one among other polymers which its electrical conductivity is modified by irradiation.

Chemoenzymatic epoxidation of alkenes with Candida antarctica lipase B and hydrogen peroxide in deep eutectic solvents

NARCIS (Netherlands)

Zhou, Pengfei; Wang, Xuping; Yang, Bo; Hollmann, F.; Wang, Yonghua

2017-01-01

Epoxides are important synthetic intermediates for the synthesis of a broad range of industrial products. This study presents a promising solution to the current limitation of enzyme instability. By using simple deep eutectic solvents such as choline chloride/sorbitol, significant stabilization

Solvation of lithium ion in dimethoxyethane and propylene carbonate

Science.gov (United States)

Chaban, Vitaly

2015-07-01

Solvation of the lithium ion (Li+) in dimethoxyethane (DME) and propylene carbonate (PC) is of scientific significance and urgency in the context of lithium-ion batteries. I report PM7-MD simulations on the composition of Li+ solvation shells (SH) in a few DME/PC mixtures. The equimolar mixture features preferential solvation by PC, in agreement with classical MD studies. However, one DME molecule is always present in the first SH, supplementing the cage formed by five PC molecules. As PC molecules get removed, DME gradually substitutes vacant places. In the PC-poor mixtures, an entire SH is populated by five DME molecules.

Radiation vulcanization of ethylene-propylene rubber with polyfunctional monomers

Energy Technology Data Exchange (ETDEWEB)

Jinhua, Wang; Yoshii, Fumio; Makuuchi, Keizo

2001-01-01

This paper reports on the sensitizing efficiency of several polyfunctional monomers to radiation vulcanization of ethylene-propylene rubber. And the results show that triethyleneglycol dimethacrylate (TEGDMA) gave the best results. TEGDMA not only lowers the vulcanization dose (D{sub v}), but also increases the tensile strength greatly. The content of TEGDMA does not affect the D{sub v} of TEGDMA-EPM, but affects the tensile strength at the D{sub v}. At best content (0.04 mol/100 g EPM), the tensile strength is increased from 6.0 to 12 MPa, and the elongation is 790% at the D{sub v}. (author)

Enhanced mechanical properties of low-surface energy thin films by simultaneous plasma polymerization of fluorine and epoxy containing polymers

Energy Technology Data Exchange (ETDEWEB)

Karaman, Mustafa, E-mail: karamanm@selcuk.edu.tr [Department of Chemical Engineering, Selçuk University, Konya, 42075 (Turkey); Advanced Technology Research & Application Center, Selçuk University, Konya, 42075 (Turkey); Uçar, Tuba [Department of Chemical Engineering, Selçuk University, Konya, 42075 (Turkey)

2016-01-30

Graphical abstract: - Highlights: • Thin films of poly(hexafluorobutyl acrylate-glycidyl methacrylate) can be deposited by PECVD. • The coated surfaces are hydrophobic due to the long fluorinated side chains. • The hydrophobicity of the coating is observed to be stable under harsh conditions. • Film durability is attributed to the mechanical strength of the films due to their epoxide functionality. - Abstract: Thin films of poly(2,2,3,4,4,4 hexafluorobutyl acrylate-glycidyl methacrylate) (P(HFBA-GMA) were deposited on different surfaces using an inductively coupled RF plasma reactor. Fluorinated polymer was used to impart hydrophobicity, whereas epoxy polymer was used for improved durability. The deposition at a low plasma power and temperature was suitable for the functionalization of fragile surfaces such as textile fabrics. The coated rough textile surfaces were found to be superhydrophobic with water contact angles greater than 150° due to the high retention of long fluorinated side chains. The hydrophobicity of the surfaces was observed to be stable after many exposures to ultrasonification tests, which is attributed to the mechanical durability of the films due to their epoxide functionality. FTIR and XPS analyses of the deposited films confirmed that the epoxide functionality of the polymers increased with increasing glycidyl methacrylate fraction in the reactor inlet. The modulus and hardness values of the films also increase with increasing epoxide functionality.

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, 10

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Ito, Masayuki; Okamoto, Jiro; Machi, Sueo.

1982-02-01

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene by continuous operation was carried out using a flow apparatus with tank type reactor of 5 liter under a constant pressure of 30 kg/cm 2 , a temperature of 40 0 C, and a propylene fraction in monomer gas of 0.1. The polymer concentration in latex reaches to steady value after two times longer operation than mean residence time of latex in the reactor. The steady polymer concentration increases accelerately with increase of the mean residence time. The polymer concentrations and the polymerization rates are 33, 70, 164 g/l-H 2 O and 35.1, 40.0, 49.5 g/h.l-H 2 O, respectively, obtained at the mean residence times of 0.94, 1.75 and 3.31 hour. The results are consistent with those in semi-batch operation under the same reaction conditions. The amounts of dissolved monomer in latex tends to decrease with decreasing the mean residence time. This shows that monomer supply by diffusion from gas phase to latex is not enough in shorter residence time of latex in the reactor. (author)

Chemical composition separation of a propylene-ethylene random copolymer by high temperature solvent gradient interaction chromatography.

Science.gov (United States)

Liu, Yonggang; Phiri, Mohau Justice; Ndiripo, Anthony; Pasch, Harald

2017-11-03

A propylene-ethylene random copolymer was fractionated by preparative temperature rising elution fractionation (TREF). The structural heterogeneity of the bulk sample and its TREF fractions was studied by high temperature liquid chromatography with a solvent gradient elution from 1-decanol to 1,2,4-trichlorobenzene. HPLC alone cannot resolve those propylene-ethylene copolymers with high ethylene content in the bulk sample, due to their low weight fractions in the bulk sample and a small response factor of these components in the ELSD detector, as well as their broad chemical composition distribution. These components can only be detected after being separated and enriched by TREF followed by HPLC analysis. Chemical composition separations were achieved for TREF fractions with average ethylene contents between 2.1 and 22.0mol%, showing that copolymers with higher ethylene contents were adsorbed stronger in the Hypercarb column and eluted later. All TREF fractions, except the 40°C fraction, were relatively homogeneous in both molar mass and chemical composition. The 40°C fraction was rather broad in both molar mass and chemical composition distributions. 2D HPLC showed that the molar masses of the components containing more ethylene units were getting lower for the 40°C fraction. HPLC revealed and confirmed that co-crystallization influences the separation in TREF of the studied propylene-ethylene copolymer. Copyright © 2017 Elsevier B.V. All rights reserved.

Iron-functionalized nanoporous silica type SBA-15: Synthesis, characterization and application in alkene epoxidation in presence of hydrogen peroxide

Directory of Open Access Journals (Sweden)

Mahdieh Ghazizadeh

2017-05-01

Full Text Available Fe(IIIsalophen complex on a SBA-15 support functionalized with (3-aminopropyltriethoxysilane as a linker. It has been synthesized and characterized by XRD, adsorption–desorption of nitrogen, SEM, FT-IR and UV–Vis. The formation of metal-salophen complex with the amino groups as connectors to the SBA-15 surface was confirmed. This material was successfully used as a heterogeneous catalyst for the epoxidation of alkenes and the effects of reaction time, different solvents and amount of catalyst on catalytic activity were investigated. This catalyst gave suitable and comparable yield and percentage conversion values. It is also stable and can be recycled and reused in the epoxidation of alkenes.

Thermal and mechanical properties of bio-based plasticizers mixtures on poly (vinyl chloride

Directory of Open Access Journals (Sweden)

Boussaha Bouchoul

2017-09-01

Full Text Available Abstract The use of mixtures of nontoxic and biodegradable plasticizers coming from natural resources is a good way to replace conventional phthalates plasticizers. In this study, two secondary plasticizers of epoxidized sunflower oil (ESO and epoxidized sunflower oil methyl ester (ESOME were synthesized and have been used with two commercially available biobased plasticizers; isosorbide diesters (ISB and acetyl tributyl citrate (ATBC in order to produce flexible PVC. Different mixtures of these plasticizers have been introduced in PVC formulations. Thermal, mechanical and morphological properties have been studied by using discoloration, thermogravimetric analysis (TGA, differential scanning calorimetry (DSC, dynamic mechanical thermal analysis (DMTA, tensile - strain and scanning electron microscopy (SEM. Studies have shown that PVC plasticization and stabilization were improved by addition of plasticizers blends containing ISB, ATBC, ESO and ESOME. An increase in the content of ESO or ESOME improved thermal and mechanical properties, whereas ESOME/ATBC formulations exhibited the best properties.

Propylene glycol energy supplementation during peripartal period in dairy cows and reproduction efficiency parameters

Directory of Open Access Journals (Sweden)

Vakanjac Slobodanka

2012-01-01

Full Text Available The aim of this work was to investigate the impact of two energy supplements based on propylene glycol in dairy cows diet on ovarian and follicular morphology, conception, insemination index and length of service period. A total number of 60 Holstein Friesian dairy cows, parity between 2-8, with an average milk production of 7000 kg/305 days of lactation were divided into three experimental groups (20 dairy cows per group. The first group of dairy cows was supplemented daily with "Energy-plus" (O1 group; 200 mL propylene-glycol supplement and the second group was supplemented with "Ketal" (O2 group; 160 mL propylene-glycol supplement, two weeks before partus until 30 days post partum. The third experimental group were non supplemented dairy cows (O3, control group. Ultrasound examination of the reproductive system using real time echo camera Falco VET 100 (ESAOTE PieMedical, Holland, B-shaped scan with linear-array endorectal 5-8 MHz probe was conducted on every animal starting from day 40 postpartum. The diameters of the ovaries (left and right and of the dominant follicle(s were recorded. Ultrasound testing was repeated on day 50 and 60 postpartum only in cows which in the meantime were not inseminated. Reproduction efficiency parameters (conception rate, number of inseminations and length of service period were recorded individually. The statistical significance of the differences between groups was tested using ANOVA with LSD test at the level of significance p<0.05, chi-square test and Kaplan-Meier survival analysis (the length of service period. There was no significant impact of the propylene glycol supplementation on the ovarian and follicular morphology at the first ultrasound examination. At the second ultrasound examination there was a significant difference between left ovarian dominant follicle diameter in the control and supplemented dairy cows (1.67±0.53 vs 1.12±0.29 and 1.11±0.35 cm, p<0.05, O3 vs O1 and O2, respectively. The

LC determination of propylene glycol in human plasma after pre-column derivatization with benzoyl chloride

NARCIS (Netherlands)

Sinjewel, A.; Swart, E.L.; Lingeman, H.; Wilhelm, A.J.

2007-01-01

A simple high-performance liquid chromatographic method, using photodiode array detection was developed for the determination of propylene glycol in human plasma and in the fluid retreived after continuous veno-venous hemofiltration. The method entailed alkaline derivatization with benzoyl chloride

Degradation and biocompatibility of a poly(propylene fumarate)-based/alumoxane nanocomposite for bone tissue engineering.

NARCIS (Netherlands)

Mistry, A.S.; Mikos, A.G.; Jansen, J.A.

2007-01-01

In this work, we evaluated the in vitro cytotoxicity and in vivo biocompatibility of a novel poly(propylene fumarate) (PPF)-based/alumoxane nanocomposite for bone tissue engineering applications. The incorporation of functionalized alumoxane nanoparticles into the PPF-based polymer was previously

Combination of supramolecular cross-linking with covalent cross-linking through epoxide ring-opening including gel studies

NARCIS (Netherlands)

Hofmeier, H.; El-Ghayoury, A.; Schubert, U.S.

2003-01-01

Terpolymers based on poly(methyl methacrylate), containing terpyridinemoieties as well as epoxide groups, were synthesized via free-radical polymerization. The products were cross-linked non-covalently with iron(II) ions and covalently by treatment with AlCl3. Both steps could be combined in

Analytical approaches for the detection of epoxides and hydroperoxides in active pharmaceutical ingredients, drug products and herbals.

Science.gov (United States)

Elder, D P; Snodin, D; Teasdale, A

2010-04-06

This review summarizes the analytical approaches reported in the literature relating to epoxide and hydroperoxide impurities. It is intended that it should provide guidance for analysts faced by the need to control such impurities, particularly where this is due to concerns relating to their potential genotoxicity. An extensive search of the literature relating to this class of impurities revealed a large number of references relating to analysis of epoxides/hydroperoxides associated with herbal remedies. Given the general applicability of the analytical methodology and due to the widespread use of herbal products the authors decided to include herbal medicines in this review. The review also reflects on the very different approaches taken in terms of the assessment/control of genotoxic impurities for such herbal remedies to that required for pharmaceutical products. Copyright 2009 Elsevier B.V. All rights reserved.

Kinetic and Mechanistic Study of the pH-Dependent Activation (Epoxidation) of Prodrug Treosulfan Including the Reaction Inhibition in a Borate Buffer.

Science.gov (United States)

Romański, Michał; Ratajczak, Whitney; Główka, Franciszek

2017-07-01

A prodrug treosulfan (T) undergoes a pH-dependent activation to epoxide derivatives. The process seems to involve an intramolecular Williamson reaction (IWR) but clear kinetic evidence is lacking. Moreover, a cis-diol system present in the T structure is expected to promote complexation with boric acid. As a result, the prodrug epoxidation would be inhibited; however, this phenomenon has not been investigated. In this article, the effect of pH on the kinetics of T conversion to its monoepoxide was studied from a mechanistic point of view. Also, the influence of boric acid on the reaction kinetics was examined. The rate constants observed for the activation of T (k obs ) in acetate, phosphate, and carbonate buffers satisfied the equation logk obs  = -7.48 + 0.96 pH. The reaction was inhibited in the excess of boric acid over T, and the k obs decreased with increasing borate buffer concentration. The experimental results were consistent with the inhibition model that included the formation of a tetrahedral, anionic T-boric acid monoester. To conclude, in nonborate buffers, the T activation to (2S,3S)-1,2-epoxybutane-3,4-diol 4-methanesulfonate follows IWR mechanism. A borate buffer changes the reaction kinetics and complicates kinetic analysis. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Combination of supramolecular cross-linking with covalent cross-linking through epoxide ring-opening including gel studies

NARCIS (Netherlands)

Hofmeier, H.; El-Ghayoury, A.; Schubert, U.S.

2003-01-01

Terpolymers based on poly(methyl methacrylate), containing terpyridine-moieties as well as epoxide groups, were synthesized via free-radical polymeri-zation. The products were cross-linked non-covalently with iron(II) ions and cova-lently by treatment with AlCl3. Both steps could be combined in

Studies on biodegradable and crosslinkable poly(castor oil fumarate)/poly(propylene fumarate) composite adhesive as a potential injectable biomaterial.

Science.gov (United States)

Mitha, M K; Jayabalan, M

2009-12-01

Biodegradable hydroxyl terminated-poly(castor oil fumarate) (HT-PCF) and poly(propylene fumarate) (HT-PPF) resins were synthesized as an injectable and in situ-cross linkable polyester resins for orthopedic applications. An injectable adhesive formulation containing this resin blend, N-vinyl pyrrolidone (NVP), hydroxy apatite, free radical initiator and accelerator was developed. The Composite adhesives containing the ratio of resin blend and NVP, 2.1:1.5, 2.1:1.2 and 2.1:1.0 set fast with tolerable exothermic temperature as a three dimensionally cross linked toughened material. Crosslink density and mechanical properties of the crosslinked composite increase with increase of NVP. The present crosslinked composite has hydrophilic character and cytocompatibility with L929 fibroblast cells.

Problems of selectivity in liquid-phase oxidation

Energy Technology Data Exchange (ETDEWEB)

Emanuel, N M

1978-07-01

Based on a kinetic analysis of a generalized scheme for radical-chain process and on published experimental results, factors determining the selectivities of various liquid-phase oxidations of organic compounds are examined, including the kinetic chain length, molecular and chain decomposition of products, and competing routes in the initiated oxidation or autoxidation of hydrocarbons to peroxides. Also discussed are selective inhibition of undesirable routes in chain reactions, e.g., styrene and acetaldehyde co-oxidation; activation of molecular oxygen by variable-valence metal compounds used as homogeneous catalysts; modeling of fermentative processes by oxidation of hydrocarbons in complex catalytic systems, e.g., hydroxylation of alkanes, epoxidation or carbonylation of olefins, or oxidation of alcohols and ketones to acids; and the mechanisms of heterogeneous catalysis in liquid-phase reactions, e.g., oxidation of alkylaromatic hydrocarbons to peroxides and co-oxidation of propylene and acetaldehyde.

Effect of molecular weight and testing rate on adhesion property of pressure-sensitive adhesives prepared from epoxidized natural rubber

International Nuclear Information System (INIS)

Khan, Imran; Poh, B.T.

2011-01-01

Research highlights: → Elucidation of adhesion property of epoxidized natural rubber (ENR 25). → Correlation of peel and shear strength with molecular weight and rate of testing. → Confirmation of miscibility of tackifier and ENR 25 by DSC and FTIR study. → Applicability of Fox equation in ENR 25/coumarone-indene resin system. -- Abstract: The dependence of peel strength and shear strength of epoxidized natural rubber (ENR 25)-based pressure-sensitive adhesive on molecular weight and rate of testing was investigated using coumarone-indene as the tackifying resin. Toluene and polyethylene terephthalate (PET) were used as the solvent and substrate respectively throughout the study. A SHEEN hand coater was used to coat the adhesive on the substrate at a coating thickness of 120 μm. All the adhesion properties were determined by a Llyod Adhesion Tester operating at different rates of testing. Result shows that peel strength and shear strength increases up to an optimum molecular weight of 6.5 x 10 4 of ENR 25. For peel strength, the observation is attributed to the combined effects of wettability and mechanical strength of rubber at the optimum molecular weight, whereas for the shear strength, it is ascribed to the increasing amount of adhesive present in the coating layer which enhances the shear resistance of the adhesive. Peel strength and shear strength also increases with increase in rate of testing, an observation which is associated to the viscoeslastic response of the adhesive. Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) study confirms the miscibility of tackifier and the ENR 25.

Estimation of the Polymerization Rate of Liquid Propylene Using Adiabatic Reaction Calorimetry and Reaction Dilatometry

NARCIS (Netherlands)

Al-haj Ali, Mohammad; Betlem, Ben; Roffel, Brian; Weickert, Günter

2007-01-01

The use of pressure-drop and constant-pressure dilatometry for obtaining rate data for liquid propylene polymerization in filled batch reactors was examined. The first method uses reaction temperature and pressure as well as the compressibility of the reactor contents to calculate the polymerization

Soluble epoxide hydrolase in the generation and maintenance of high blood pressure in spontaneously hypertensive rats

NARCIS (Netherlands)

Koeners, Maarten P.; Wesseling, Sebastiaan; Ulu, Arzu; Lopez Sepulveda, Rocio; Morisseau, Christophe; Braam, Branko; Hammock, Bruce D.; Joles, Jaap A.

Koeners MP, Wesseling S, Ulu A, Sepulveda RL, Morisseau C, Braam B, Hammock BD, Joles JA. Soluble epoxide hydrolase in the generation and maintenance of high blood pressure in spontaneously hypertensive rats. Am J Physiol Endocrinol Metab 300: E691-E698, 2011. First published January 25, 2011; doi:

Effects of Polyethylene Grafted Maleic Anhydride on the Mechanical, Morphological, and Swelling Properties of Poly (Vinyl Chloride / Epoxidized Natural Rubber / Kenaf Core Powder Composites

Directory of Open Access Journals (Sweden)

Rohani Abdul Majid

2014-10-01

Full Text Available The effects of polyethylene grafted maleic anhydride (PE-g-MA on the properties of poly (vinyl chloride/epoxidized natural rubber (PVC/ENR kenaf core powder composites were studied, with four different loadings of kenaf core powder (5, 10, 15, and 20 phr. The tensile properties indicated that the strength and elongation at break of the composites exhibited an increase for samples with PE-g-MA. Morphological analysis using a scanning electron microscope (SEM showed better dispersion of kenaf fiber with the addition of PE-g-MA and less kenaf powder agglomeration. Furthermore, the swelling index indicated that composites with PE-g-MA showed lower toluene absorption than composites without PE-g-MA.

Synthesis and characterization of supported heteropolymolybdate nanoparticles between silicate layers of Bentonite with enhanced catalytic activity for epoxidation of alkenes

International Nuclear Information System (INIS)

Salavati, Hossein; Rasouli, Nahid

2011-01-01

Highlights: → The PVMo and nanocomposite catalyst (PVMo/Bentonite) as catalyst for epoxidation of alkenes. → The composite catalyst showed higher catalytic activity than parent heteropolymolybdate (PVMo). →The use of ultrasonic irradiation increased the conversions and reduced the reaction times. → The H 2 O 2 is a green and eco-friendly oxidant in this catalytic system. -- Abstract: A new heterogeneous catalyst (PVMo/Bentonite) consisting of vanadium substituted heteropolymolybdate with Keggin-type structure Na 5 [PV 2 Mo 10 O 40 ].14H 2 O (PVMo) supported between silicate layers of bentonite has been synthesized by impregnation method and characterized using X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, UV-vis diffuse reflectance spectroscopy, transmission electron microscopy and elemental analysis. X-ray diffraction and scanning electron microscopy analysis indicated that PVMo was finely dispersed into layers of bentonite as support. The PVMo/Bentonite used as an efficient heterogeneous catalyst for epoxidation of alkenes. Various cyclic and linear alkenes were oxidized into the corresponding epoxides in high yields and selectivity with 30% aqueous H 2 O 2 . The catalyst was reused several times, without observable loss of activity and selectivity. The obtained results showed that the catalytic activity of the PVMo/Bentonite was higher than that of pure heteropolyanion (PVMo).

End-group characterisation of poly(propylene glycol)s by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS).

Science.gov (United States)

Jackson, Anthony T; Slade, Susan E; Thalassinos, Konstantinos; Scrivens, James H

2008-10-01

The end-group functionalisation of a series of poly(propylene glycol)s has been characterised by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS). A series of peaks with mass-to-charge ratios that are close to that of the precursor ion were used to generate information on the end-group functionalities of the poly(propylene glycol)s. Fragment ions resulting from losses of both of the end groups were noted from some of the samples. An example is presented of how software can be used to significantly reduce the length of time involved in data interpretation (which is typically the most time-consuming part of the analysis).

Multivalent contrast agents based on Gd-DTPA-terminated poly (propylene imine) dendrimers for Magnetic Resonance Imaging

NARCIS (Netherlands)

Langereis, S.; Lussanet, de Q.G; Genderen, van M.H.P.; Backes, W.H.; Meijer, E.W.

2004-01-01

A convenient methodol. has been developed for the synthesis of gadolinium-diethylenetriaminepentaacetic acid (Gd-DTPA)-terminated poly(propylene imine) dendrimers as contrast agents for magnetic resonance imaging (MRI). In our strategy, isocyanate-activated, tert-butyl-protected DTPA analogs were

Pore size control of Pitch-based activated carbon fibers by pyrolytic deposition of propylene

International Nuclear Information System (INIS)

Xie Jinchuan; Wang Xuhui; Deng Jiyong; Zhang Lixing

2005-01-01

In this paper, we attempted to narrow the pore size of Pitch-based activated carbon fiber (Pitch-ACF) by chemical vapor deposition (CVD) of propylene at 700 deg. C. The BET equation was used to estimate the specific surface areas. The micropore volumes were determined using DR equation, t-plot and α s -plot, and mesopore surface areas were determined by t-plot and α s -plot. The pore size distribution (PSD) of micropores and mesopore was investigated by micropore analysis method (MP method) and MK method, respectively. The relation between the graphite-like crystal interlayer distance and pore size was analyzed by X-ray diffraction (XRD). The results showed that the pore size of Pitch-ACF was gradually narrowed with increasing deposition time. The catalytic activation of Ni was attempted when Pitch-ACF was modified simultaneously by pyrolysis of propylene. The results obtained from the analysis of PSD of micropores, mesopores and macropores in Ni-P-ACF by density function theory (DFT) showed that the pore structure and surface chemistry were greatly changed due to introducing nickel catalyst

Warfarin traps human vitamin K epoxide reductase in an intermediate state during electron transfer

Science.gov (United States)

Shen, Guomin; Cui, Weidong; Zhang, Hao; Zhou, Fengbo; Huang, Wei; Liu, Qian; Yang, Yihu; Li, Shuang; Bowman, Gregory R.; Sadler, J. Evan; Gross, Michael L.; Li, Weikai

2017-01-01

Although warfarin is the most widely used anticoagulant worldwide, the mechanism by which warfarin inhibits its target, human vitamin K epoxide reductase (hVKOR), remains unclear. Here we show that warfarin blocks a dynamic electron-transfer process in hVKOR. A major fraction of cellular hVKOR is at an intermediate redox state of this process containing a Cys51-Cys132 disulfide, a characteristic accommodated by a four-transmembrane-helix structure of hVKOR. Warfarin selectively inhibits this major cellular form of hVKOR, whereas disruption of the Cys51-Cys132 disulfide impairs warfarin binding and causes warfarin resistance. Relying on binding interactions identified by cysteine alkylation footprinting and mass spectrometry coupled with mutagenesis analysis, we are able to conduct structure simulations to reveal a closed warfarin-binding pocket stabilized by the Cys51-Cys132 linkage. Understanding the selective warfarin inhibition of a specific redox state of hVKOR should enable the rational design of drugs that exploit the redox chemistry and associated conformational changes in hVKOR. PMID:27918545

Microwave absorption properties of barium titanate/epoxide resin composites

International Nuclear Information System (INIS)

Chen Xiaodong; Wang Guiqin; Duan Yuping; Liu Shunhua

2007-01-01

Nano-barium titanate (BT) was prepared by a sol-gel method. The prepared powders were characterized by x-ray powder diffraction and transmission electron microscopy. The complex relative dielectric permittivity (ε = ε' - jε-prime) and magnetic permeability (μ = μ' - jμ-prime) of the BT powders were measured in the frequency range 8 ∼ 18 GHz. The BT/epoxide resin (EP) composite with different volume contents was investigated. The effects of thickness on the BT/EP composite were studied. It was found that an optimum thickness and contents of the absorber can yield the maximum reflection loss which could be obtained over a broad frequency region in the X and Ku bands. Our results indicate that BT could be a promising microwave absorption material

Progress in Characterizing Thermal Degradation of Ethylene-Propylene Rubber

Energy Technology Data Exchange (ETDEWEB)

Fifield, Leonard S. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Huang, Qian [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Childers, Matthew I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Correa, Miguel [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shin, Yongsoon [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zwoster, Andy [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2016-08-26

Ethylene-propylene rubber (EPR) is one of the two most common nuclear cable insulation materials. A large fraction of EPR-insulated cables in use in the nuclear industry were manufactured by The Okonite Company. Okoguard® is the name of the medium voltage thermoset EPR manufactured by The Okonite Company. Okoguard® has been produced with silane-treated clay filler and the characteristic pink color since the 1970’s. EPR is complex material that undergoes simultaneous reactions during thermal aging including oxidative and thermal cleavage and oxidative and thermal crosslinking. This reaction complexity makes precise EPR service life prediction from accelerated aging using approaches designed for single discreet reactions such as the Arrhenius approach problematic. Performance data and activation energies for EPR aged at conditions closer to service conditions will improve EPR lifetime prediction. In this report pink Okoguard® EPR insulation material has been thermally aged at elevated temperatures. A variety of characterization techniques have been employed to track material changes with aging. It was noted that EPR aged significant departure in aging behavior seemed to occur at accelerated aging temperatures between 140°C and 150°C at around 20 days of exposure. This may be due to alternative degradation mechanisms being accessed at this higher temperature and reinforces the need to perform accelerated aging for Okoguard® EPR service life prediction at temperatures below 150°C.

21 CFR 172.856 - Propylene glycol mono- and diesters of fats and fatty acids.

Science.gov (United States)

2010-04-01

... fatty acids. 172.856 Section 172.856 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... diesters of fats and fatty acids. Propylene glycol mono- and diesters of fats and fatty acids may be safely... and/or fatty acids in compliance with § 172.860 and/or oleic acid derived from tall oil fatty acids in...

Preparation and characterization of starch grafted with toluene poly (propylene oxide diisocyanate

Directory of Open Access Journals (Sweden)

D.C. Dragunski

2001-01-01

Full Text Available Amylopectin-rich starch samples (Amidex 4001 Corn Products Brasil Ingredientes Industriais Ltda. were grafted with polyethers with the purpose of obtaining new materials for application as solid polymeric electrolytes. Grafting reaction was performed by the addition of starch dissolved in DMSO to toluene poly(propylene oxide diisocyanate (Resibras dissolved in the same solvent. This reaction produced a film with good mechanical properties. The film samples were characterized by 13C-NMR, FTIR, DSC, X-Ray and SEM. The FTIR spectrum shows a sharp NH band and a very small urethane band. The 13C-NMR spectrum revealed a peak at 20 ppm, that can be attributed to the CH3 of the polyether chain, and two small peaks at 117 and 140 ppm, attributed to the aromatic ring. The X-ray diffractograms also indicated that after the grafting reaction, the samples of amylopectin-rich starch are more amorphous. Moreover, the glass transition temperature (Tg dropped from 50 °C to -11 °C. These results indicate formation of grafted products and the low Tg of the samples suggests that polyether-grafted starch is a good candidate to obtain solid polymeric electrolytes.

Morphological Development of Melt Crystallized Poly(propylene oxide) by In Situ AFM: Formation of Banded Spherulites

NARCIS (Netherlands)

Beekmans, L.G.M.; Hempenius, Mark A.; Vancso, Gyula J.

2004-01-01

The morphology of poly(propylene oxide) (PPO) crystals grown from the melt was investigated. The spherulites of the optically pure S polymers displayed a regular pattern of concentric rings as observed by polarizing optical microscopy, while the stereocopolymer developed irregularly banded, or

Further characterization of benzo[a]pyrene diol-epoxide (BPDE)-induced comet assay effects.

Science.gov (United States)

Bausinger, Julia; Schütz, Petra; Piberger, Ann Liza; Speit, Günter

2016-03-01

The present study aims to further characterize benzo[a]pyrene diol-epoxide (BPDE)-induced comet assay effects. Therefore, we measured DNA effects by the comet assay and adduct levels by high-performance liquid chromatography (HPLC) in human lymphocytes and A549 cells exposed to (±)-anti-benzo[a]pyrene-7,8-diol 9,10-epoxide [(±)-anti-BPDE] or (+)-anti-benzo[a]pyrene-7,8-diol 9,10-epoxide [(+)-anti-BPDE]. Both, the racemic form and (+)-anti-BPDE, which is the most relevant metabolite with regard to mutagenicity and carcinogenicity, induced DNA migration in cultured lymphocytes in the same range of concentrations to a similar extent in the alkaline comet assay after exposure for 2h. Nevertheless, (+)-anti-BPDE induced significantly enhanced DNA migration after 16 and 18h post-cultivation which was not seen in response to (±)-anti-BPDE. Combination of the comet assay with the Fpg (formamidopyrimidine-DNA glycosylase) protein did not enhance BPDE-induced effects and thus indicated the absence of Fpg-sensitive sites (oxidized purines, N7-guanine adducts, AP-sites). The aphidicolin (APC)-modified comet assay suggested significant excision repair activity of cultured lymphocytes during the first 18h of culture after a 2 h-exposure to BPDE. In contrast to these repair-related effects measured by the comet assay, HPLC analysis of stable adducts did not reveal any significant removal of (+)-anti-BPDE-induced adducts from lymphocytes during the first 22h of culture. On the other hand, HPLC measurements indicated that A549 cells repaired about 70% of (+)-anti-BPDE-induced DNA-adducts within 22h of release. However, various experiments with the APC-modified comet assay did not indicate significant repair activity during this period in A549 cells. The conflicting results obtained with the comet assay and the HPLC-based adduct analysis question the real cause for BPDE-induced DNA migration in the comet assay and the reliability of the APC-modified comet assay for the

(SalenMn(III Catalyzed Asymmetric Epoxidation Reactions by Hydrogen Peroxide in Water: A Green Protocol

Directory of Open Access Journals (Sweden)

Francesco Paolo Ballistreri

2016-07-01

Full Text Available Enantioselective epoxidation reactions of some chosen reactive alkenes by a chiral Mn(III salen catalyst were performed in H2O employing H2O2 as oxidant and diethyltetradecylamine N-oxide (AOE-14 as surfactant. This procedure represents an environmentally benign protocol which leads to e.e. values ranging from good to excellent (up to 95%.

Modification of carbon nanotubes with fluorinated ionic liquid for improving processability of fluoro-ethylene-propylene

Energy Technology Data Exchange (ETDEWEB)

Ma, Hongyang; Chu, Benjamin; Hsiao, Benjamin S.

2017-02-01

Fluorinated ionic liquid (F-IL), 1-(3-perfluorooctylpropyl)-3-methylimidazolium bis(perfluoroethylsufonyl)amine, had been successfully prepared and employed to modify multi-wall carbon nanotubes (MWCNTs) for improving the processability of fluoro-ethylene-propylene (FEP). The thermally decomposed temperature of F-IL was higher than 350 °C measured by thermal gravimetric analysis (TGA) which indicated that the fluorinated ionic liquid could be suitable for melting blend with FEP (blending at 290 °C) by a twin-screw extruder. Through “cation-π” interaction between the imidazolium cation of F-IL and the graphene surface of MWCNTs, MWCNTs can be modified with F-IL and used as nanofillers to improve the dispersity of MWCNTs in fluorocopolymer FEP verified by SEM images of the FEP nanocomposite. The structural characterization and mechanical property of FEP nanocomposite during the deformation were investigated by tensile experiments and simultaneous time-resolved wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques.

STUDY OF EPOXIDE DECYCLISATION OF CARYOPHYLENE OXIDE WITH SYNTHETIC ZEOLITE AS CATALYSTS

Directory of Open Access Journals (Sweden)

Winarto Haryadi

2010-06-01

Full Text Available The reaction of epoxide ring opening of caryophillene oxide has been done using zeolite H-Y, H-sodalit, and H-ZSM-5 as catalysts. The reactions were done in two types, there were in dioxane solvent at temperature of 110 oC and without solvent at temperature of 175 oC. The catalyst weight was 10 % from caryophillene oxide weight, and the time of reaction was four hours. The product of reaction was analyzed using GC, FTIR, and GC-MS. The reactions of caryophillene oxide in dioxane solvent with the three kinds of zeolites did not give any targeted product. Whereas, the reactions without solvent gave three main products, there was one compound with one group of secondary hidroxyl (secondary alcohol, and two compounds of ketone from caryophillene. The reaction product of caryophillene oxide obtained without using solvent with the three type of catalysts were then compared. Conversion of three main products produced by H-ZSM-5 catalyst, H-sodalit catalyst and H-Y catalyst were 82.11 %, 54.92 % and 38.53 % respectively. For that reason, the transformation of caryophillene oxide using H-ZSM-5 catalyst was considered to be the best selective product. The alcohol product was resulted from reaction between caryophillene oxide and Bronsted acid, and  the ketone products was resulted from the reaction with Lewis acid in zeolite.   Keywords: Epoxide ring opening, HY, H-sodalit and HZSM-5

Evaluation of permanent deformation and durability of epoxidized natural rubber modified asphalt mix

Science.gov (United States)

Al-Mansob, Ramez A.; Ismail, Amiruddin; Rahmat, Riza Atiq O. K.; Nazri Borhan, Muhamad; Alsharef, Jamal M. A.; Albrka, Shaban Ismael; Rehan Karim, Mohamed

2017-09-01

The road distresses have caused too much in maintenance cost. However, better understandings of the behaviours and properties of asphalt, couples with greater development in technology, have allowed paving technologists to examine the benefits of introducing additives and modifiers. As a result, modifiers such as polymers are the most popular modifiers used to improve the performance of asphalt mix. This study was conducted to investigate the use of epoxidized natural rubber (ENR) to be mixed with asphalt mix. Tests were conducted to investigate the performance characteristics of ENR-asphalt mixes, where the mixes were prepared according to the wet process. Mechanical testing on the ENR-asphalt mixes have demonstrated that the asphalt mix permanent deformation performance at high temperature was found to be improved compared to the base mixes. However, the durability studies have indicated that ENR-asphalt mixes are slightly susceptible with the presence of moisture. The durability of the ENR-asphalt mixes were found to be enhanced in term of permanent deformation at high and intermediate temperatures compared to the base asphalt mixes. As conclusion, asphalt pavement performance can be enhanced by using ENR as modifier to face the major road distresses.

Assessment of epoxidized soy bean oil (ESBO) migrating into foods: comparison with ESBO-like epoxy fatty acids in our normal diet.

Science.gov (United States)

Fankhauser-Noti, Anja; Fiselier, Katell; Biedermann-Brem, Sandra; Grob, Koni

2006-08-01

Epoxidized soy bean oil (ESBO) was found to be toxic for rats, but the toxic constituent is unknown. It became an issue as the migration from the gaskets in the lids for jars into oily foods regularly far exceeds the European legal limit (overall migration limit and specific migration limit derived from the tolerable daily intake (TDI)). In the context of risk management it was of interest to determine the epoxidized fatty acids of ESBO in those foods of our normal diet which are expected to contain the highest concentrations, i.e., oxidized edible oils (including degraded frying oils), fried foods, bakery ware and roasted meat. The contribution of epoxy oleic acid from ESBO to our diet turned out to be negligible. If this acid were the toxic component in ESBO, the toxicological assessment would primarily be a warning regarding oxidized fats and oils. The contribution of diepoxy linoleic acid from ESBO might be similar to the exposure from oxidized fats and oils of our diet, whereas the intake of triepoxy linolenic acid from ESBO exceeds that from normal food by around two orders of magnitude. Hence use of an epoxidized edible oil virtually free of linolenic acid would be inconspicuous in our diet.

Double photoionization of propylene oxide: A coincidence study of the ejection of a pair of valence-shell electrons

Science.gov (United States)

Falcinelli, Stefano; Vecchiocattivi, Franco; Alagia, Michele; Schio, Luca; Richter, Robert; Stranges, Stefano; Catone, Daniele; Arruda, Manuela S.; Mendes, Luiz A. V.; Palazzetti, Federico; Aquilanti, Vincenzo; Pirani, Fernando

2018-03-01

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality. In the present work, a photoelectron-photoion-photoion coincidence technique, using an ion-imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV energy range, permits us (i) to observe six double ionization fragmentation channels, their relative yields being accounted for about two-thirds by the couple (C2H4+, CH2O+) and one-fifth by (C2H3+, CH3O+); (ii) to measure thresholds for their openings as a function of photon energy; and (iii) to unravel a pronounced bimodality for a kinetic-energy-released distribution, fingerprint of competitive non-adiabatic mechanisms.

(Salen)Ti(Ⅳ)-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

Institute of Scientific and Technical Information of China (English)

Zheng Hong ZHOU; Zhao Ming LI; Bing LIU; Kang Ying LI; Li Xin WANG; Guo Feng ZHAO; Qi Lin ZHOU; Chu Chi TANG

2006-01-01

The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a (salen)Ti(Ⅳ) complex formed in situ from the reaction of Ti(OPr-i)4 and the chiral Schiff base derived from (1R,2R)-(+)-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity (up to 73% ee).

Benzo(a)pyrene diol epoxides as intermediates in nucleic acid binding in vivo and in vitro

DEFF Research Database (Denmark)

Weinstein, I.B.; Jeffrey, A.M.; Jennette, K.W.

1976-01-01

Evidence has been obtained that a specific isomer of a diol epoxide derivative of benzo(a)pyrene, (+/-)-7 beta,8alpha-dihydroxy-9alpha, 10alpha-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene, is an intermediate in the binding of benzo(a)pyrene to RNA in cultured bovine bronchial mucosa. An adduct is for...

Simultaneous Saccharification and Fermentation of Sugar Beet Pulp with Mixed Bacterial Cultures for Lactic Acid and Propylene Glycol Production

Directory of Open Access Journals (Sweden)

Joanna Berlowska

2016-10-01

Full Text Available Research into fermentative production of lactic acid from agricultural by-products has recently concentrated on the direct conversion of biomass, whereby pure sugars are replaced with inexpensive feedstock in the process of lactic acid production. In our studies, for the first time, the source of carbon used is sugar beet pulp, generated as a by-product of industrial sugar production. In this paper, we focus on the simultaneous saccharification of lignocellulosic biomass and fermentation of lactic acid, using mixed cultures with complementary assimilation profiles. Lactic acid is one of the primary platform chemicals, and can be used to synthesize a wide variety of useful products, including green propylene glycol. A series of controlled batch fermentations was conducted under various conditions, including pretreatment with enzymatic hydrolysis. Inoculation was performed in two sequential stages, to avoid carbon catabolite repression. Biologically-synthesized lactic acid was catalytically reduced to propylene glycol over 5% Ru/C. The highest lactic acid yield was obtained with mixed cultures. The yield of propylene glycol from the biological lactic acid was similar to that obtained with a water solution of pure lactic acid. Our results show that simultaneous saccharification and fermentation enables generation of lactic acid, suitable for further chemical transformations, from agricultural residues.

Immersion calorimetry as a tool to evaluate the catalytic performance of titanosilicate materials in the epoxidation of cyclohexene.

Science.gov (United States)

Vernimmen, Jarian; Guidotti, Matteo; Silvestre-Albero, Joaquin; Jardim, Erika O; Mertens, Myrjam; Lebedev, Oleg I; Van Tendeloo, Gustaaf; Psaro, Rinaldo; Rodríguez-Reinoso, Francisco; Meynen, Vera; Cool, Pegie

2011-04-05

Different types of titanosilicates are synthesized, structurally characterized, and subsequently catalytically tested in the liquid-phase epoxidation of cyclohexene. The performance of three types of combined zeolitic/mesoporous materials is compared with that of widely studied Ti-grafted-MCM-41 molecular sieve and the TS-1 microporous titanosilicate. The catalytic test results are correlated with the structural characteristics of the different catalysts. Moreover, for the first time, immersion calorimetry with the same substrate molecule as in the catalytic test reaction is applied as an extra means to interpret the catalytic results. A good correlation between catalytic performance and immersion calorimetry results is found. This work points out that the combination of catalytic testing and immersion calorimetry can lead to important insights into the influence of the materials structural characteristics on catalysis. Moreover, the potential of using immersion calorimetry as a screening tool for catalysts in epoxidation reactions is shown.

Synthesis of Carbasugars from Aldonolactones: Ritter-Type Epoxide Opening of Polyhydroxylated Aminocyclopentanes

DEFF Research Database (Denmark)

Lundt, Inge; Johansen, Steen Karsk; Kornø, Hanne Tøfting

1999-01-01

Using the cis-fused cyclopentane-1,4-lactone, 1(R),5(S)-7(R),8(R)-dihydroxy-2-oxabicyclo[3.3.0]oct-3-one (1), as starting material, 5-deoxycarba-*-L-xylo-hexofuranose (6) together with ?- (12) and ?-1-amino-1,5-dideoxycarba-L-xylo-hexofuranose (16) have been prepared using a number...... of stereoselective transformations. The key step was the regioselective opening of the epoxide 1(R),5(S)-7(R),8(R)-epoxy-2-oxabicyclo[3.3.0]oct-3-one (4) with different nucleophiles....

Epoxide resin coatings of cans - substance transfer to oil-containing foods possible

OpenAIRE

German Federal Institute for Risk Assessment

2016-01-01

Oily foods in cans can contain levels of Cyclo-di-BADGE (CdB) that present a health risk for high consumers. This is the result of a health risk assessment of the Federal Institute for Risk Assessment (BfR) in which the institute analysed data on the CdB content of canned fish preserved in oil. CdB is a molecule consisting of Bisphenol A (BPA) and Bisphenol A diglycidyl ether (BADGE). It is formed as a by-product during the production of epoxide resins which are, for example, used for the int...

Characterization of nylon 6/poly(propylene oxide) polymeric mixture by combined NMR techniques

International Nuclear Information System (INIS)

Costa, Dilma Alves; Oliveira, Clara Marize F.; Tavares, Maria Ines B.

1995-01-01

Polymeric mixtures aim to improve physical or chemical properties of materials. This mixtures can be compatible or not. The compatibility between polymers determine changes of properties. This work has presented a detailed study where nylon 6 and poly(propylene oxide) mixture was analysed by 13 C NMR in the solid state, and NMR spectra were shown and explained. The molecular mobility as well as the compatibility have been observed and discussed

Precursor effect on the property and catalytic behavior of Fe-TS-1 in butadiene epoxidation

Science.gov (United States)

Wu, Mei; Zhao, Huahua; Yang, Jian; Zhao, Jun; Song, Huanling; Chou, Lingjun

2017-11-01

The effect of iron precursor on the property and catalytic behavior of iron modified titanium silicalite molecular sieve (Fe-TS-1) catalysts in butadiene selective epoxidation has been studied. Three Fe-TS-1 catalysts were prepared, using iron nitrate, iron chloride and iron sulfate as precursors, which played an important role in adjusting the textural properties and chemical states of TS-1. Of the prepared Fe-TS-1 catalysts, those modified by iron nitrate (FN-TS-1) exhibited a significant enhanced performance in butadiene selective epoxidation compared to those derived from iron sulfate (FS-TS-1) or iron chloride (FC-TS-1) precursors. To obtain a deep understanding of their structure-performance relationship, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Temperature programmed desorption of NH3 (NH3-TPD), Diffuse reflectance UV-Vis spectra (DR UV-Vis), Fourier transformed infrared spectra (FT-IR) and thermal gravimetric analysis (TGA) were conducted to characterize Fe-TS-1 catalysts. Experimental results indicated that textural structures and acid sites of modified catalysts as well as the type of Fe species influenced by the precursors were all responsible for the activity and product distribution.

Evaluation of propylene glycol and glycerol infusions as treatments for ketosis in dairy cows.

Science.gov (United States)

Piantoni, P; Allen, M S

2015-08-01

To evaluate propylene glycol (PG) and glycerol (G) as potential treatments for ketosis, we conducted 2 experiments lasting 4 d each in which cows received one bolus infusion per day. Blood was collected before infusion, over 240min postinfusion, as well as 24 h postinfusion. Experiment 1 used 6 ruminally cannulated cows (26±7 d in milk) randomly assigned to 300-mL infusions of PG or G (both ≥99.5% pure) in a crossover design experiment with 2 periods. Within each period, cows were assigned randomly to infusion site sequence: abomasum (A)-cranial reticulorumen (R) or the reverse, R-A. Glucose precursors were infused into the R to simulate drenching and the A to prevent metabolism by ruminal microbes. Glycerol infused in the A increased plasma glucose concentration the most (15.8mg/dL), followed by PG infused in the R (12.6mg/dL), PG infused in the A (9.11mg/dL), and G infused in the R (7.3mg/dL). Infusion of PG into the R increased plasma insulin and insulin area under the curve (AUC) the most compared with all other treatments (7.88 vs. 2.13μIU/mL and 321 vs. 31.9min×μIU/mL, respectively). Overall, PG decreased plasma BHBA concentration after infusion (-6.46 vs. -4.55mg/dL) and increased BHBA AUC (-1,055 vs. -558min ×mg/dL) compared with G. Plasma NEFA responses were not different among treatments. Experiment 2 used 8 ruminally cannulated cows (22±5 d in milk) randomly assigned to treatment sequence in a Latin square design experiment balanced for carryover effects. Treatments were 300mL of PG, 300mL of G, 600mL of G (2G), and 300mL of PG + 300mL of G (GPG), all infused into the R. Treatment contrasts compared PG with each treatment containing glycerol (G, 2G, and GPG). Propylene glycol increased plasma glucose (14.0 vs. 5.35mg/dL) and insulin (7.59 vs. 1.11μIU/mL) concentrations compared with G, but only tended to increase glucose and insulin concentrations compared with 2G. Propylene glycol increased AUC for glucose (1,444 vs. 94.3mg/dL) and insulin (326

(Liquid + liquid) equilibrium data for the system (propylene glycol + water + tetraoctyl ammonium 2-methyl-1-naphthoate)

NARCIS (Netherlands)

Garcia Chavez, L.Y.; Shazad, Maryam; Schuur, B.; Haan, de A.B.

2012-01-01

Propylene glycol (PG) is an important low toxic glycol, widely used in the food, cosmetics, pharmaceutical and the chemical industries. The recovery of PG from aqueous streams using conventional unit operations such as evaporation is highly energy demanding because of the large amounts of water that

Nylon-6/rubber blends: 6. Notched tensile impact testing of nylon-6(ethylene-propylene rubber) blends

NARCIS (Netherlands)

Dijkstra, Krijn; Dijkstra, K.; ter Laak, J.A.; ter Laak, J.; Gaymans, R.J.

1994-01-01

The deformation and fracture behaviour of nylon-6/EPR (ethylene-propylene rubber) blends is studied as a function of strain rate and rubber content. Therefore, tensile experiments are conducted on notched specimens over a broad range of draw speeds (including strain rates as encountered in normal

Tuning PIM-PI-Based Membranes for Highly Selective Transport of Propylene/Propane

KAUST Repository

Swaidan, Ramy J.

2016-12-06

To date there exists a great deal of energetic and economic inefficiency in the separation of olefins from paraffins because the principal means of achieving industrial purity requirements is accomplished with very energy intensive cryogenic distillation. Mitigation of the severe energy intensity of the propylene/propane separation has been identified as one of seven chemical separations which can change the landscape of global energy use, and membranes have been targeted as an emerging technology because they offer scalability and lower capital and operating costs. The focus of this work was to evaluate a new direction of material development for the very industrially relevant propylene/propane separation using membranes. The objective was to develop a rational design approach for generating highly selective membranes using a relatively new platform of materials known as polyimides of intrinsic microporosity (PIM-PIs), the prospects of which have never been examined for the propylene/propane separation. Structurally, PIMs comprise relatively inflexible macromolecular architectures integrating contortion sites that help disrupt packing and trap microporous free volume elements (< 20 Å). To date most of the work reported in the literature on this separation is based on conventional low free volume 6FDA-based polyimides which in the best case show moderate C3H6/C3H8 selectivities (<20) with C3H6 permeabilities too low to garner industrial interest. Due to propylene and propane’s relatively large molecular size, we hypothesized that the use of more open structures can provide greater accessibility to the pores necessary to enhance membrane sieving and flux. It has been shown for numerous key gas separations that introduction of microporosity into a polymer structure can defy the notorious permeability/selectivity tradeoff curve and induce simultaneous boosts in both permeability and selectivity. The cornerstone approach to designing state of the art high

Combined gas-phase oxidation of methane and ethylene

International Nuclear Information System (INIS)

Pogosyan, N.M.; Pogosyan, M.D.

2009-01-01

It is established that depending on the reaction conditions combined oxidation of methane and ethylene may result in ethylene and propylene oxides with high selectivity with respect to the process, where in the initial reaction mixture methane is replaced by the same quantity of nitrogen. The formed additional methyl radicals increase the yield of all reaction products except CO. At low temperatures methyl radicals react with oxygen resulting in methyl peroxide radicals, which in turn, reacting with ethylene provide its epoxidation and formation of other oxygen-containing products. At high temperatures as a result of addition reaction between methyl radicals and ethylene, propyl radicals are formed that, in turn yield propylene. Alongside with positive influence on the yield of reaction products, methane exerts negative influence upon the conversion, that is it decreases the rate of ethylene and oxygen conversion, simultaneously decreasing significantly the yield of CO

In situ XAS study of the Mn(III)(salen)Br catalyzed synthesis of cyclic organic carbonates from epoxides and CO2

DEFF Research Database (Denmark)

Jutz, Fabian; Grunwaldt, Jan-Dierk; Baiker, Alfons

2009-01-01

In situ X-ray absorption spectroscopy at the Mn K- and Br K-edge was employed to study the cycloaddition of carbon dioxide to propylene oxide and styrene oxide, catalyzed by Mn(III) salen bromide complexes. Three homogeneous complexes with varying salen ligand structure and one complex immobilized...... coordination of the bromine neighbors to the Mn central atom was also evidenced by EXAFS spectra, e.g. loss of Br backscattering in the Mn K-EXAFS spectra and the Mn-backscattering in the Br K-edge spectra. In the catalytic studies it was observed that propylene oxide usually reacted much faster than styrene...

The Profile of Anti-inflammatory Activity of Syzigium Aromaticum Volatile Oil in Lotion with Variation Composition of Oleic Acid and Propylene Glycol as Enhancer

Directory of Open Access Journals (Sweden)

Fitriah Ardiawijianti Iriani

2017-08-01

Full Text Available Essential oil of clove (Syzygium aromaticum containing eugenol has an anti-inflammatory activity. The study was aimed to develop the formulation of lotion by adding of oleic acid and propylene glycol as penetration enhancer. The effect of enhancer composition was also studied. Lotion was prepared with the composition of oleic acid (AO and propylene glycol (PG as follow: 1:0 (FI, 0,5:0,5 (FII, 0:1 (FIII. Capacity an anti-inflammatory of formulation based on parameters of the amount of cells with COX-2 expression, the number of inflammatory cells and the epidermis thickness was evaluated using male mouse strain BALb/C induced by crotton oil as inflammatory agents. The results showed that the increasing composition propylene glycol caused the decreasing of the amount of cells with COX-2 expression (p <0.05, the inflammatory cells (P <0.05 and the epidermis thickness (p <0.05

In situ epoxide generation by dimethyldioxirane oxidation and the use of epichlorohydrin in the flow synthesis of a library of β-amino alcohols.

Science.gov (United States)

Cossar, Peter J; Baker, Jennifer R; Cain, Nicholas; McCluskey, Adam

2018-04-01

The flow coupling of epichlorohydrin with substituted phenols, while efficient, limits the nature of the epoxide available for the development of focused libraries of β-amino alcohols. This limitation was encountered in the production of analogues of 1-(4-nitrophenoxy)-3-((2-((4-(trifluoromethyl)pyrimidin-2-yl)amino)ethyl)amino)propan-2-ol 1 , a potential antibiotic lead. The in situ (flow) generation of dimethyldoxirane (DMDO) and subsequent flow olefin epoxidation abrogates this limitation and afforded facile access to structurally diverse β-amino alcohols. Analogues of 1 were readily accessed either via (i) a flow/microwave hybrid approach, or (ii) a sequential flow approach. Key steps were the in situ generation of DMDO, with olefin epoxidation in typically good yields and a flow-mediated ring opening aminolysis to form an expanded library of β-amino alcohols 1 and 10a - 18g , resulting in modest ( 11a , 21%) to excellent ( 12g , 80%) yields. Alternatively flow coupling of epichlorohydrin with phenols 4a - 4m (22%-89%) and a Bi(OTf) 3 catalysed microwave ring opening with amines afforded a select range of β-amino alcohols, but with lower levels of aminolysis regiocontrol than the sequential flow approach.

Iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of propylene to acrolein

International Nuclear Information System (INIS)

Patel, B.M.; Price, G.L.

1990-01-01

This paper reports on iron-tellurium-selenium mixed oxide catalysts prepared by coprecipitation from aqueous solution investigated for the propylene to acrolein reaction in the temperature range 543-773 K. Infrared spectroscopy, electron dispersive X-ray analysis, X-ray diffraction, and isotopic tracer techniques have also been employed to characterize this catalytic system. Properties of the Fe-Te-Se mixed oxide catalysts have been compared with Fe-Te mixed oxides in an effort to deduce the functionality of Se. The selenium in the Fe-Te-Se-O catalyst has been found to be the hydrocarbon activating site. The activation energies for the acrolein and carbon dioxide formation are 71 and 54 kJ/mol, respectively. Reactions carried out with 18 O 2 have shown lattice oxygen to be primarily responsible for the formation of both acrolein and carbon dioxide. The initial and rate-determining step for acrolein formation is hydrogen abstraction as determined by an isotope effect associated with the C 3 D 6 reaction. No isotope effect is observed for carbon dioxide formation from C 3 D 6 suggesting that CO 2 is formed by parallel, not consecutive, oxidation of propylene

Preferential hydroxylation over epoxidation catalysis by a horseradish peroxidase mutant: a cytochrome P450 mimic.

Science.gov (United States)

de Visser, Sam P

2007-10-25

Density functional theory calculations are presented on the catalytic properties of a horseradish peroxidase mutant whereby the axial nitrogen atom is replaced by phosphorus. This mutant has never been studied experimentally and only one theoretical report on this system is known (de Visser, S. P. J. Phys. Chem. B 2006, 110, 20759-20761). Thus, a one-atom substitution in horseradish peroxidase changes the properties of the catalytic center of the enzyme to more cytochrome P450-type qualities. In particular, the phosphorus-substituted horseradish peroxidase mutant reacts with substrates via a unique reactivity pattern, whereby alkanes are regioselectively hydroxylated even in the presence of a double bond. Reaction barriers of propene epoxidation and hydroxylation are almost identical to ones observed for a cytochrome P450 catalyst and significantly higher than those obtained for a horseradish peroxidase catalyst. It is shown that the regioselectivity difference is entropy and thermally driven and that the electron-transfer processes that occur during the reaction mechanism follow cytochrome P450-type patterns in the hydroxylation reaction.

Radiochemical oxidation of an ethylene-propylene-hexadiene terpolymer

International Nuclear Information System (INIS)

Verdu, J.; Pinel, B.; Gueguen, V.; Audouin, L.

1996-01-01

The γ ray initiated oxidation of an ethylene-propylene-hexadiene terpolymer (molar ratios 87/12/1) was studied by IR spectrophotometry in the 40-90 deg C temperature range, with dose rates varying from 10 to 2500 Gy h -1 and integrated doses up to 100 kGy. Bulk (∼ 8 mm) and thin (∼ 0.1 mm) samples were studied. It appears that the oxidation is diffusion controlled in the bulk samples and non diffusion controlled in thin films. A kinetic study of IR spectral changes in these latter reveals that vinylene groups of the hexadiene monomer unit disappear in the early period of exposure, presumably by addition reactions with peroxy radicals. A very simplified mechanistic scheme allows a satisfying modelling of this process whose rate is almost proportional to the dose rate (irradiation intensity). (authors)

Effect of the Compatibilizer Upon the Properties of Styrene-butadiene Rubber Organoclay Nanocomposites

Directory of Open Access Journals (Sweden)

M. Tavakoli

2013-01-01

Full Text Available Nanocomposite vulcunizates based on styrene-butadiene rubber (SBR, organoclay and a conventional sulfur curing system were prepared by melt blending process in an internal mixer. In order to study the effects of the type of interfacial compatibilizer on the properties of SBR and clay nanoparticles,three types of compatibilizers, maleic anhydride grafted ethylene-propylene diene rubber (EPDM-g-MAH, acrylonitrile-butadiene rubber (NBR and epoxidized natural rubber (ENR50 have been used. The nanocomposites have been compared together from view point of their curing behavior, rheological and mechanical properties. The developed microstructure and dynamics of the macromolecular chains in proximity of the clay nanolayers have been characterized using X-ray diffraction (XRD, scanning electron microscopy (SEM, and melt rheo-mechanical spectroscopy (RMS. Curing behavior of the prepared nanocomposites has been evaluated using a rubber curing rheometer. EPDM-g-MAH and ENR50 showed to enhance the interactions between SBR chains into clay tactoids much stronger than NBR as a compatibilizer. These were consistent with the dynamic mechanical thermal analysis (DMTA data as well as macroscale mechanical properties tested on the samples.

Correlation between the size and the magnetic properties of Ag2+ clusters loaded on ceria surface and their catalytic performance in the total oxidation of propylene. EPR study

Science.gov (United States)

Hany, Sara; Skaf, Mira; Aouad, Samer; Gennequin, Cédric; Labaki, Madona; Abi-Aad, Edmond; Aboukaïs, Antoine

2018-03-01

Three different types of Ag2+ ions ("a", "b", and "c") have been identified and examined by electron paramagnetic resonance (EPR) on 10% wt Ag/CeO2 prepared by impregnation method. One of them, Ag2+(b), behaves differently than the two others, Ag2+(a) and Ag2+(c), under redox atmospheres. The fact that, in reducing conditions (vacuum, propylene, hydrogen, and carbon black), Ag2+(a) and Ag2+(c) species were more easily reduced than Ag2+(b) ones, could not explain the catalytic performance and stability of this latter species compared to the first ones in the reaction of total oxidation of propylene. The EPR technique evidenced that Ag2+(b) species form, upon propene oxidation, a cluster. This cluster is composed of two parallel electron spins (dimer) and three nuclear spins (trimer). It seems that before propylene oxidation, Ag2+(b) clusters were ferromagnetic. This ferromagnetic character of Ag2+(b) species may explain their better catalytic performance, in propylene oxidation, than those of Ag2+(a) and Ag2+(c) ones.

Síntese e caracterização de dispersões aquosas de poliuretanos à base de copolímeros em bloco de poli(glicol etilênico e poli(glicol propilênico Synthesis and characterization of polyurethane aquous dispersions based on poly(ethylene glycol and poly(propylene glycol block copolymers

Directory of Open Access Journals (Sweden)

Fernanda M. B. Coutinho

2008-01-01

Full Text Available Non-polluting polyurethane aqueous dispersions, with 40% of solids content, were synthesized based on block copolymers of poly(ethylene glycol and poly(propylene glycol (PEG-b-PPG, with PEG hydrophilic segments content of 7 and 25%, poly(propylene glycol (PPG, dimethylolpropionic acid (DMPA, isophorone diisocyanate (IPDI, and hydrazine. Different formulations were synthesized by varying the equivalent-grams ratios between isocyanate and hydroxyl groups (NCO/OH and PPG and (PEG-b-PPG. The presence of high amounts of PEG in the formulations provoked the formation of gels. Average particle size and viscosity of the dispersions were determined. Mechanical properties and water absorption resistance of cast films were evaluated.

New hybrid nanofluid containing encapsulated paraffin wax and sand nanoparticles in propylene glycol-water mixture: Potential heat transfer fluid for energy management

International Nuclear Information System (INIS)

Manikandan, S.; Rajan, K.S.

2017-01-01

Highlights: • Hybrid nanofluid containing sand nanoparticles & encapsulated paraffin wax prepared. • Specific heat of hybrid nanofluid 9% greater than that of PG-water mixture. • Specific heat & thermal conductivity enhanced at optimum paraffin wax concentration. • Hybrid nanofluid with 1 wt.% paraffin wax & 1 vol% sand nanoparticles best suited. - Abstract: The reduction in specific heat commonly encountered due to the addition of nanoparticles to a heat transfer fluid such as propylene glycol-water mixture, can be overcome by co-dispersing surfactant-encapsulated paraffin wax, leading to formation of a hybrid nanofluid. Experimental investigations have been carried out on the preparation and evaluation of thermophysical properties of a hybrid nanofluid containing pluronic P-123 encapsulated paraffin wax (70–120 nm diameter, 1–5 wt.%) and sand nanoparticles (1 vol%) in propylene glycol-water mixture. The comparison of results of differential scanning calorimetry of pure paraffin wax and encapsulated paraffin wax revealed encapsulation efficiency of 84.4%. The specific heat of hybrid nanofluids monotonously increased with paraffin wax concentration, with 9.1% enhancement in specific heat for hybrid nanofluid containing 5 wt.% paraffin wax, in comparison to propylene glycol-water mixture. There exists an optimum paraffin wax concentration (1 wt.%) for the hybrid nanofluid at which the combination of various thermophysical properties such as specific heat, thermal conductivity and viscosity are favorable for use as heat transfer fluid. Such a hybrid nanofluid can be used as a substitute for propylene glycol-water mixture in solar thermal systems.

Niobium(v) chloride and imidazolium bromides as efficient dual catalyst systems for the cycloaddition of carbon dioxide and propylene oxide

KAUST Repository

Wilhelm, Michael E.; Anthofer, Michael H.; Reich, Robert M.; D'Elia, Valerio; Basset, Jean-Marie; Herrmann, Wolfgang A.; Cokoja, Mirza; Kü hn, Fritz

2014-01-01

The application of niobium(v) chloride and several imidazolium bromides as catalyst systems for the cycloaddition of propylene oxide (PO) with carbon dioxide to propylene carbonate (PC) is reported. A set of 31 different imidazolium bromides has been synthesized with varying substituents at all five imidazolium ring atoms, of which 17 have not been reported before. The impact of different substitution patterns (steric and electronic changes and solubility in PO) at the imidazolium ring on the catalytic activity was investigated. The optimisation of the catalyst structure allows for the valorisation of carbon dioxide under mild reaction conditions with high reaction rates in very good yield and selectivity for PC. This journal is © the Partner Organisations 2014.

Niobium(v) chloride and imidazolium bromides as efficient dual catalyst systems for the cycloaddition of carbon dioxide and propylene oxide

KAUST Repository

Wilhelm, Michael E.

2014-02-19

The application of niobium(v) chloride and several imidazolium bromides as catalyst systems for the cycloaddition of propylene oxide (PO) with carbon dioxide to propylene carbonate (PC) is reported. A set of 31 different imidazolium bromides has been synthesized with varying substituents at all five imidazolium ring atoms, of which 17 have not been reported before. The impact of different substitution patterns (steric and electronic changes and solubility in PO) at the imidazolium ring on the catalytic activity was investigated. The optimisation of the catalyst structure allows for the valorisation of carbon dioxide under mild reaction conditions with high reaction rates in very good yield and selectivity for PC. This journal is © the Partner Organisations 2014.

Epoxidation of soybean oil with [MoO{sub 2}(acac){sub 2}]/TBHP Catalytic system in [bmim][PF{sub 6}]; Epoxidacao do oleo de soja com o sistema catalitico [MoO{sub 2}(acac){sub 2}]/TBHP em [bmim][PF{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Farias, Maritana [Instituto Federal de Educacao, Ciencia e Tecnologia Sul-rio-grandense, Pelotas, RS (Brazil); Martinelli, Marcia, E-mail: maritana@pelotas.ifsul.edu.br [Universidade Federal do Rio Grande do Sul, Porto Alegre, RS (Brazil). Inst. de Quimica. Dept. de Quimica Inorganica

2012-07-01

Epoxidation of soybean oil was investigated using 1-n-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF{sub 6}] ionic liquid as biphasic medium with molybdenum(VI) acetylacetonate complex and tert-butyl hydroperoxide TBHP as oxidizing agent. Reaction conditions were molar ratio TBHP:number of double bonds of oil:catalyst of 100:100:1, reaction temperature of 60 deg C and reaction time between 2 and 24 h. The proposed system showed catalytic activity for epoxidation reactions under tested conditions. Reuse of ionic liquid/catalyst system for epoxidation reactions was also investigated. Evaluation of epoxidation observed in this catalytic system was done by quantitative {sup 1}H NMR data. (author)

Anhydrous ZnCl2: A Highly Efficient Reagent for Facile and Regioselective Conversion of Epoxides to β-Chlorohydrins

Directory of Open Access Journals (Sweden)

Ronak Eisavi

2016-01-01

Full Text Available Facile conversion of structurally different epoxides to the corresponding β-chlorohydrins was carried out successfully with anhydrous ZnCl2 in CH3CN. The reactions were carried out within 10-50 min to give β-chlorohydrins with perfect regioselectivity and high yields (80-97%.

Synthesis of Biolubricant Basestocks from Epoxidized Soybean Oil

Directory of Open Access Journals (Sweden)

Rosa Turco

2017-10-01

Full Text Available This work deals with the preparation of biolubricant basestocks through the ring-opening reaction of epoxidized soybean oil (ESO by alcohols in presence of solid acid catalysts (SAC-13 resin. To this end, different experimental runs were carried out in a lab-scale reactor, analyzing the effect of the alcohol (methanol, ethanol, 2-propanol, 2-butanol, catalyst mass loading (from 1 to 10 wt % with respect to the oil mass and operating temperature (60–90 °C. The main focus of investigation was oxirane conversion. The study was complemented by FT-IR, 1H NMR and kinematic viscosity characterization of the different products of the ring-opening reaction. Experimental conversion data were fitted through a suitable kinetic model. Values of the best-fitting parameters in terms of rate constant, activation energy and catalyst reaction order were obtained, and were potentially useful for the design of an industrial process.

Induction of hepatic aryl hydrocarbon hydroxylase and epoxide hydrase in Wistar rats pretreated with oral methadone hydrochloride.

Science.gov (United States)

Bellward, G D; Gontovnick, L S; Otten, M

1977-01-01

Methadone-HCl added to the drinking water of adult female Wistar rats for 4 weeks produced an increase in the aryl hydrocarbon hydroxylase activity of the hepatic microsomal fraction to 222% of control levels. No change was seen in epoxide hydrase activity. In contrast, when male rats were treated similarly, there was an increase in epoxide hydrase activity to 212% of controls with no change in aryl hydrocarbon hydroxylase activity. No such changes were observed when the subcutaneous route of administration or chronic, low-dose, intraperitoneal injections were used. There were no differences in hepatic cytochrome P-450 or protein concentrations in treated animals as compared to their respective control groups. Control studies were carried out with quinine sulfate in the drinking water to decrease water intake to the level of the methadone-treated group. No elevation in either enzyme activity occurred in this control group. Similarly, paired-feeding studies showed the elevation of enzyme activity to be due to the methadone, not food deprivation. The effects of concurrent therapy of methadone with phenobarbital sodium or 3-methylcholanthrene were compared.

Bifunctional nanocrystalline MgO for chiral epoxy ketones via Claisen-Schmidt condensation-asymmetric epoxidation reactions.

Science.gov (United States)

Choudary, Boyapati M; Kantam, Mannepalli L; Ranganath, Kalluri V S; Mahendar, Koosam; Sreedhar, Bojja

2004-03-24

Design and development of a truly nanobifunctional heterogeneous catalyst for the Claisen-Schmidt condensation (CSC) of benzaldehydes with acetophenones to yield chalcones quantitatively followed by asymmetric epoxidation (AE) to afford chiral epoxy ketones with moderate to good yields and impressive ee's is described. The nanomagnesium oxide (aerogel prepared) NAP-MgO was found to be superior over the NA-MgO and CM-MgO in terms of activity and enantioselectivity as applicable in these reactions. An elegant strategy for heterogenization of homogeneous catalysts is presented here to evolve single-site chiral catalysts for AE by a successful transfer of molecular chemistry to surface metal-organic chemistry with the retention of activity, selectivity/enantioselectivity. Brønsted hydroxyls are established as sole contributors for the epoxidation reaction, while they add on to the CSC, which is largely driven by Lewis basic O2-sites. Strong hydrogen-bond interactions between the surface -OH on MgO and -OH groups of diethyl tartrate are found inducing enantioselectivity in the AE reaction. Thus, the nanocrystalline NAP-MgO with its defined shape, size, and accessible OH groups allows the chemisorption of TBHP, DET, and olefin on its surface to accomplish single-site chiral catalysts to provide optimum ee's in AE reactions.

Significance of the lipid phase in the dynamics and functions of the xanthophyll cycle as revealed by PsbS overexpression in tobacco and in-vitro de-epoxidation in monogalactosyldiacylglycerol micelles.

Science.gov (United States)

Hieber, A David; Kawabata, Osamu; Yamamoto, Harry Y

2004-01-01

The dynamics of the xanthophyll cycle relative to non-photochemical quenching (NPQ) were examined in tobacco plants overexpressing violaxanthin de-epoxidase (VDE), PsbS and PsbS+VDE for effects on NPQ and violaxanthin (V) de-epoxidation over a range of light intensities. Induction of de-epoxidation and NPQ increased in overexpressed VDE and PsbS plants, respectively. Surprisingly, under low light, overexpressing PsbS enhanced de-epoxidation in addition to NPQ. The effect was hypothesized as due to PsbS binding zeaxanthin (Z) or inducing the binding of Z within the quenching complex, thus shifting the equilibrium toward higher de-epoxidation states. Studies in model systems show that Z can stereospecifically inhibit VDE activity against violaxanthin. This effect, observed under conditions of limiting lipid concentration, was interpreted as product feedback inhibition. These results support the hypothesis that the capacity of the thylakoid lipid phase for xanthophylls is limited and modulates xanthophyll-cycle activity, in conjunction with the release of V and binding of Z by pigment-binding proteins. These modulating factors are incorporated into a lipid-matrix model that has elements of a signal transduction system wherein the light-generated protons are the signal, VDE the signal receptor, Z the secondary messenger, the lipid phase the transduction network, and Z-binding proteins the targets.

The Epoxidation of Limonene over the TS-1 and Ti-SBA-15 Catalysts

Directory of Open Access Journals (Sweden)

Agnieszka Wróblewska

2014-11-01

Full Text Available Limonene belongs to a group of very important intermediates used in the production of fine chemicals. This monoterpene compound can be obtained from peels of oranges or lemon which are a (biomass waste from the orange juice industry. Thus, limonene is a renewable, easy available and a relatively cheap compound. This work presents preliminary studies on the process of limonene epoxidation over zeolite type catalysts such as: TS-1 and Ti-SBA-15. In these studies methanol was used as a solvent and as an oxidizing agent a 60 wt % hydrogen peroxide solution was applied. The activity of each catalyst was investigated for four chosen temperatures (0 °C, 40 °C, 80 °C and 120 °C. The reaction time was changed from 0.5 to 24 h. For each catalyst the most beneficial conditions (the appropriate temperature and the reaction time have been established. The obtained results were compared and the most active catalyst was chosen. These studies have also shown different possible ways of limonene transformation, not only in the direction of 1,2-epoxylimonene and its corresponding diol, but also in direction of carveol, carvone and perillyl alcohol—compounds with a lot of applications. The possible mechanisms of formation of the allylic oxidation products were proposed.

Combination of natural fiber Boehmeria nivea (ramie) with matrix epoxide for bullet proof vest body armor

Energy Technology Data Exchange (ETDEWEB)

Anggoro, Didi Dwi, E-mail: anggorophd@gmail.com; Kristiana, Nunung, E-mail: nuna.c631@gmail.com [Master of Chemical Engineering, Faculty of Engineering, Diponegoro University Jln. Prof. Sudharto, Tembalang, Semarang, 50239 (Indonesia)

2015-12-29

Ballistic protection equipment, such as a bulletproof vest, is a soldier’s most important means of preserving life and survivability in extreme combat conditions. The bulletproof vests are designed to protect the user’s chest from injury without disturbing the ability to perform his duties. Aromatic polyamide or aramid fibers known under the trade name Kevlar, Trawon and so is synthetic fiber materials commonly used in the manufacture of bulletproof vests. This synthetic fibers have high tensile strength and ductility. Kevlar is expensive and imported material. In this study, will introduce local natural raw materials, ramie fiber (Boehmeria nivea) which is cheaper and environmentally friendly. It has enough tenacity and tensile strength as a bulletproof vest. This experiment uses two panels, there are Panel A as front surface of Panel B. Panel A is a combination of ramie and epoxide matrix, while panel B is only ramie. From several variations of experimental combinations between Panel A and Panel B, optimal combination obtained with 16 layers of panel A and 31-34 layers of panel B which is able to protect againts cal. 7.65 mm × 17 mm (.32 ACP) bullet fired through pistol .32 Pindad from a distance of 20 meters. Panel with a size of 20 cm × 20 cm has a total thickness between 12,922 to13,745 mm and a total weight between 506,26 to 520,926gram. Scanning electron microscopy (SEM) observations indicated that the porosity and surface area of the ramie fiber is smooth, fiber surfaces showed topography with micropores. SEM also showed well-arranged structure of fibers bonding. Energy Dispersive X-ray (EDX) analysis indicated 100 % carbon contents in ramie fiber. Test result indicates that panel from composite ramie-epoxide can reach the level 1of International Standard of NIJ - 010104. Compared to panel from polyester fiber, the panel from composite ramie-epoxide (0,50-0,52 kg) is lighter weight than panel polyester fiber (1,642 kg)

Combination of natural fiber Boehmeria nivea (ramie) with matrix epoxide for bullet proof vest body armor

International Nuclear Information System (INIS)

Anggoro, Didi Dwi; Kristiana, Nunung

2015-01-01

Ballistic protection equipment, such as a bulletproof vest, is a soldier’s most important means of preserving life and survivability in extreme combat conditions. The bulletproof vests are designed to protect the user’s chest from injury without disturbing the ability to perform his duties. Aromatic polyamide or aramid fibers known under the trade name Kevlar, Trawon and so is synthetic fiber materials commonly used in the manufacture of bulletproof vests. This synthetic fibers have high tensile strength and ductility. Kevlar is expensive and imported material. In this study, will introduce local natural raw materials, ramie fiber (Boehmeria nivea) which is cheaper and environmentally friendly. It has enough tenacity and tensile strength as a bulletproof vest. This experiment uses two panels, there are Panel A as front surface of Panel B. Panel A is a combination of ramie and epoxide matrix, while panel B is only ramie. From several variations of experimental combinations between Panel A and Panel B, optimal combination obtained with 16 layers of panel A and 31-34 layers of panel B which is able to protect againts cal. 7.65 mm × 17 mm (.32 ACP) bullet fired through pistol .32 Pindad from a distance of 20 meters. Panel with a size of 20 cm × 20 cm has a total thickness between 12,922 to13,745 mm and a total weight between 506,26 to 520,926gram. Scanning electron microscopy (SEM) observations indicated that the porosity and surface area of the ramie fiber is smooth, fiber surfaces showed topography with micropores. SEM also showed well-arranged structure of fibers bonding. Energy Dispersive X-ray (EDX) analysis indicated 100 % carbon contents in ramie fiber. Test result indicates that panel from composite ramie-epoxide can reach the level 1of International Standard of NIJ - 010104. Compared to panel from polyester fiber, the panel from composite ramie-epoxide (0,50-0,52 kg) is lighter weight than panel polyester fiber (1,642 kg)

Determination of the Mechanical Properties of Rubber by FT-NIR

OpenAIRE

Pornprasit, Rattapol; Pornprasit, Philaiwan; Boonma, Pruet; Natwichai, Juggapong

2016-01-01

Mechanical tests, for example, tensile and hardness tests, are usually used to evaluate the properties of rubber materials. In this work, mechanical properties of selected rubber materials, that is, natural rubber (NR), styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), and ethylene propylene diene monomer (EPDM), were evaluated using a near infrared (NIR) spectroscopy technique. Here, NR/NBR and NR/EPDM blends were first prepared. All of the samples were then scanned using a FT-...

Zirconium(IV)-Catalyzed Ring Opening of on-DNA Epoxides in Water.

Science.gov (United States)

Fan, Lijun; Davie, Christopher P

2017-05-04

DNA-encoded library technology (ELT) has spurred wide interest in the pharmaceutical industry as a powerful tool for hit and lead generation. In recent years a number of "DNA-compatible" chemical modifications have been published and used to synthesize vastly diverse screening libraries. Herein we report a newly developed, zirconium tetrakis(dodecyl sulfate) [Zr(DS) 4 ] catalyzed ring-opening of on-DNA epoxides in water with amines, including anilines. Subsequent cyclization of the resulting on-DNA β-amino alcohols leads to a variety of biologically interesting, nonaromatic heterocycles. Under these conditions, a library of 137 million on-DNA β-amino alcohols and their cyclization products was assembled. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of soybean oil epoxidation with peracetic acid formed in situ in the presence of an ion exchange resin: Pseudo-homogeneous model

Directory of Open Access Journals (Sweden)

Janković Milovan

2017-01-01

Full Text Available A kinetic model was proposed for the epoxidation of vegetable oils with peracetic acid formed in situ from acetic acid and hydrogen peroxide in the presence of an acidic ion exchange resin as a catalyst. The model is pseudo-homogeneous with respect to the catalyst. Besides the main reactions of peracetic acid and epoxy ring formation, the model takes into account the side reaction of epoxy ring opening with acetic acid. The partitioning of acetic acid and peracetic acid between the aqueous and organic phases and the change in the phases’ volumes during the process were considered. The temperature dependency of the apparent reaction rate coefficients is described by a reparameterized Arrhenius equation. The constants in the proposed model were estimated by fitting the experimental data obtained for the epoxidations of soybean oil conducted under defined reaction conditions. The highest epoxy yield of 87.73% was obtained at 338 K when the mole ratio of oil unsaturation:acetic acid:hydrogen peroxide was 1:0.5:1.35 and when the amount of the catalyst Amberlite IR-120H was 4.04 wt.% of oil. Compared to the other reported pseudo-homogeneous models, the model proposed in this study better correlates the change of double bond and epoxy group contents during the epoxidation process. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45022

Mechanisms of interaction of radiation with matter

International Nuclear Information System (INIS)

Geacintov, N.E.; Pope, M.

1993-01-01

This project is concerned with the mechanisms by which polynuclear aromatic (PNA) compounds on the one hand, and ionizing radiation on the other, cause damage to DNA. PNA compounds constitute an important class of environmental pollutants derived from energy-related sources which, upon metabolic activation to diolepoxide derivatives, produce bulky PNA-DNA lesions interfere with the normal DNA replication and transcription processes, and give rise to mutations and the initiation of tumors. Chiral and other stereochemical effects play a key role in determining the biological effects of a given PNA diol epoxide and the potentially mutagenic lesions which are formed. New and efficient methods for synthesizing stereochemically pure and precisely positioned PNA diol epoxide-DNA lesions in small DNA fragments are reported here. We have elucidated the structures of three stereoisomeric benzo[a]pyrene diol epoxide-DNA adducts. How these adducts affect on DNA polymerase fidelity, transcription, and DNA repair are currently being investigated with respect to detailed structure-biological activity correlations. Spectroscopic techniques such as circular dichroism, fluorescence, and photoionization play an important role in the characterizations of the PNA adducts. A new method was developed for measuring the lifetimes as well as the energies of picosecond duration electronically excited states. Using this technique, it is proposed that short-lived (15 ps) charge-transfer (CT) states in the PNA compound tetracene are activated by a 20 ps laser pulse; an unusual external photoemission echo do to the recombination of CT states is observed 85 ps after the pulse

NH3-SCR on Cu, Fe and Cu + Fe exchanged beta and SSZ-13 catalysts: Hydrothermal aging and propylene poisoning effects

International Nuclear Information System (INIS)

Wang, Aiyong; Wang, Yilin; Walter, Eric D.; Washton, Nancy M.

2017-01-01

Cu, Fe and Cu + Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH 4 /Beta, and NH 4 /SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 °C and SSZ-13 supported catalysts were aged at 750 °C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N 2 adsorption-desorption, electron paramagnetic resonance (EPR), 27 Al-nuclear magnetic resonance ( 27 Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further tested with standard NH 3 -SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH 3 -SCR activity, N 2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. In conclusion, at elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N 2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene.

Nanobody based immunoassay for human soluble epoxide hydrolase detection using polyHRP for signal enhancement—the rediscovery of polyHRP

Science.gov (United States)

Soluble epoxide hydrolase (sEH) is a potential pharmacological target for treating hypertension, vascular inflammation, cancer, pain and multiple cardiovascular related diseases. A variable domain of a heavy chain only antibody (termed sdAb, nanobody or VHH) possesses advantages of small size, high ...

Altered Escherichia coli membrane protein assembly machinery allows proper membrane assembly of eukaryotic protein vitamin K epoxide reductase.

Science.gov (United States)

Hatahet, Feras; Blazyk, Jessica L; Martineau, Eugenie; Mandela, Eric; Zhao, Yongxin; Campbell, Robert E; Beckwith, Jonathan; Boyd, Dana

2015-12-08

Functional overexpression of polytopic membrane proteins, particularly when in a foreign host, is often a challenging task. Factors that negatively affect such processes are poorly understood. Using the mammalian membrane protein vitamin K epoxide reductase (VKORc1) as a reporter, we describe a genetic selection approach allowing the isolation of Escherichia coli mutants capable of functionally expressing this blood-coagulation enzyme. The isolated mutants map to components of membrane protein assembly and quality control proteins YidC and HslV. We show that changes in the VKORc1 sequence and in the YidC hydrophilic groove along with the inactivation of HslV promote VKORc1 activity and dramatically increase its expression level. We hypothesize that such changes correct for mismatches in the membrane topogenic signals between E. coli and eukaryotic cells guiding proper membrane integration. Furthermore, the obtained mutants allow the study of VKORc1 reaction mechanisms, inhibition by warfarin, and the high-throughput screening for potential anticoagulants.

Evaluation of the precision-cut liver and lung slice systems for the study of induction of CYP1, epoxide hydrolase and glutathione S-transferase activities.

Science.gov (United States)

Pushparajah, Daphnee S; Umachandran, Meera; Plant, Kathryn E; Plant, Nick; Ioannides, Costas

2007-02-28

The principal objective was to ascertain whether precision-cut tissue slices can be used to evaluate the potential of chemicals to induce CYP1, epoxide hydrolase and glutathione S-transferase activities, all being important enzymes involved in the metabolism of polycyclic aromatic hydrocarbons. Precision-cut rat liver and lung slices were incubated with a range of benzo[a]pyrene concentrations for various time periods. A rise in the O-deethylation of ethoxyresorufin was seen in both liver and lung slices exposed to benzo[a]pyrene, which was accompanied by increased CYP1A apoprotein levels. Pulmonary CYP1B1 apoprotein levels and hepatic mRNA levels were similarly enhanced. Elevated epoxide hydrolase and glutathione S-transferase activities were also observed in liver slices following incubation for 24h; similarly, a rise in apoprotein levels of both enzymes was evident, peak levels occurring at the same time point. When mRNA levels were monitored, a rise in the levels of both enzymes was seen as early as 4h after incubation, but maximum levels were attained at 24 h. In lung slices, induction of epoxide hydrolase by benzo[a]pyrene was observed after a 24-h incubation, and at a concentration of 1 microM; a rise in apoprotein levels was seen at this time point. Glutathione S-transferase activity was not inducible in lung slices by benzo[a]pyrene but a modest increase was observed in hepatic slices. Collectively, these studies confirmed CYP1A induction in rat liver slices and established that CYP1B1 expression, and epoxide hydrolase and glutathione S-transferase activities are inducible in precision-cut tissue slices.

Optimization and validation of bioanalytical SPE – HPLC method for the simultaneous determination of carbamazepine and its main metabolite, carbamazepine-10, 11-epoxide, in plasma

Directory of Open Access Journals (Sweden)

Jasmina Tonic – Ribarska

2012-03-01

Full Text Available Carbamazepine is widely used as an antiepileptic drug in the treatment of partial and generalized tonic-clonic seizures. Carbamazepine 10,11-epoxide is the most important metabolite of carbamazepine, because it is a pharmacologically active compound with anticonvulsant properties. According to that, the routine analysis of carbamazepine 10,11-epoxide along with carbamazepine may provide optimal therapeutic monitoring of carbamazepine treatment. The aim of this study was to optimize and validate a simple and reliable solid - phase extraction method followed by RP-HPLC for the simultaneous determination of plasma levels of carbamazepine and carbamazepine-10,11-epoxide, in order to assure the implementation of the method for therapeutic monitoring. The extraction of the analytes from the plasma samples was performed by means of a solid-phase extraction procedure. The separation was carried out on a reversed-phase column using isocratic elution with acetonitrile and water (35:65, v/v as a mobile phase. The temperature was 30°C and UV detection was set at 220 nm. The extraction yield values were more than 98% for all analytes, measured at four concentration levels of the linear concentration range. The method displayed excellent selectivity, sensitivity, linearity, precision and accuracy. Stability studies indicate that stock solutions and plasma samples were stabile under different storage conditions at least during the observed period. The method was successfully applied to determine the carbamazepine and carbamazepine-10,11-epoxide in plasma of epileptic patients treated with carbamazepine as monotherapy and in polytherapy. In conclusion, the proposed method is suitable for application in therapeutic drug monitoring of epileptic patients undergoing treatment with carbamazepine.

Hofmeister effect of salt mixtures on thermo-responsive poly(propylene oxide)

DEFF Research Database (Denmark)

Moghaddam, Saeed Zajforoushan; Thormann, Esben

2015-01-01

of aqueous solutions of poly(propylene oxide) is affected by mixtures of ions with different location in the Hofmeister series. Our results show that the Hofmeister effects of pure salt species are not always linearly additive and that the relative effect of some ions can be reversed depending...... on the composition of the salt mixture as well as by the absolute and relative concentration of the different species. We suggest that these results can lead to a better understanding of the potential role of the Hofmeister effect in regulation of biological processes, which does always take place in salt mixtures...... rather than solutions containing just single salt species....

The fabrication of porous 4A-zeolite-supported Ag nanoparticles catalysts and its catalytic activity for styrene epoxidation

Directory of Open Access Journals (Sweden)

Youkui Wu

Full Text Available Binderless hierarchically porous 4A-zeolite has been successful produced through hydrothermal crystallization, in which silicon-aluminum sol binded to the carbon nanofibers (CNFs, that is to say, where the CNFs powder was coated during the crystallization 4A-zeolite. The mixing of silica-alumina sol and CNFs was only a simple physical mixing process. The samples of micropores-macroporous hierarchical 4A-zeolite (P-4A-zeolite was analyzed by a series of characterization techniques, such as field emission scanning electron microscope (FESEM, transmission electron microscopy (TEM, simultaneous thermal analysis (STA and CO2 adsorption-desorption (BET and BJH, and so on. In addition, the adsorption test of silver nanoparticles was carried out. The characterization results indicated the presence of micropores and the formation of macroporous. At the same time, silver adsorption test proved that the prepared P-4A-zeolite had good adsorption performance and the catalytic performance of Ag/P-4A-zeolite was further investigated through the epoxidation of styrene. Keywords: Carbon nanofibers, Porous 4A-zeolite, Silver nanoparticles, Styrene epoxidation

Sulfonation of vulcanized ethylene-propylene-diene terpolymer membranes

International Nuclear Information System (INIS)

Barroso-Bujans, F.; Verdejo, R.; Lozano, A.; Fierro, J.L.G.; Lopez-Manchado, M.A.

2008-01-01

In the present work, sulfonation of previously vulcanized ethylene propylene diene terpolymer (EPDM) membranes was developed in a swelling solvent with acetyl sulfate. This procedure avoids the need to pre-dissolve the raw polymer. The reaction conditions were optimized in terms of solvent type, reaction time, acetyl sulfate concentration and film thickness to obtain the maximum degree of sulfonation of the polymer. The sulfonation procedure presented in this study yields a degree of sulfonation comparable to the chlorosulfonic acid procedure. Sulfonic acid groups were detected by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, and quantified by titrations. Proton conductivity and water uptake were measured by means of impedance spectroscopy and swelling measurements, respectively, and were correlated with the degree of sulfonation. Tensile strength and Young's modulus of sulfonated EPDM increased with the degree of sulfonation, while elongation at break remained constant. Thermal stability of the sulfonated EPDM was studied by simultaneous thermogravimetry-mass spectroscopy

Benzo(a)pyrene diol epoxides as intermediates in nucleic acid binding in vitro and in vivo.

Science.gov (United States)

Weinstein, I B; Jeffrey, A M; Jennette, K W; Blobstein, S H; Harvey, R G; Harris, C; Autrup, H; Kasai, H; Nakanishi, K

1976-08-13

Evidence has been obtained that a specific isomer of a diol epoxide derivative of benzo(a)pyrene, (+/-)-7 beta,8alpha-dihydroxy-9alpha, 10alpha-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene, is an intermediate in the binding of benzo(a)pyrene to RNA in cultured bovine bronchial mucosa. An adduct is formed between position 10 of this derivative and the 2-amino group of guanine.

Composite TiO2/hydrocarbon plasma polymer films prepared by magnetron sputtering of TiO2 and poly(propylene)

Czech Academy of Sciences Publication Activity Database

Drabik, M.; Hanuš, J.; Kousal, J.; Choukourov, A.; Biederman, H.; Slavínská, D.; Macková, Anna; Pešička, J.

2007-01-01

Roč. 4, č. 6 (2007), s. 654-663 ISSN 1612-8850 Institutional research plan: CEZ:AV0Z10480505 Keywords : composite thin films * magnetron * poly(propylene) (PP) Subject RIV: BE - Theoretical Physics Impact factor: 2.132, year: 2007

Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

KAUST Repository

Zwaschka, Gregor; Rondelli, Manuel; Krause, Maximilian; Rö tzer, Marian David; Hedhili, Mohamed N.; Heiz, Ulrich; Basset, Jean-Marie; Schweinberger, Florian; D'Elia, Valerio

2018-01-01

The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

KAUST Repository

Zwaschka, Gregor

2018-01-22

The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

NMR study of the epoxidation of liquid hydrolyzed poly-butadiene and meta-chloro-per-benzoic acid; Estudo atraves de RMN da reacao de epoxidacao de polibutadieno liquido hidroxilado (PBLH) e acido m-cloro perbenzoico (AMCPB)

Energy Technology Data Exchange (ETDEWEB)

Aguiar, Marcelo [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica; Akcelrud, L [Universidade Federal, Rio de Janeiro, RJ (Brazil). Escola de Quimica; Menezes, Sonia Cabral de [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

1994-12-31

This work presents a study concerning the selectivity of the different configurations of the double bond present in liquid hydrolyzed poly-butadiene towards the epoxidation reaction with meta-chloro-per-benzoic acid through hydrogen-1, carbon-13 NMR aiming the production of new materials, varying the epoxidation level 12 refs., 7 figs., 4 tabs.

Effects of propylene glycol supplementation on blood indicators of hepatic function, body condition score, milk fat-protein concentration and reproductive performance of dairy cows

Directory of Open Access Journals (Sweden)

Silviu Ionuţ Borş

2014-01-01

Full Text Available The aim of the present study was to determine the effects of propylene glycol on metabolic variables of hepatic function, body condition score, milk fat-protein concentration and reproductive performance of dairy cows after ending administration. Postparturient dairy cows (n = 200 of Holstein Friesian breed were divided into two groups of 100 individuals. The experimental group received during days 0-7 post partum an oral daily dose of 600 ml of propylene glycol; the control group was without any supplement. The hepatic enzymes, glucose, cholesterol and serum albumin were measured on days 10-15, 45-50 and 70 post partum. Reproduction indicators of dairy cows were calculated from the farm recording data and the milk data record from a regular dairy control (days 10, 20, 30, and 50 post partum. Animals that received propylene glycol in the first 7 days post partum had reduced activities of aspartate transaminase and gamma-glutamyl transferase, elevated cholesterol concentration (P 0.05 and low milk fat percentage (P P 0.05. Our results suggest that some blood indicators of hepatic function, milk fat concentration and calving to first oestrus interval can be improved for 70 days post partum by the use of propylene glycol drenching in the first 7 days post partum. The beneficial effect of this treatment could be evaluated by easily available data, which can be used by practitioners in the field to analyze fertility problems in dairy herds and more exactly to examine whether metabolic stress, among other factors, is involved in the fertility problem.

Microencapsulation of Epoxidized Linseed Oil Liquid Cross-Linker in Poly(N-vinyl-pyrrolidone): Optimization by a Design-of-Experiments Approach

NARCIS (Netherlands)

Senatore, D.; Laven, J.; Benthem, van R.A.T.M.; La Camera, D.; With, de G.

2010-01-01

A liquid cross-linker, epoxidized linseed oil (ELO), was encapsulated in a plastic with a high glass transition temperature (poly(N-vinyl-2-pyrrolidone); PVP). The process parameters of the spray-drying employed were optimized by a Design-of-Experiments (DoE) approach. Three factors concerning both

New eco-friendly random copolyesters based on poly(propylene cyclohexanedicarboxylate: Structure-properties relationships

Directory of Open Access Journals (Sweden)

L. Genovese

2015-11-01

Full Text Available A series of novel random copolymers of poly(propylene 1,4-cyclohexanedicarboxylate (PPCE containing neo -pentyl glycol sub-unit (P(PCExNCEy were synthesized and characterized in terms of molecular and solid-state properties. In addition, biodegradability studies in compost have been conducted. The copolymers displayed a high and similar thermal stability with respect to PPCE. At room temperature, all the copolymers appeared as semicrystalline materials: the main effect of copolymerization was a lowering of crystallinity degree (χc and a decrease of the melting temperature compared to the parent homopolymer. In particular, Wide Angle X-Ray diffraction (WAXD measurements indicated that P(PCExNCEy copolymers are characterized by cocrystallization, PNCE counits cocrystallizing in PPCE crystalline phase. Final properties and biodegradation rate of the materials under study were strictly dependent on copolymer composition and χc. As a matter of fact, the elastic modulus and the elongation at break decreased and increased, respectively, as neopentyl glycol cyclohexanedicarboxylate (NCE unit content was increased. The presence of a rigid-amorphous phase was evidenced by means of Dynamic Mechanical Thermal Analysis (DMTA analysis in all the samples under investigation. Lastly, the biodegradation rate of P(PCExNCEy copolymers was found to slightly increase with the increasing of NCE molar content.

Studies on whole cell fluorescence-based screening for epoxide hydrolases and Baeyer-Villiger monooxygenases

International Nuclear Information System (INIS)

Bicalho, Beatriz; Chen, Lu S.; Marsaioli, Anita J.; Grognux, Johann; Reymond, Jean-Louis

2004-01-01

Biocatalysis reactions were performed on microtiter plates (200 μL) aiming at the utilization of fluorogenic substrates (100 μmol L -1 ) for rapid whole cell screening for epoxide hydrolases (EHs) and Baeyer-Villiger monooxygenases (BVMOs). A final protocol was achieved for EHs, with 3 new enzymatic sources being detected (Agrobacterium tumefaciens, Pichia stipitis, Trichosporom cutaneum). The fluorogenic assay for BVMO did not work as expected. However, an approach to possible variables involved (aeration; pH) provided the first detection of a BVMO activity in T. cutaneum. (author)

Omeprazole increases the efficacy of a soluble epoxide hydrolase inhibitor in a PGE2 induced pain model

International Nuclear Information System (INIS)

Goswami, Sumanta Kumar; Inceoglu, Bora; Yang, Jun; Wan, Debin; Kodani, Sean D.; Trindade da Silva, Carlos Antonio; Morisseau, Christophe; Hammock, Bruce D.

2015-01-01

Epoxyeicosatrienoic acids (EETs) are potent endogenous analgesic metabolites produced from arachidonic acid by cytochrome P450s (P450s). Metabolism of EETs by soluble epoxide hydrolase (sEH) reduces their activity, while their stabilization by sEH inhibition decreases both inflammatory and neuropathic pain. Here, we tested the complementary hypothesis that increasing the level of EETs through induction of P450s by omeprazole (OME), can influence pain related signaling by itself, and potentiate the anti-hyperalgesic effect of sEH inhibitor. Rats were treated with OME (100 mg/kg/day, p.o., 7 days), sEH inhibitor TPPU (3 mg/kg/day, p.o.) and OME (100 mg/kg/day, p.o., 7 days) + TPPU (3 mg/kg/day, p.o., last 3 days of OME dose) dissolved in vehicle PEG400, and their effect on hyperalgesia (increased sensitivity to pain) induced by PGE 2 was monitored. While OME treatment by itself exhibited variable effects on PGE 2 induced hyperalgesia, it strongly potentiated the effect of TPPU in the same assay. The significant decrease in pain with OME + TPPU treatment correlated with the increased levels of EETs in plasma and increased activities of P450 1A1 and P450 1A2 in liver microsomes. The results show that reducing catabolism of EETs with a sEH inhibitor yielded a stronger analgesic effect than increasing generation of EETs by OME, and combination of both yielded the strongest pain reducing effect under the condition of this study. - Highlights: • The soluble epoxide hydrolase (sEH) inhibitor TPPU is anti-hyperalgesic. • Omeprazole potentiates the anti-hyperalgesic actions of TPPU. • This potentiation is associated with increased P450 activity. • The potentiation is associated with an increase in fatty acid epoxide/diol ratio. • Joint use of sEH inhibitors and P450 inducers could result in drug–drug interactions.

Cloning, characterization and heterologous expression of epoxide hydrolase-encoding cDNA sequences from yeasts belonging to the genera Rhodotorula and Rhodosporidium

NARCIS (Netherlands)

Visser, H.; Weijers, C.A.G.M.; Ooyen, van A.J.J.; Verdoes, J.C.

2002-01-01

Epoxide hydrolase-encoding cDNA sequences were isolated from the basidiomycetous yeast species Rhodosporidium toruloides CBS 349, Rhodosporidium toruloides CBS 14 and Rhodotorula araucariae CBS 6031 in order to evaluate the molecular data and potential application of this type of enzymes. The

Stereoselectivity and substrate specificity in the kinetic resolution of methyl-substituted 1-oxaspiro[2.5]octanes by Rhodotorula glutinis epoxide hydrolase

NARCIS (Netherlands)

Weijers, C.A.G.M.; Meeuwse, P.; Herpers, R.L.J.M.; Franssen, M.C.R.; Sudhölter, E.J.R.

2005-01-01

[GRAPHICS] The kinetic resolution of a range of methyl-substituted 1-oxaspiro[2.5]octanes by yeast epoxide hydrolase (YEH) from Rhodotorula glutinis has been investigated. The structural determinants of substrate specificity and stereoselectivity of YEH toward these substrates appeared to be the

Reactions of transition metal complexes with cyclic ethers

International Nuclear Information System (INIS)

Milstein, D.

1977-02-01

Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

Electrochemical Interrogation of G3-Poly(propylene thiophenoimine Dendritic Star Polymer in Phenanthrene Sensing

Directory of Open Access Journals (Sweden)

Hlamulo R. Makelane

2015-09-01

Full Text Available A novel dendritic star-copolymer, generation 3 poly(propylene thiophenoimine (G3PPT-co-poly(3-hexylthiophene (P3HT star co-polymer on gold electrode (i.e., Au|G3PPT-co-P3HT was used as a sensor system for the determination of phenanthrene (PHE. The G3PPT-co-P3HT star co-polymer was synthesized via in situ electrochemical co-polymerization of generation 3 poly (propylene thiophenoimine and poly (3-hexylthiophene on gold electrode. 1HNMR spectroscopy was used to determine the regioregularity of the polymer composites, whereas Fourier transform infrared spectroscopy and scanning electron microscopy were used to study their structural and morphological properties. Au|G3PPT-co-P3HT in the absence of PHE, exhibited reversible electrochemistry attributable to the oligo (thiophene ‘pendants’ of the dendrimer. PHE produced an increase in the voltammetric signals (anodic currents due to its oxidation on the dendritic material to produce catalytic current, thereby suggesting the suitability of the Au|G3PPT-co-P3HT electrode as a PHE sensor. The electrocatalysis of PHE was made possible by the rigid and planar oligo-P3HT species (formed upon the oxidation of the oligo (thiophene pendants of the star-copolymer, which allowed the efficient capture (binding and detection (electrocatalytic oxidation of PHE molecules.

Effects of a single glucocorticoid injection on propylene glycol-treated cows with clinical ketosis.

Science.gov (United States)

van der Drift, Saskia G A; Houweling, Martin; Bouman, Marina; Koets, Ad P; Tielens, Aloysius G M; Nielen, Mirjam; Jorritsma, Ruurd

2015-05-01

This study investigated the metabolic effects of glucocorticoids when administered to propylene glycol-treated cows with clinical ketosis. Clinical ketosis was defined by depressed feed intake and milk production, and a maximal score for acetoacetate in urine. All cows received 250 mL oral propylene glycol twice daily for 3 days and were randomly assigned to a single intramuscular injection with sterile isotonic saline solution (n = 14) or dexamethasone-21-isonicotinate (n = 17). Metabolic blood variables were monitored for 6 days and adipose tissue variables for 3 days. β-Hydroxybutyrate (BHBA) concentrations in blood decreased in all cows during treatment, but were lower in glucocorticoid-treated cows. Cows treated with glucocorticoids had higher plasma glucose and insulin concentrations, whereas concentrations of non-esterified fatty acids, 3-methylhistidine and growth hormone were unaffected. mRNA expression of hormone-sensitive lipase, BHBA receptor and peroxisome proliferator-activated receptor type γ in adipose tissue was not affected. This shows that lipolytic effects do not appear to be important in ketotic cows when glucocorticoids are combined with PG. Plasma 3-methyl histidine concentrations were similar in both groups, suggesting that glucocorticoids did not increase muscle breakdown and that the greater rise in plasma glucose in glucocorticoid-treated cows may not be due to increased supply of glucogenic amino acids from muscle. Copyright © 2015 Elsevier Ltd. All rights reserved.

Anti-parallel dimer and tetramer formation of propylene carbonate

Directory of Open Access Journals (Sweden)

Ayana Tagawa

2017-09-01

Full Text Available Raman scattering and infrared (IR absorption spectra of enantiopure (R-propylene carbonate ((RPC and racemic propylene carbonate (PC were recorded at room temperature, 25 °C, in benzene (Bz solution and in the pure liquid state to investigate the presence of dimers and other higher order intermolecular associations. (RPC and PC both demonstrated a strong C=O stretching vibrational band. The band exhibited changes in its shape and resonance wavenumber highly dependent on the concentrations of PCs, whereas a difference between the chirality of (RPC and PC had little influence. In an extremely dilute condition, doubly split bands were observed at 1807 and 1820 cm-1 in both Raman and IR spectra, which are assigned to the characteristic bands of isolated monomeric PCs. An additional band appeared at 1795 cm-1 in a dilute to concentrated regime, and its magnitude strengthened with increasing concentrations accompanied with slight increasing in the magnitude of 1807 cm-1 band in Raman spectra, while an increase in the magnitude of 1807 cm-1 band was clearly greater than that of 1795 cm-1 band in IR spectra. The spectrum changes at 1795 and 1807 cm-1 were attributed to characteristics of anti-parallel dimer formation of PCs caused by strong dipole-dipole interactions between C=O groups. Moreover, another additional signal was clearly observed at 1780-1790 cm-1 in a concentrated regime, and became the primary signal in the pure liquid state with slight increasing in the intensity of 1795 cm-1 band in Raman spectra. On the other hand, in IR spectra the observed increasing of 1780-1790 cm-1 band was much less than that of 1795 cm-1 band. These newly found spectrum changes in the concentrated regime are attributed to the formation of anti-parallel tetramers of PCs based on the characteristics of band selection rule found in Raman and IR spectra. Equilibrium constants for the anti-parallel dimer (KD and tetramer formation (KT of PCs in Bz solution and in

Developed Hybrid Model for Propylene Polymerisation at Optimum Reaction Conditions

Directory of Open Access Journals (Sweden)

Mohammad Jakir Hossain Khan

2016-02-01

Full Text Available A statistical model combined with CFD (computational fluid dynamic method was used to explain the detailed phenomena of the process parameters, and a series of experiments were carried out for propylene polymerisation by varying the feed gas composition, reaction initiation temperature, and system pressure, in a fluidised bed catalytic reactor. The propylene polymerisation rate per pass was considered the response to the analysis. Response surface methodology (RSM, with a full factorial central composite experimental design, was applied to develop the model. In this study, analysis of variance (ANOVA indicated an acceptable value for the coefficient of determination and a suitable estimation of a second-order regression model. For better justification, results were also described through a three-dimensional (3D response surface and a related two-dimensional (2D contour plot. These 3D and 2D response analyses provided significant and easy to understand findings on the effect of all the considered process variables on expected findings. To diagnose the model adequacy, the mathematical relationship between the process variables and the extent of polymer conversion was established through the combination of CFD with statistical tools. All the tests showed that the model is an excellent fit with the experimental validation. The maximum extent of polymer conversion per pass was 5.98% at the set time period and with consistent catalyst and co-catalyst feed rates. The optimum conditions for maximum polymerisation was found at reaction temperature (RT 75 °C, system pressure (SP 25 bar, and 75% monomer concentration (MC. The hydrogen percentage was kept fixed at all times. The coefficient of correlation for reaction temperature, system pressure, and monomer concentration ratio, was found to be 0.932. Thus, the experimental results and model predicted values were a reliable fit at optimum process conditions. Detailed and adaptable CFD results were capable

Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

Science.gov (United States)

Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

2003-09-17

We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

Poly(propylene)/aspen/liquid polybutadiene composites: maximization of impact strength, tensile and modulus by statistical experimental design

Czech Academy of Sciences Publication Activity Database

Kokta, B. V.; Michálková, Danuše; Fortelný, Ivan; Kruliš, Zdeněk

2007-01-01

Roč. 18, č. 2 (2007), s. 106-111 ISSN 1042-7147 Grant - others:Network of Centres of Excellence(EU) AUTO21 Institutional research plan: CEZ:AV0Z40500505 Source of funding: R - rámcový projekt EK Keywords : poly butadiene * composites * poly (propylene) (pp) Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.504, year: 2007

cis-Stilbene and (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)benzene as mechanistic probes in the Mn(III)(salen)-catalyzed epoxidation: influence of the oxygen source and the counterion on the diastereoselectivity of the competitive concerted and radical-type oxygen transfer.

Science.gov (United States)

Adam, Waldemar; Roschmann, Konrad J; Saha-Möller, Chantu R; Seebach, Dieter

2002-05-08

cis-Stilbene (1) has been epoxidized by a set of diverse oxygen donors [OxD], catalyzed by the Mn(III)(salen)X complexes 3 (X = Cl, PF(6)), to afford a mixture of cis- and trans-epoxides 2. The cis/trans ratios range from 29:71 (extensive isomerization) to 92:8, which depends both on the oxygen source [OxD] and on the counterion X of the catalyst. When (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)-benzene (4) is used as substrate, a mechanistic probe which differentiates between radical and cationic intermediates, no cationic ring-opening products are found in this epoxidation reaction; thus, isomerized epoxide product arises from intermediary radicals. The dependence of the diastereoselectivity on the oxygen source is rationalized in terms of a bifurcation step in the catalytic cycle, in which concerted Lewis-acid-activated oxygen transfer competes with stepwise epoxidation by the established Mn(V)(oxo) species. The experimental counterion effect is attributed to the computationally assessed ligand-dependent reaction profiles and stereoselectivities of the singlet, triplet, and quintet spin states available to the manganese species.

Compositional analysis of nitrile terminated poly(propylene imine) dendrimers by high-performance liquid chromatography combined with electrospray mass spectrometry

NARCIS (Netherlands)

van der Wal, S; Mengerink, Y; Brackman, JC; de Brabander, EMM; Jeronimus-Stratingh, CM; Bruins, AP

1998-01-01

Separation methods for nitrile terminated poly(propylene imine) dendrimers were developed to monitor and optimize their large scale production. Detailed analyses of defects within a dendrimer generation were performed by HPLC at alkaline pH (sodium hydroxide) on a polymer-based column or at neutral

Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

KAUST Repository

Szeto, Kaï Chung; Mazoyer, Etienne; Merle, Nicolas; Norsic, Sé bastien; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2013-01-01

Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

KAUST Repository

Szeto, Kaï Chung

2013-09-06

Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

UV stabilization of wood by nano metal oxides dispersed in propylene glycol.

Science.gov (United States)

Nair, Sreeja; Nagarajappa, Giridhar B; Pandey, Krishna K

2018-06-01

Nanoparticles of some of the metal oxides are known to have high UV protective efficiency. The UV filtering efficiency of nanoparticles invariably depends on their size and stability in the dispersion. In the present work, a stable dispersion of nanoparticles of three metal oxides, zinc oxide (ZnO), cerium oxide (CeO 2 ) and titanium dioxide (TiO 2 ), was prepared in propylene glycol (PG) using ultrasonication. The method is easy and useful as no additional surfactant or dispersant is needed. The particle size and its distribution was confirmed by Scanning Electron Microscopy and Dynamic Light Scattering. The stability of dispersion was assessed by UV-visible absorption spectroscopy. The UV stability of wood surfaces of Wrightia tinctoria coated with nanodispersions of ZnO, CeO 2 and TiO 2 was evaluated under laboratory conditions in an accelerated weathering tester. Changes in the colour and FTIR spectra of exposed specimens were measured periodically. Rapid colour darkening (yellowing) was observed in uncoated and PG coated specimens. In contrast, nanodispersion coated specimens prevented photo-yellowing considerably with significant reduction in colour changes examined by CIE L*, a*, b* and ΔE*. Increase in concentration of nanoparticles in the dispersion imparted higher resistance to UV induced degradation. However, increased concentration of nanoparticles reduced the transparency of the coating. FTIR analysis indicated rapid degradation of lignin in uncoated and PG coated specimens due to UV exposure. Coating of wood surfaces with nanodispersions restricted lignin degradation. The study also demonstrates the potential of propylene glycol as a dispersant for developing stable and efficient UV protective nanodispersions for wood coating. Copyright © 2018 Elsevier B.V. All rights reserved.

EFSA CEF Panel (EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids), 2014. Scientific Opinion on Flavouring Group Evaluation 82, Revision 1 (FGE.82Rev1): Consideration of Epoxides evaluated by the JECFA (65 th meeting)

DEFF Research Database (Denmark)

Beltoft, Vibe Meister; Binderup, Mona-Lise; Frandsen, Henrik Lauritz

evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of five epoxides evaluated by the JECFA at the 65th meeting in 2005. This revision is made due to inclusion of one additional substance, beta-ionone epoxide [FL-no: 07.170], cleared...

Direct Partial Oxidations Using Molecular Oxygen - Final Report

Energy Technology Data Exchange (ETDEWEB)

Kemp, Richard [Univ. of New Mexico, Albuquerque, NM (United States)

2017-11-01

In 2006, Richard A. Kemp (University of New Mexico) and Karen I. Goldberg (University of Washington) formed a team and began to investigate new strategies to accomplish direct selective aerobic oxidations, with a particular emphasis on the epoxidation of propylene and higher olefins. This DOE-BES funded project was renewed twice and concluded after a no-cost extension earlier this year. Multiple novel strategies involving homogeneous catalyst systems were initiated and investigated during the award. Important fundamental understanding and insight concerning requirements for promotion of aerobic olefin epoxidation was generated. During the tenure of this project, new knowledge was generated concerning the synthesis, characterization and aerobic reactivity of metal hydrides and hydroxides. Key results describing synthetic strategies and optimization of the preparation of mononuclear late metal hydrides were published. The team reported the first example of O2 insertion into a Pd-H bond, a reaction which had been proposed in the literature but never previously observed. Our experimental investigation of the mechanism was later followed by computational work, and a description of what is now referred to as the Hydrogen Atom Abstraction (HAA) pathway for this reaction has been widely accepted in the community. After investigation of many other late metal hydrides, both experimentally and computationally, the team put together a chapter that included a description of key contributing factors that allow reaction by the HAA mechanism. A brief sampling of other classic papers from our project include hydrogenolysis reactions of late metal hydroxide and alkoxide complexes, the synthesis of nickel-hydrides, and the involvement of hemilabile ligands in promoting new reaction pathways.

The stability of the three transmembrane and the four transmembrane human vitamin K epoxide reductase models

Science.gov (United States)

Wu, Sangwook

2016-04-01

The three transmembrane and the four transmembrane helix models are suggested for human vitamin K epoxide reductase (VKOR). In this study, we investigate the stability of the human three transmembrane/four transmembrane VKOR models by employing a coarse-grained normal mode analysis and molecular dynamics simulation. Based on the analysis of the mobility of each transmembrane domain, we suggest that the three transmembrane human VKOR model is more stable than the four transmembrane human VKOR model.

Immobilization of surface active compounds on polymer supports using glow discharge processess. 1. Sodium dodecyl sulfate on poly(propylene)

NARCIS (Netherlands)

Terlingen, J.G.A.; Terlingen, Johannes G.A.; Feijen, Jan; Hoffman, Allan S.

1993-01-01

A new method has been developed in which a reversibly adsorbed layer of a surfactant (sodium dodecyl sulfate, SDS) is covalently immobilized in one step onto a hydrophobic substrate (poly(propylene), PP) by applying an argon plasma treatment. The adsorption of SDS from aqueous solutions onto PP

Lutein from Deepoxidation of Lutein Epoxide Replaces Zeaxanthin to Sustain an Enhanced Capacity for Nonphotochemical Chlorophyll Fluorescence Quenching in Avocado Shade Leaves in the Dark1

Science.gov (United States)

Förster, Britta; Pogson, Barry James; Osmond, Charles Barry

2011-01-01

Leaves of avocado (Persea americana) that develop and persist in deep shade canopies have very low rates of photosynthesis but contain high concentrations of lutein epoxide (Lx) that are partially deepoxidized to lutein (L) after 1 h of exposure to 120 to 350 μmol photons m−2 s−1, increasing the total L pool by 5% to 10% (ΔL). Deepoxidation of Lx to L was near stoichiometric and similar in kinetics to deepoxidation of violaxanthin (V) to antheraxanthin (A) and zeaxanthin (Z). Although the V pool was restored by epoxidation of A and Z overnight, the Lx pool was not. Depending on leaf age and pretreatment, the pool of ΔL persisted for up to 72 h in the dark. Metabolism of ΔL did not involve epoxidation to Lx. These contrasting kinetics enabled us to differentiate three states of the capacity for nonphotochemical chlorophyll fluorescence quenching (NPQ) in attached and detached leaves: ΔpH dependent (NPQΔpH) before deepoxidation; after deepoxidation in the presence of ΔL, A, and Z (NPQΔLAZ); and after epoxidation of A+Z but with residual ΔL (NPQΔL). The capacity of both NPQΔLAZ and NPQΔL was similar and 45% larger than NPQΔpH, but dark relaxation of NPQΔLAZ was slower. The enhanced capacity for NPQ was lost after metabolism of ΔL. The near equivalence of NPQΔLAZ and NPQΔL provides compelling evidence that the small dynamic pool ΔL replaces A+Z in avocado to “lock in” enhanced NPQ. The results are discussed in relation to data obtained with other Lx-rich species and in mutants of Arabidopsis (Arabidopsis thaliana) with increased L pools. PMID:21427278

Use of epoxidized natural rubber as a compatibilizer in silica-filled natural rubber tire tread compounds ; Verwendung von epoxydiertem Naturkautschuk als Verträglichkeitsvermittler in Zusammensetzungen aus kieselsäuregefülltem Naturkautschuk für Reifenlaufflächen

NARCIS (Netherlands)

Sengloyluan, K.; Sahakaro, Kannika; Noordermeer, Jacobus W.M.

2012-01-01

Silica-reinforced natural rubber (NR) tire tread compounds with epoxidized natural rubber (ENR) as a compatibilizer are investigated. ENR contents of 2.5-15.0 phr, with epoxide levels of 10, 38 and 51 mol%, are used. The addition of ENRs, especially ENR-38 and ENR-51, as compatibilizers decreases

MWCNTs-reinforced epoxidized linseed oil plasticized polylactic acid nanocomposite and its electroactive shape memory behaviour.

Science.gov (United States)

Alam, Javed; Alam, Manawwer; Raja, Mohan; Abduljaleel, Zainularifeen; Dass, Lawrence Arockiasamy

2014-10-31

A novel electroactive shape memory polymer nanocomposite of epoxidized linseed oil plasticized polylactic acid and multi-walled carbon nanotubes (MWCNTs) was prepared by a combination of solution blending, solvent cast technique, and hydraulic hot press moulding. In this study, polylactic acid (PLA) was first plasticized by epoxidized linseed oil (ELO) in order to overcome the major limitations of PLA, such as high brittleness, low toughness, and low tensile elongation. Then, MWCNTs were incorporated into the ELO plasticized PLA matrix at three different loadings (2, 3 and 5 wt. %), with the aim of making the resulting nanocomposites electrically conductive. The addition of ELO decreased glass transition temperature, and increased the elongation and thermal degradability of PLA, as shown in the results of differential scanning calorimetry (DSC), tensile test, and thermo gravimetric analysis (TGA). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to observe surface morphology, topography, and the dispersion of MWCNTs in the nanocomposite. Finally, the electroactive-shape memory effect (electroactive-SME) in the resulting nanocomposite was investigated by a fold-deploy "U"-shape bending test. As per the results, the addition of both ELO and MWCNTs to PLA matrix seemed to enhance its overall properties with a great deal of potential in improved shape memory. The 3 wt. % MWCNTs-reinforced nanocomposite system, which showed 95% shape recovery within 45 s at 40 DC voltage, is expected to be used as a preferential polymeric nanocomposite material in various actuators, sensors and deployable devices.

Surface science study of selective ethylene epoxidation catalyzed by the Ag(110) surface: Structural sensitivity

International Nuclear Information System (INIS)

Campbell, C.T.

1984-01-01

The selective oxidation of ethylene to ethylene epoxide (C 2 H 4 +1/2O 2 →C 2 H 4 O) over Ag is the simplest example of kinetically controlled, selective heterogeneous catalysis. We have studied the steady-state kinetics and selectivity of this reaction for the first time on a clean, well-characterized Ag(110) surface by using a special apparatus which allows rapid (approx.20 s) transfer between a high-pressure catalytic microreactor and an ultrahigh vacuum surface analysis (AES, XPS, LEED, TDS) chamber. The effects of temperature and reactant pressures upon the rate and selectivity are virtually identical on Ag(110) and supported, high surface area Ag catalysts. The absolute specific rate (per Ag surface atom) is, however, some 100-fold higher for Ag(110) than for high surface area catalysts. This is related to the well-known structural sensitivity of this reaction. It is postulated that a small percentage of (110) planes (or [110]-like sites) are responsible for most of the catalytic activity of high surface area catalysts. The high activity of the (110) plane is attributed to its high sticking probability for dissociative oxygen adsorption, since the rate of ethylene epoxidation is shown in a related work [Ref. 1: C. T. Campbell and M. T. Paffett, Surf. Sci. (in press)] to be proportional to the coverage of atomically adsorbed oxygen at constant temperature and ethylene pressure

Digital micromirror device (DMD)-based 3D printing of poly(propylene fumarate) scaffolds.

Science.gov (United States)

Mott, Eric J; Busso, Mallory; Luo, Xinyi; Dolder, Courtney; Wang, Martha O; Fisher, John P; Dean, David

2016-04-01

Our recent investigations into the 3D printing of poly(propylene fumarate) (PPF), a linear polyester, using a DMD-based system brought us to a resin that used titanium dioxide (TiO2) as an ultraviolet (UV) filter for controlling cure depth. However, this material hindered the 3D printing process due to undesirable lateral or "dark" curing (i.e., in areas not exposed to light from the DMD chip). Well known from its use in sunscreen, another UV filter, oxybenzone, has previously been used in conjunction with TiO2. In this study we hypothesize that combining these two UV filters will result in a synergistic effect that controls cure depth and avoids dark cure. A resin mixture (i.e., polymer, initiator, UV filters) was identified that worked well. The resin was then further characterized through mechanical testing, cure testing, and cytotoxicity testing to investigate its use as a material for bone tissue engineering scaffolds. Results show that the final resin eliminated dark cure as shown through image analysis. Mechanically the new scaffolds proved to be far weaker than those printed from previous resins, with compressive strengths of 7.8 ± 0.5 MPa vs. 36.5 ± 1.6 MPa, respectively. The new scaffolds showed a 90% reduction in elastic modulus and a 74% increase in max strain. These properties may be useful in tissue engineering applications where resorption is required. Initial cytotoxicity evaluation was negative. As hypothesized, the use of TiO2 and oxybenzone showed synergistic effects in the 3D printing of PPF tissue engineering scaffolds. Copyright © 2015 Elsevier B.V. All rights reserved.

Omeprazole increases the efficacy of a soluble epoxide hydrolase inhibitor in a PGE{sub 2} induced pain model

Energy Technology Data Exchange (ETDEWEB)

Goswami, Sumanta Kumar; Inceoglu, Bora; Yang, Jun; Wan, Debin; Kodani, Sean D. [Department of Entomology and Nematology, UC Davis Comprehensive Cancer Center, University of California, Davis, CA (United States); Trindade da Silva, Carlos Antonio [Department of Entomology and Nematology, UC Davis Comprehensive Cancer Center, University of California, Davis, CA (United States); Department of Genetics and Biochemistry, Federal University of Uberlandia, MG (Brazil); Morisseau, Christophe [Department of Entomology and Nematology, UC Davis Comprehensive Cancer Center, University of California, Davis, CA (United States); Hammock, Bruce D., E-mail: bdhammock@ucdavis.edu [Department of Entomology and Nematology, UC Davis Comprehensive Cancer Center, University of California, Davis, CA (United States)

2015-12-15

Epoxyeicosatrienoic acids (EETs) are potent endogenous analgesic metabolites produced from arachidonic acid by cytochrome P450s (P450s). Metabolism of EETs by soluble epoxide hydrolase (sEH) reduces their activity, while their stabilization by sEH inhibition decreases both inflammatory and neuropathic pain. Here, we tested the complementary hypothesis that increasing the level of EETs through induction of P450s by omeprazole (OME), can influence pain related signaling by itself, and potentiate the anti-hyperalgesic effect of sEH inhibitor. Rats were treated with OME (100 mg/kg/day, p.o., 7 days), sEH inhibitor TPPU (3 mg/kg/day, p.o.) and OME (100 mg/kg/day, p.o., 7 days) + TPPU (3 mg/kg/day, p.o., last 3 days of OME dose) dissolved in vehicle PEG400, and their effect on hyperalgesia (increased sensitivity to pain) induced by PGE{sub 2} was monitored. While OME treatment by itself exhibited variable effects on PGE{sub 2} induced hyperalgesia, it strongly potentiated the effect of TPPU in the same assay. The significant decrease in pain with OME + TPPU treatment correlated with the increased levels of EETs in plasma and increased activities of P450 1A1 and P450 1A2 in liver microsomes. The results show that reducing catabolism of EETs with a sEH inhibitor yielded a stronger analgesic effect than increasing generation of EETs by OME, and combination of both yielded the strongest pain reducing effect under the condition of this study. - Highlights: • The soluble epoxide hydrolase (sEH) inhibitor TPPU is anti-hyperalgesic. • Omeprazole potentiates the anti-hyperalgesic actions of TPPU. • This potentiation is associated with increased P450 activity. • The potentiation is associated with an increase in fatty acid epoxide/diol ratio. • Joint use of sEH inhibitors and P450 inducers could result in drug–drug interactions.

Studies on Poly(propylene fumarate-co-caprolactone diol Thermoset Composites towards the Development of Biodegradable Bone Fixation Devices

Directory of Open Access Journals (Sweden)

M. Jayabalan

2009-01-01

Full Text Available The effect of reinforcement in the cross-linked poly(propylene fumarate-co-caprolactone diol thermoset composites based on Kevlar fibres and hydroxyapatite was studied. Cross-linked poly(propylene fumarate-co-caprolactone diol was also studied without any reinforcement for comparison. The reinforcing fibre acts as a barrier for the curing reaction leading to longer setting time and lesser cross-link density. The fibre and HA reinforced composites have almost the same compressive strength. Nonreinforced material undergoes greater degree of swelling. Among the reinforced materials, the hydroxyapatite reinforced composite has a much higher swelling percentage than the fibre reinforced one. The studies on in vitro degradation of the cured materials reveal hydrolytic degradation in Ringer's solution and PBS medium during aging. All the three materials are found to swell initially in Ringer's solution and PBS medium during aging and then undergo gradual degradation. Compression properties of these cross-linked composites increase with aging; HA reinforced composite has the highest compressive strength and compressive modulus, whereas the aged fibre-reinforced composite has the least compressive strength and modulus.

Studies on Poly(propylene fumarate-co-caprolactone diol) Thermoset Composites towards the Development of Biodegradable Bone Fixation Devices.

Science.gov (United States)

Jayabalan, M

2009-01-01

The effect of reinforcement in the cross-linked poly(propylene fumarate-co-caprolactone diol) thermoset composites based on Kevlar fibres and hydroxyapatite was studied. Cross-linked poly(propylene fumarate-co-caprolactone diol) was also studied without any reinforcement for comparison. The reinforcing fibre acts as a barrier for the curing reaction leading to longer setting time and lesser cross-link density. The fibre and HA reinforced composites have almost the same compressive strength. Nonreinforced material undergoes greater degree of swelling. Among the reinforced materials, the hydroxyapatite reinforced composite has a much higher swelling percentage than the fibre reinforced one. The studies on in vitro degradation of the cured materials reveal hydrolytic degradation in Ringer's solution and PBS medium during aging. All the three materials are found to swell initially in Ringer's solution and PBS medium during aging and then undergo gradual degradation. Compression properties of these cross-linked composites increase with aging; HA reinforced composite has the highest compressive strength and compressive modulus, whereas the aged fibre-reinforced composite has the least compressive strength and modulus.

Degradability of composites, prepared from ethylene-propylene copolymer and jute fiber under accelerated aging and biotic environments

International Nuclear Information System (INIS)

Kumar, Annamalai Pratheep; Singh, Raj Pal; Sarwade, Bhimrao D.

2005-01-01

The utilization of natural fiber as reinforcement for the thermoplastic composites is growing not only for ecological concern but also for wide range of applications. In the present article, three types of composites were prepared by melt mixing of ethylene-propylene (EP) copolymer and (i) 3% NaOH treated jute fiber, (ii) 17.5% NaOH treated jute fiber and (iii) commercial microcrystalline cellulose powder using maleated EP copolymer as compatibilizer. The obtained composites were characterized by Fourier transform infrared spectroscopy (FTIR), Thermal gravimetric analysis (TGA) and microscopic measurements. The durability of the composites was evaluated under polychromatic irradiation (λ ≥ 290 nm) and composting condition for different time intervals. It was found that the treatments on the natural fiber have influenced the service life of the end product. Composites made from microcrystalline cellulose showed better mechanical properties as well as photo-resistance. The specimen containing 3% NaOH treated fiber exhibited relatively lowest photo-resistance and biosusceptibility. It was found that the composites were less durable under both abiotic and biotic conditions in comparison of the neat polymer matrix

Microsomal epoxide hydrolase gene polymorphisms and risk of chronic obstructive pulmonary disease: A comprehensive meta-analysis

OpenAIRE

LI, HUI; FU, WEI-PING; HONG, ZE-HUI

2012-01-01

Microsomal epoxide hydrolase (EPHX1) is an enzyme involved in the detoxification the products of smoking and is proposed to be a genetic factor for the development of chronic obstructive pulmonary disease (COPD). Two functional polymorphisms of EPHX1, T113C and A139G, have been analyzed in numerous studies to assess the COPD risk attributed to these variants. However, the conclusions were controversial. We performed a comprehensive meta-analysis to clarify these findings. A total of 24 studie...

THE EFFECTS OF ORAL ADMINISTRATION OF PROPYLENE GLYCOL AND CALCIUM PROPIONATE IN DAIRY COWS

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C. GAVAN

2009-10-01

Full Text Available This study was designed to determine the effects of the oral administration of propylene glycol and calcium propionate on performance of dairy cows. Treatments were 10 l water (control, 10 l water+300 ml propylene glycol (GP and 10 l water+500 g calcium propionate (CP. Animals were mainly of Holstein breeds and were fed and managed in a commercial setting. The cows were divided randomly into an experimental group, n=24 (n=12 with PG and n=12 with CP and a control group, n=11. Cows received the assigned treatment within 10 hours of calving and 24 hours after calving. Health events were recorded during calving and for the first 21 days in milk (DIM. Health examinations were performed on cows that appeared not well. The cows were milked three times daily and milk production was recorded electronically. Milk solid content and somatic cell score were determinate from three consecutive milking weekly till 20 DIM and than monthly till 110 DIM. Retained placenta, hypocalcaemia, displaced abomasums, ketosis and metritis were low in treatment groups (with PG and CP. The cows receiving PG had 2.8 Kg/day grater milk production than control group. The cows receiving CP had 1.7 kg/day grater milk production than control group. Prophylactic administration of PG and CP drenches to Holstein cows may be justified by potentially higher milk yields and reduced health complications.

Adsorption and separation of propane and propylene by porous hexacyanometallates

International Nuclear Information System (INIS)

Autie-Castro, G.; Autie, M.; Reguera, E.; Moreno-Tost, R.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.; Santamaria-Gonzalez, J.

2011-01-01

The separation capability for mixtures of propane and propylene by porous frameworks representatives of transition metal hexacyanometallates was studied from adsorption data under equilibrium conditions at 273.15 K and from inverse gas chromatography profiles at different column temperatures. Samples of two porous solids were considered; Cd 3 [Co(CN) 6 ] 2 , which is representative of Prussian blue analogues (cubic structure) with a porous framework related to vacancies for building block, and Zn 3 [Co(CN) 6 ] 2 (rhombohedral phase) where the porous framework results from the tetrahedral coordination for the Zn atoms. The two materials were found to be able for the mixtures separation, with the highest separation ability for the rhombohedral phase under equilibrium conditions but, in dynamic conditions the cubic one shown a better separation, which was ascribed to a kinetic contribution related to a smaller windows size.

Thermoset coatings from epoxidized sucrose soyate and blocked, bio-based dicarboxylic acids.

Science.gov (United States)

Kovash, Curtiss S; Pavlacky, Erin; Selvakumar, Sermadurai; Sibi, Mukund P; Webster, Dean C

2014-08-01

A new 100% bio-based thermosetting coating system was developed from epoxidized sucrose soyate crosslinked with blocked bio-based dicarboxylic acids. A solvent-free, green method was used to block the carboxylic acid groups and render the acids miscible with the epoxy resin. The thermal reversibility of this blocking allowed for the formulation of epoxy-acid thermoset coatings that are 100% bio-based. This was possible due to the volatility of the vinyl ethers under curing conditions. These systems have good adhesion to metal substrates and perform well under chemical and physical stress. Additionally, the hardness of the coating system is dependent on the chain length of the diacid used, making it tunable. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extrusion-based 3D printing of poly(propylene fumarate) scaffolds with hydroxyapatite gradients

Science.gov (United States)

Trachtenberg, Jordan E.; Placone, Jesse K.; Smith, Brandon T.; Fisher, John P.; Mikos, Antonios G.

2017-01-01

The primary focus of this work is to present the current challenges of printing scaffolds with concentration gradients of nanoparticles with an aim to improve the processing of these scaffolds. Furthermore, we address how print fidelity is related to material composition and emphasize the importance of considering this relationship when developing complex scaffolds for bone implants. The ability to create complex tissues is becoming increasingly relevant in the tissue engineering community. For bone tissue engineering applications, this work demonstrates the ability to use extrusion-based printing techniques to control the spatial deposition of hydroxyapatite (HA) nanoparticles in a 3D composite scaffold. In doing so, we combined the benefits of synthetic, degradable polymers, such as poly(propylene fumarate) (PPF), with osteoconductive HA nanoparticles that provide robust compressive mechanical properties. Furthermore, the final 3D printed scaffolds consisted of well-defined layers with interconnected pores, two critical features for a successful bone implant. To demonstrate a controlled gradient of HA, thermogravimetric analysis was carried out to quantify HA on a per-layer basis. Moreover, we non-destructively evaluated the tendency of HA particles to aggregate within PPF using micro-computed tomography (µCT). This work provides insight for proper fabrication and characterization of composite scaffolds containing particle gradients and has broad applicability for future efforts in fabricating complex scaffolds for tissue engineering applications. PMID:28125380

Effect of propylene glycol on adipose tissue mobilization in postpartum over-conditioned Holstein cows

DEFF Research Database (Denmark)

Bjerre-Harpøth, Vibeke; Storm, Adam Christian; Eslamizad, M

2015-01-01

Our objective was to investigate the quantitative and qualitative effects of propylene glycol (PG) allocation on postpartum adipose tissue mobilization in over-conditioned Holstein cows. Nine ruminally cannulated and arterially catheterized cows were, at parturition, randomly assigned to a ruminal...... from –7 to 7 DIM. Postpartum feed intake and milk yield was not affected by PG allocation. The body content of lipid was not affected by treatment, but tended to decrease from 4 to 29 DIM with both treatments. Except for the first week postpartum, no difference in plasma nonesterified fatty acids...

Nonlinear dielectric spectroscopy of propylene carbonate derivatives

Science.gov (United States)

Casalini, R.; Roland, C. M.

2018-04-01

Nonlinear dielectric measurements were carried out on two strongly polar liquids, 4-vinyl-1,3-dioxolan-2-one (VPC) and 4-ethyl-1,3-dioxolan-2-one (EPC), having chemical structures differing from propylene carbonate (PC) only by the presence of a pendant group. Despite their polarity, the compounds are all non-associated, "simple" liquids. From the linear component of the dielectric response, the α relaxation peak breadth was found to be invariant at a fixed value of the relaxation time, τα. From spectra from the nonlinear component, the number of dynamically correlated molecules was determined; it was also constant at fixed τα. Thus, two manifestations of dynamic heterogeneity depend only on the time constant for structural reorientation. More broadly, the cooperativity of molecular motions for non-associated glass-forming materials is connected to (i.e., reciprocally governs) the time scale. The equation of state for the two liquids was also obtained from density measurements made over a broad range of pressures and temperatures. Using these data, it was determined that the relaxation times of both liquids conform to density scaling. The effect of density, relative to thermal effects, on the α relaxation increases going from PC < VPC < EPC.

Hepatitis B spliced protein (HBSP) promotes the carcinogenic effects of benzo [alpha] pyrene by interacting with microsomal epoxide hydrolase and enhancing its hydrolysis activity

International Nuclear Information System (INIS)

Chen, Jin-Yan; Chen, Wan-Nan; Jiao, Bo-Yan; Lin, Wan-Song; Wu, Yun-Li; Liu, Ling-Ling; Lin, Xu

2014-01-01

The risk of hepatocellular carcinoma (HCC) increases in chronic hepatitis B surface antigen (HBsAg) carriers who often have concomitant increase in the levels of benzo[alpha]pyrene-7,8-diol-9,10-epoxide(±) (BPDE)-DNA adduct in liver tissues, suggesting a possible co-carcinogenesis of Hepatitis B virus (HBV) and benzo[alpha]pyrene in HCC; however the exact mechanisms involved are unclear. The interaction between hepatitis B spliced protein (HBSP) and microsomal epoxide hydrolase (mEH) was confirmed using GST pull-down, co-immunoprecipitation and mammalian two-hybrid assay; the effects of HBSP on mEH-mediated B[alpha]P metabolism was examined by high performance liquid chromatography (HPLC); and the influences of HBSP on B[alpha]P carcinogenicity were evaluated by bromodeoxyuridine cell proliferation, anchorage-independent growth and tumor xenograft. HBSP could interact with mEH in vitro and in vivo, and this interaction was mediated by the N terminal 47 amino acid residues of HBSP. HBSP could greatly enhance the hydrolysis activity of mEH in cell-free mouse liver microsomes, thus accelerating the metabolism of benzo[alpha]pyrene to produce more ultimate carcinnogen, BPDE, and this effect of HBSP requires the intact HBSP molecule. Expression of HBSP significantly increased the formation of BPDE-DNA adduct in benzo[alpha]pyrene-treated Huh-7 hepatoma cells, and this enhancement was blocked by knockdown of mEH. HBSP could enhance the cell proliferation, accelerate the G1/S transition, and promote cell transformation and tumorigenesis of B[alpha]P-treated Huh-7 hepatoma cells. Our results demonstrated that HBSP could promote carcinogenic effects of B[alpha]P by interacting with mEH and enhancing its hydrolysis activity

Soluble Epoxide Hydrolase Inhibitory Activity of Selaginellin Derivatives from Selaginella tamariscina

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Jang Hoon Kim

2015-12-01

Full Text Available Selaginellin derivatives 1–3 isolated from Selaginella tamariscina were evaluated for their inhibition of soluble epoxide hydrolase (sEH to demonstrate their potential for the treatment of cardiovascular disease. All selaginellin derivatives (1–3 inhibited sEH enzymatic activity and PHOME hydrolysis, in a dose-dependent manner, with IC50 values of 3.1 ± 0.1, 8.2 ± 2.2, and 4.2 ± 0.2 μM, respectively. We further determined that the derivatives function as non-competitive inhibitors. Moreover, the predicted that binding sites and interaction between 1–3 and sEH were solved by docking simulations. According to quantitative analysis, 1–3 were confirmed to have high content in the roots of S. tamariscina; among them, selaginellin 3 exhibited the highest content of 189.3 ± 0.0 μg/g.

A PLS-based extractive spectrophotometric method for simultaneous determination of carbamazepine and carbamazepine-10,11-epoxide in plasma and comparison with HPLC

Science.gov (United States)

Hemmateenejad, Bahram; Rezaei, Zahra; Khabnadideh, Soghra; Saffari, Maryam

2007-11-01

Carbamazepine (CBZ) undergoes enzyme biotransformation through epoxidation with the formation of its metabolite, carbamazepine-10,11-epoxide (CBZE). A simple chemometrics-assisted spectrophotometric method has been proposed for simultaneous determination of CBZ and CBZE in plasma. A liquid extraction procedure was operated to separate the analytes from plasma, and the UV absorbance spectra of the resultant solutions were subjected to partial least squares (PLS) regression. The optimum number of PLS latent variables was selected according to the PRESS values of leave-one-out cross-validation. A HPLC method was also employed for comparison. The respective mean recoveries for analysis of CBZ and CBZE in synthetic mixtures were 102.57 (±0.25)% and 103.00 (±0.09)% for PLS and 99.40 (±0.15)% and 102.20 (±0.02)%. The concentrations of CBZ and CBZE were also determined in five patients using the PLS and HPLC methods. The results showed that the data obtained by PLS were comparable with those obtained by HPLC method.