Sample records for mesitylene

  1. Synthesis and characterization of luminescent tricationic salts of mesitylene and stilbazolium moieties (United States)

    Jo, Tae Soo; McCurdy, William L.; Tanthmanatham, Ontida; Kim, Tae K.; Han, Haesook; Bhowmik, Pradip K.; Heinrich, Benoît; Donnio, Bertrand


    A series of luminescent tricationic salts having mesitylene and stilbazolium moieties with various organic counterions were synthesized by using quaternization and metathesis reactions. Their chemical structures were characterized by 1H, 19F and 13C NMR spectroscopy, and elemental analysis. Their crystalline and amorphous properties were examined by differential scanning calorimetry, polarized optical microscopy, and variable-temperature X-ray diffraction studies. Their thermal stabilities were determined by thermogravimetric analyses, which were in the broad temperature ranges of 239-317 °C in nitrogen. Their optical properties were studied by UV-Vis and photoluminescent spectroscopy. The light-emission properties were dependent on the polarity of organic solvents (positive solvatochromism) but independent on the chemical structures of organic counterions. They emitted blue light in various organic solvents in a broad range of wavelengths of 470-497 nm, but emitted green light in a narrow range of wavelengths of 506-515 nm in their solid states.

  2. Design of a cold-neutron source for the Bariloche LINAC with solid mesitylene as moderator material

    International Nuclear Information System (INIS)

    Torres, Lourdes; Granada, J.R.


    We present the results of calculations performed with the code MCNP-4C relative to the neutron-field behaviour within the moderator for the Bariloche-LINAC cold-neutron source, using mesitylene at 89 K as moderating material. Throughout the design calculations we used preliminary nuclear-data libraries for that material that were previously generated and partially validated. The optimum dimensions for a slab and a cylindrical moderator were obtained, with and without a premoderator, from the point of view of neutron production and time-width of the neutron pulse

  3. FT-IR and FT-Raman, NMR and UV spectroscopic investigation and hybrid computational (HF and DFT) analysis on the molecular structure of mesitylene. (United States)

    Kose, E; Atac, A; Karabacak, M; Nagabalasubramanian, P B; Asiri, A M; Periandy, S


    The spectroscopic properties of mesitylene were investigated by FT-IR, FT-Raman, UV, (1)H and (13)C NMR techniques. The geometrical parameters and energies have been obtained from density functional theory (DFT) B3LYP method and Hartree-Fock (HF) method with 6-311++G(d,p) and 6-311G(d,p) basis sets calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (OPDOS) diagrams analysis were presented. (13)C and (1)H NMR chemical shifts were calculated by using the gauge-invariant atomic orbital (GIAO) method. The electronic properties, such as excitation energies, oscillator strength, wavelengths, HOMO and LUMO energies, were performed by time-dependent density functional theory (TD-DFT) results complements with the experimental findings. The results of the calculations were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) and thermodynamic properties were performed. Reduced density gradient (RDG) of the mesitylene was also given to investigate interactions of the molecule. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Volumetric, Viscometric and Excess Properties of Binary Mixtures of 1-Iodobutane with Benzene, Toluene, o-Xylene, m-Xylene, p-Xylene, and Mesitylene at Temperatures from 303.15 to 313.15 K


    Sharma, Sangita; Thakkar, Khushbu; Patel, Paras; Makavana, Madhuresh


    Densities and viscosities have been determined for binary mixtures of 1-iodobutane with benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene at 303.15, 308.15, and 313.15 K for the entire composition range at atmospheric pressure. The excess molar volumes, , deviations in viscosity, Δη, and excess Gibbs’ free energy of activation flow, Δ have been calculated from the experimental values. The experimental data were fitted to Redlich-Kister polynomial equation. The variations of these...

  5. Excess and deviation properties for the binary mixtures of methylcyclohexane with benzene, toluene, p-xylene, mesitylene, and anisole at T = (298.15, 303.15, and 308.15) K

    International Nuclear Information System (INIS)

    Baragi, Jagadish G.; Aralaguppi, Mrityunjaya I.


    Experimental data on density, viscosity, and refractive index at T = (298.15, 303.15, and 308.15) K, while speed of sound values at T = 298.15 K are presented for the binary mixtures of (methylcyclohexane + benzene), methylbenzene (toluene), 1,4-dimethylbenzene (p-xylene), 1,3,5-trimethylbenzene (mesitylene), and methoxybenzene (anisole). From these data of density, viscosity, and refractive index, the excess molar volume, the deviations in viscosity, molar refraction, speed of sound, and isentropic compressibility have been calculated. The computed values have been fitted to Redlich-Kister polynomial equation to derive the coefficients and estimate the standard errors. Variations in the calculated excess quantities for these mixtures have been studied in terms of molecular interactions between the component liquids and the effects of methyl and methoxy group substitution on benzene ring

  6. Volumetric, Viscometric and Excess Properties of Binary Mixtures of 1-Iodobutane with Benzene, Toluene, o-Xylene, m-Xylene, p-Xylene, and Mesitylene at Temperatures from 303.15 to 313.15 K

    Directory of Open Access Journals (Sweden)

    Sangita Sharma


    Full Text Available Densities and viscosities have been determined for binary mixtures of 1-iodobutane with benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene at 303.15, 308.15, and 313.15 K for the entire composition range at atmospheric pressure. The excess molar volumes, , deviations in viscosity, Δη, and excess Gibbs’ free energy of activation flow, Δ have been calculated from the experimental values. The experimental data were fitted to Redlich-Kister polynomial equation. The variations of these parameters with composition of the mixtures and temperature have been discussed in terms of molecular interactions occurring in these mixtures. Further, the viscosities of these binary mixtures were calculated theoretically from their corresponding pure component data by using empirical relations like Bingham, Arrhenius and Eyring, Kendall and Munroe, Hind, Katti and Chaudhari, Grunberg and Nissan, and Tamura and Kurata. Comparison of various interaction parameters has been expressed to explain the intermolecular interactions between iodobutane and selected hydrocarbons.

  7. Synthesis and Properties of the Heterospin (S1 = S2 = (1)/2) Radical-Ion Salt Bis(mesitylene)molybdenum(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl. (United States)

    Pushkarevsky, Nikolay A; Semenov, Nikolay A; Dmitriev, Alexey A; Kuratieva, Natalia V; Bogomyakov, Artem S; Irtegova, Irina G; Vasilieva, Nadezhda V; Bode, Bela E; Gritsan, Nina P; Konstantinova, Lidia S; Woollins, J Derek; Rakitin, Oleg A; Konchenko, Sergey N; Ovcharenko, Victor I; Zibarev, Andrey V


    Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene/1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = (1)/2) radical-ion salt [MoMes2](+)[1](-) (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) and monotonically decreases with lowering of the temperature. In the temperature range 2-300 K, the molar magnetic susceptibility of 2 is well-described by the Curie-Weiss law with parameters C and θ equal to 0.78 cm(3) K mol(-1) and -31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2](+)[1](-) and [CrCp*2](+)[1](-), i.e., changing the cation [MAr2](+) 3d atom M = Cr (Z = 24) with weak spin-orbit coupling (SOC) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product.

  8. Mesitylene-Cored Glucoside Amphiphiles (MGAs) for Membrane Protein Studies: Importance of Alkyl Chain Density in Detergent Efficacy

    DEFF Research Database (Denmark)

    Cho, Kyung Ho; Ribeiro, Orquidea; Du, Yang


    Detergents serve as useful tools for membrane protein structural and functional studies. Their amphipathic nature allows detergents to associate with the hydrophobic regions of membrane proteins whilst maintaining the proteins in aqueous solution. However, widely used conventional detergents...... developed xylene-linked maltoside agents (XMAs) with two alkyl chains and a conventional detergent (DDM). When these agents were evaluated for four membrane proteins including a G protein-coupled receptor (GPCR), some agents such as MGA-C13 and MGA-C14 resulted in markedly enhanced stability of membrane...... proteins compared to both DDM and the XMAs. This favourable behaviour is due likely to the increased hydrophobic density provided by the extra alkyl chain. Thus, this study not only describes new glucoside agents with potential for membrane protein research, but also introduces a new detergent design...

  9. Half-pseudoferrocene cations from nucleophilic addition of o-carboranyl anions to the [(eta(6)-mesitylene)(2)Fe](2+) dication

    Czech Academy of Sciences Publication Activity Database

    Bakardjiev, Mario; Štíbr, Bohumil; Holub, Josef; Růžička, A.; Padělková, Z.


    Roč. 41, č. 23 (2012), s. 7151-7155 ISSN 1477-9226 R&D Projects: GA ČR(CZ) GAP207/11/0705 Keywords : trialkylaluminum reagens * Iron complexes * reduction * biscarborane * B10C2H12 Subject RIV: CA - Inorganic Chemistry Impact factor: 3.806, year: 2012

  10. 4,4′,4′′-Tris(2-pyridyl-2,2′,2′′-[(2,4,6-trimethylbenzene-1,3,5-triyltris(methylenetris(sulfanediyl]tripyrimidine

    Directory of Open Access Journals (Sweden)

    Ya-Wen Zhang


    Full Text Available The title compound, C39H33N9S3, features a mesitylene unit substituted with three thioether arms. The distances from the center of mesitylene unit to the N atoms of the three pyridine rings in the arms are 10.05 (1, 9.94 (3 and 8.79 (3 Å. The crystal structure shows weak intramolecular C—H...N hydrogen bonds.

  11. Structural Characteristics and Swelling Mechanism of Two Commercial Nitrile-Butadiene Elastomers in Various Fluids (United States)


    reported here. The fluids used in these investigations included toluene, o- xylene , p- xylene , mesitylene, HISOL- 15, n-hexane, ethanol, tert-butyl...were monitored as a function of time. Structural characterization of the elastomer was done using x-ray diffraction and FTIR spectroscopy. Time...fluids are reported here. The fluids used in these investigations included toluene, o- xylene , p- xylene , mesitylene, HISOL-15, n-hexane, ethanol, tert

  12. Moderators for the design of a cold neutron source for the RA 3 reactor

    International Nuclear Information System (INIS)

    Cantargi, F; Sbaffoni, M; Granada, R


    The cold neutron production of hydrogenous materials was studied, taking into account their radiation resistance, for the conceptual design of a cold neutron source for the RA-3 reactor.Low spontaneous release of chemical energy was found in mesitylene.Libraries for hidrogen in mesitylene were generated using the NJOY nuclear processing system and the resulting cross sections were compared with experimental data.Good agreement between measurements and calculations was found in those cases where data are available.New calculations using the RA-3 geometry and these validated libraries will be performed [es

  13. An easy assembled fluorescent sensor for dicarboxylates and acidic amino acids

    Directory of Open Access Journals (Sweden)

    Albert W. M. Lee


    Full Text Available Two mesitylene based neutral receptors 1 and 2 bearing two thiourea binding sites were constructed as fluorescent probes for sensing dicarboxylates. Their binding affinities toward dicarboxylates, aspartate and glutamate have been investigated in acetonitrile solution by fluorescence titration experiments. Both fluorescent sensors exhibited some ability to discriminate the antipodal forms of aspartate and glutamate.

  14. Ruthenium-catalysed synthesis of 2- and 3-substituted quinolines from anilines and 1,3-diols

    DEFF Research Database (Denmark)

    Monrad, Rune Nygaard; Madsen, Robert


    A straightforward synthesis of substituted quinolines is described by cyclocondensation of anilines with 1,3-diols. The reaction proceeds in mesitylene solution with catalytic amounts of RuCl3·xH 2O, PBu3 and MgBr2·OEt2. The transformation does not require any stoichiometric additives and only...


    African Journals Online (AJOL)


    In a similar fashion, the difference in reactivity of dimers p-cymene and mesitylene ruthenium toward the oxalato ligand was also previously observed by .... of 2, it becomes irregular, without being split, with the appearance of two shoulders before 1700 cm-1 at 1680 and 1660 cm-1. This connotes the effect of the ligand ...

  16. Integrated Photonic Orbital Angular Momentum Multiplexing and Demultiplexing on Chip (United States)


    curves for various commercially available BCB formulations. ....................................... 81 Figure 134 BCB degree of polymerization as a...function of temperature and time. ................................... 82 Figure 135 SEM image of ultra-thin BCB bonding layer between Si and InP...wafers, obtained using 1:12 BCB : mesitylene solution

  17. Measurement of cold neutron spectra at a model of cryogenic moderator of the IBR-2M reactor

    International Nuclear Information System (INIS)

    Kulikov, S.A.; Chernikov, A.N.; Shabalin, E.P.; Kalinin, I.V.; Morozov, V.M.; Novikov, A.G.; Puchkov, A.V.


    The article is dedicated to methods and results of experimental determination of cold neutron spectra from solid mesitylene at neutron moderator temperatures 10-50 K. Experiments were fulfilled at the DIN-2PI spectrometer of the IBR-2 reactor. The main goals of this work were to examine a system of constants for Monte Carlo calculation of cryogenic moderators of the IBR-2M reactor and to determine the temperature dependence of cold neutron intensity from the moderator. A reasonable agreement of experimental and calculation results for mesitylene at 20 K has been obtained. The cold neutron intensity at temperature of moderator 10 K is about 1.8 times higher than at T=50 K

  18. Temperature Dependence of the Inhibition of Positronium by Chlorine- Substituted Hydrocarbons in Non-Polar Liquids

    DEFF Research Database (Denmark)

    Wikander, G.; Mogensen, O.E.; Pedersen, Niels Jørgen


    Positron annihilation lifetime spectra were measured for solutions of 1,2,3,5-C6H2Cl4 in hexane, toluene, m-xylene and mesitylene, CCl4 in hexane and toluene, and C2HCl3 in n-hexane for concentrations below 1 M and at various temperatures between −30°C and 67°C. The Ps inhibition by C6H2Cl4...... was roughly 14 times stronger at −30°C than at 67°C in toluene, m-xylene, and mesitylene, while that of CCl4 displayed hardly any temperature dependence in hexane and toluene. Previously, the Ps inhibition by C6H2Cl4 in various liquids at 20°C was explained by a competition between electron pick off...

  19. Optimized sub thermal neutron source to Linac of CAB

    International Nuclear Information System (INIS)

    Torres, L; Granada, R


    We present the results of calculations performed with the code M C N P relative to the neutron field behavior within the moderator for the Bariloche-Linac cold neutron source, using polyethylene as pre moderator and solid mesitylene as moderating material at 90 K.The optimum dimensions for a moderator were obtained, with and without a pre moderator, from the point of view of neutron production and time-width of the neutron pulse.Finally, we adopted for our cold neutron source, a slab pre moderator of P L E at room temperature, and a cylindrical moderator of mesitylene at 90 K with a cooler system of stainless steel with windows of Zircaloy-4 [es

  20. Solution phase chemical synthesis of nano aluminium particles stabilized in poly(vinylpyrrolidone) and poly(methylmethacrylate) matrices. (United States)

    Ghanta, Sekher Reddy; Muralidharan, Krishnamurthi


    The reduction of aluminium trichloride by lithium aluminium hydride in the presence of poly(vinylpyrrolidone) or poly(methylmethacrylate) in mesitylene yielded nano aluminium particles in the matrices of respective polymers. Solution phase synthesis methodology was used successfully to produce composites of various Al/polymer ratios. The composites were characterized by powder XRD patterns and 27Al-NMR with MAS spectroscopic study. The method was useful to produce up to 10 g of nano aluminium that were pure and stable.

  1. Phase transitions on (liquid + liquid) equilibria for (water + 1-methylnaphthalene + light aromatic hydrocarbon) ternary systems at T = (563, 573, and 583) K

    International Nuclear Information System (INIS)

    Togo, Masaki; Inamori, Yoshiki; Shimoyama, Yusuke


    Highlights: ► Mixtures of (water + 1-methylnaphthalene + light aromatic hydrocarbon) are focused. ► Phase transition pressures on (liquid + liquid) equilibria were measured. ► Effects of aromatic hydrocarbons on phase transition pressure are investigated. ► Phase transition pressures are discussed using dielectric constants of hydrocarbons. - Abstract: Phase transitions for (water + 1-methylnaphthalene + light aromatic hydrocarbon) ternary systems are observed at their (liquid + liquid) equilibria at T = (563, 573, and 583) K and (8.6 to 25.0) MPa. The phase transition pressures at T = (563, 573, and 583) K were measured for the five species of light aromatic hydrocarbons, o-, m-, p-xylenes, ethylbenzene, and mesitylene. The measurements of the phase transition pressures were carried out by changing the feed mole fraction of water and 1-methylnaphthalene in water free, respectively. Effects of the feed mole fraction of water on the phase transition pressures are very small. Increasing the feed mole fraction of 1-methylnaphthalene results in decreasing the phase transition pressures at constant temperature. The slopes depending on the feed mole fraction for 1-methylnaphthalene at the phase transition pressures are decreased with increasing temperature for (water + 1-methylnaphthalene + p-xylene), (water + 1-methylnaphthalene + o-xylene), and (water + 1-methylnaphthalene + mesitylene) systems. For xylene isomers, the highest and lowest of the phase transition pressures are obtained in the case of p- and o-xylenes, respectively. The phase transition pressures for ethylbenzene are lower than those in the case of p-xylene. The similar phase transition pressures are given for p-xylene and mesitylene.

  2. Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

    DEFF Research Database (Denmark)

    Ghalehshahi, Hajar Golshadi; Madsen, Robert


    into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver......A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2 CO3 and 2.5-3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted...

  3. Jet Fuel Exacerbated Noise-Induced Hearing Loss: Focus on Prediction of Central Auditory Processing Dysfunction (United States)


    acids were eluted next using 3 mL ethyl ether- acetic acid (100:2) and the neutral phospholipids were eluted using 3 mL methanol. Lastly, acidic...phospholipids were eluted using 3 mL of hexane-isopropanol-ethanol-0.1 M ammonium acetate in water-formic acid (420:350:100:50:0.5) containing 5 percent...K.G., Federsel, R.J. and Freundt, K.J. 1986. Rise of inhaled toluene, ethyl benzene, % m-xylene, or mesitylene in rat blood after treatment with

  4. Influence of diluents on the extraction of nitric acid by methyl-n-diheptylamine

    International Nuclear Information System (INIS)

    Shvedov, V.P.; Kopyrin, A.A.; Titov, V.S.


    The influence of certain aromatic diluents (mesitylene, p-xylene, toluene, benzene, and nitrobenzene) on the extraction of nitric acid by methyl-n-diheptylamine was investigated according to the reaction of neutralization. The equilibrium constants of this reaction were determined at a constant ionic strength in the aqueous phase (1 M LiNo 3 ; μ=1). Using a thermochemical method, the solvating ability of the diluents considered was estimated. The distribution of methyl-n-heptylamine nitrate between the aqueous and organic phases with various diluents was investigated by a colorimetric method. The data obtained were used to characterize the influence of the solvents on extraction

  5. Chlorination of (PheboxIr(mesityl(OAc by Thionyl Chloride

    Directory of Open Access Journals (Sweden)

    Meng Zhou


    Full Text Available Pincer (PheboxIr(mesityl(OAc (2 (Phebox = 3,5-dimethylphenyl-2,6-bis(oxazolinyl complex, formed by benzylic C-H activation of mesitylene (1,3,5-trimethylbenzene using (PheboxIr(OAc2OH2 (1, was treated with thionyl chloride to rapidly form 1-(chloromethyl-3,5-dimethylbenzene in 50% yield at 23 °C. A green species was obtained at the end of reaction, which decomposed during flash column chromatography to form (PheboxIrCl2OH2 in 87% yield.

  6. The Acidity of the HBr/AlBr3 System: Stabilization of Crystalline Protonated Arenes and Their Acidity in Bromoaluminate Ionic Liquids. (United States)

    Scholz, Franziska; Himmel, Daniel; Eisele, Lea; Unkrig, Wiebke; Martens, Arthur; Schlüter, Peter; Krossing, Ingo


    Bulk protonated mesitylene, toluene, and benzene bromoaluminate salts were stabilized and characterized in the superacidic system HBr/n AlBr3 with NMR spectroscopy and X-ray analysis of [HC6 H3 (CH3 )3 ](+) [AlBr4 ](-) (1), [HC6 H5 (CH3 )](+) [AlBr4 ](-) (2), and [C6 H7 ](+) [Al2 Br7 ](-) ⋅C6 H6 (3). Protonation attempts in bromoaluminate ILs led to a complete protonation of mesitylene, and a protonation degree of up to 15 % for toluene in the IL BMP(+) [Al2 Br7 ](-) . Benzene could only be protonated in the more acidic IL BMP(+) [Al3 Br10 ](-) , with a degree of 25 %. Protonation attempts on aromatics provide evidence that the bromoaluminate ILs tolerate superacidic environments. On the basis of the absolute Brønsted acidity scale, quantum chemical calculations confirmed the superacidic properties, and rank the acidities in ILs down to a pHabs value of 164 with an error of less than one pH unit compared with experimental findings. The neat AlBr3 /HBr system even may reach acidities down to pHabs 163. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Study of Electrical Transport Properties of Thin Films Used as HTL and as Active Layer in Organic Solar Cells, through Impedance Spectroscopy Measurements

    Directory of Open Access Journals (Sweden)

    Camilo A. Otalora


    Full Text Available Impedance spectroscopy (IS is used for studying the electrical transport properties of thin films used in organic solar cells with structure ITO/HTL/active layer/cathode, where PEDOT:PSS (poly(3,4-ethylenedioxythiophene:polystyrene sulfonic acid and CuPC (tetrasulfonated copper-phthalocyanine were investigated as HTL (hole transport layer and P3HT:PCBM (poly-3-hexylthiophene:phenyl-C61-butyric acid methyl ester blends prepared from mesitylene and chlorobenzene based solutions were studied as active layer and Ag and Al were used as cathode. The study allowed determining the influence of the type of solvent used for the preparation of the active layer as well as the speed at which the solvents are removed on the carriers mobility. The effect of exposing the layer of P3HT to the air on its mobility was also studied. It was established that samples of P3HT and P3HT:PCBM prepared using mesitylene as a solvent have mobility values significantly higher than those prepared from chlorobenzene which is the solvent most frequently used. It was also determined that the mobility of carriers in P3HT films strongly decreases when this sample is exposed to air. In addition, it was found that the electrical properties of P3HT:PCBM thin films can be improved by removing the solvent slowly which is achieved by increasing the pressure inside the system of spin-coating during the film growth.

  8. Highly Efficient and Reproducible Nonfullerene Solar Cells from Hydrocarbon Solvents

    KAUST Repository

    Wadsworth, Andrew


    With chlorinated solvents unlikely to be permitted for use in solution-processed organic solar cells in industry, there must be a focus on developing nonchlorinated solvent systems. Here we report high-efficiency devices utilizing a low-bandgap donor polymer (PffBT4T-2DT) and a nonfullerene acceptor (EH-IDTBR) from hydrocarbon solvents and without using additives. When mesitylene was used as the solvent, rather than chlorobenzene, an improved power conversion efficiency (11.1%) was achieved without the need for pre- or post-treatments. Despite altering the processing conditions to environmentally friendly solvents and room-temperature coating, grazing incident X-ray measurements confirmed that active layers processed from hydrocarbon solvents retained the robust nanomorphology obtained with hot-processed chlorinated solvents. The main advantages of hydrocarbon solvent-processed devices, besides the improved efficiencies, were the reproducibility and storage lifetime of devices. Mesitylene devices showed better reproducibility and shelf life up to 4000 h with PCE dropping by only 8% of its initial value.

  9. Design of a cold neutron source for 25MeV Linac of CAB (Centro Atomico Bariloche - Argentina)

    International Nuclear Information System (INIS)

    Torres, Lourdes


    Cold neutrons are widely used in fields of research such as the dynamics of solids and liquids, the investigation of magnetic materials, material science, biology, and nuclear physics in general. Accelerator-based cold neutron sources have already proved to be well adapted to perform neutron scattering studies in all those fields.In this work we present the design of a cold neutron source in the electron Linac-based pulsed source at Centro Atomico Bariloche.The objective of this work is to develop an inexpensive yet efficient cold source with a simple moderator material.Although ideal materials for that purpose would be solid methane or liquid H2, due to economical and safety reasons light water ice, benzene or solid mesitylene were considered as cold moderators. In order to proceed with the design and optimization process of the neutron source, total cross sections for light water ice, benzene and mesitylene were measured at low temperature and thermal nuclear data libraries for such materials had to be developed.The purpose of these calculations was to optimize shape and size for the moderator at a working temperature.To calculations were performed using the MCNP-4C code and our libraries, together with files for (free-atom) carbon, hydrogen and oxygen at that temperature.The geometry studied consisted of a neutron source and different moderator (slab, cylindrical slab, grids, and sets premoderator - moderator with and without coupled).To simplify the system cooler, the slab geometry was changed to a coin shaped moderator using liquid nitrogen as cooler.From the variety of simulations performed, it was clear that a premoderator was necessary to obtain higher intensities.Furthermore, with a premoderator the thickness of the moderator was reduced, simplifying the cooling system.Finally, we adopted for our cold neutron source, a slab premoderator of PLE at room temperature, and a cylindrical moderator of mesitylene at 89K with a cooler system of stainless steel with

  10. Investigation into radiolysis of tbp labelled with 32P in the 30%tbp-diluent-HNO3 systems

    International Nuclear Information System (INIS)

    Novak, M.; Novak, Z.; Rokhon', A.


    Phosphorus-containing compounds, prepared by radiolysis of the TBP-diluent-HNO 3 system, are determined quantitatively. Effects of the HNO 3 concentration and the diluent type upon the degree of the TBP decomposition in the system under investigation were determined as well. To separate the TBP decomposition products the thin layer chromatography method was used, and for the quantitative determination TBP, labelled with 32 P was used. As a result of TBP radiolysis except dibutyl phosphate and monobutylphosphate other compounds are prepared, which contain phosphorus in a molecule, besides, their quantity depends on the nitric acid concentration and the diluent type (n-dodecan, carbon tetrachloride, mesitylen), together with which TBP was irradiated. The prepared compounds are grouped in the aqueous and organic phases

  11. Effect of coal-derived-liquid solvent on the hydrogenation and restrictive diffusion of nickel porphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, C.H.; Massoth, F.E.; Lee, S.Y.; Seader, J.D. (University of Utah, Salt Lake City, UT (USA). Dept. of Fuels Engineering)


    Hydrogenation of nickel porphyrins was carried out at 335{degree}C and 50 atm hydrogen pressure with two Ni-Mo/alumina catalysts of different pore sizes. Solvents employed were a triple-hydrotreated coal-derived-liquid and four pure hydrocarbons (n-decane, decalin, tetralin, and mesitylene). Reaction rates in the hydrotreated coal-derived-liquid solvent were higher than those in pure solvents with higher hydrogen solubilities. The results were attributed to the greater hydrogen-donor ability of the hydrotreated coal-derived-liquid solvent. Reaction rates of different catalyst particle sizes were used to calculate effective diffusivities under processing conditions. Reactivity was significantly affected by catalyst deactivation via coke buildup at catalyst pore mouths. Accounting for this additional diffusional constraint, restrictive diffusion in the coal-liquid solvent under processing conditions was found to be in reasonable agreement with approximate hydrodynamic theory for non-reactive conditions. 33 refs., 6 figs., 4 tabs.

  12. Adsorption of probe molecules in pillared interlayered clays: Experiment and computer simulation

    Energy Technology Data Exchange (ETDEWEB)

    Gallardo, A., E-mail:; Guil, J. M.; Lomba, E.; Almarza, N. G.; Khatib, S. J. [Instituto de Química Física Rocasolano, CSIC, Serrano 119, E-28006 Madrid (Spain); Cabrillo, C.; Sanz, A. [Instituto de Estructura de la Materia, CSIC, Serrano 123, E-28006 Madrid (Spain); Pires, J. [Centro de Química e Bioquímica da Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal)


    In this paper we investigate the adsorption of various probe molecules in order to characterize the porous structure of a series of pillared interlayered clays (PILC). To that aim, volumetric and microcalorimetric adsorption experiments were performed on various Zr PILC samples using nitrogen, toluene, and mesitylene as probe molecules. For one of the samples, neutron scattering experiments were also performed using toluene as adsorbate. Various structural models are proposed and tested by means of a comprehensive computer simulation study, using both geometric and percolation analysis in combination with Grand Canonical Monte Carlo simulations in order to model the volumetric and microcalorimetric isotherms. On the basis of this analysis, we propose a series of structural models that aim at accounting for the adsorption experimental behavior, and make possible a microscopic interpretation of the role played by the different interactions and steric effects in the adsorption processes in these rather complex disordered microporous systems.

  13. Densities and volumetric properties of (N-acetylmorpholine + aromatic hydrocarbon) binary mixtures from T = (293.15 to 343.15) K

    International Nuclear Information System (INIS)

    Abu-Daabes, Malyuba A.; Awwad, Akl M.; Al-Ani, Hawzen A.


    The experimental densities, ρ for binary mixtures of (N-acetylmorpholine + benzene, +toluene, +ethylbenzene, and +mesitylene) have been measured at temperatures from (293.15 to 343.15) K and atmospheric pressure over the whole mole fraction range. From these results, excess molar volumes V E have been calculated and fitted to the Redlich-Kister polynomial equation. The V E values are negative over the whole mole fraction range and at all temperatures. Thermal expansion coefficients α i , apparent molar volumes Vφ i , and partial molar volumes at infinite dilution V i ∞ have been calculated. The variation of these properties with composition and temperature of the binary mixtures are discussed in terms of molecular interactions

  14. Carbon dioxide hydrogenation to aromatic hydrocarbons by using an iron/iron oxide nanocatalyst. (United States)

    Wang, Hongwang; Hodgson, Jim; Shrestha, Tej B; Thapa, Prem S; Moore, David; Wu, Xiaorong; Ikenberry, Myles; Troyer, Deryl L; Wang, Donghai; Hohn, Keith L; Bossmann, Stefan H


    The quest for renewable and cleaner energy sources to meet the rapid population and economic growth is more urgent than ever before. Being the most abundant carbon source in the atmosphere of Earth, CO2 can be used as an inexpensive C1 building block in the synthesis of aromatic fuels for internal combustion engines. We designed a process capable of synthesizing benzene, toluene, xylenes and mesitylene from CO2 and H2 at modest temperatures (T = 380 to 540 °C) employing Fe/Fe3O4 nanoparticles as catalyst. The synthesis of the catalyst and the mechanism of CO2-hydrogenation will be discussed, as well as further applications of Fe/Fe3O4 nanoparticles in catalysis.

  15. Carbon dioxide hydrogenation to aromatic hydrocarbons by using an iron/iron oxide nanocatalyst

    Directory of Open Access Journals (Sweden)

    Hongwang Wang


    Full Text Available The quest for renewable and cleaner energy sources to meet the rapid population and economic growth is more urgent than ever before. Being the most abundant carbon source in the atmosphere of Earth, CO2 can be used as an inexpensive C1 building block in the synthesis of aromatic fuels for internal combustion engines. We designed a process capable of synthesizing benzene, toluene, xylenes and mesitylene from CO2 and H2 at modest temperatures (T = 380 to 540 °C employing Fe/Fe3O4 nanoparticles as catalyst. The synthesis of the catalyst and the mechanism of CO2-hydrogenation will be discussed, as well as further applications of Fe/Fe3O4 nanoparticles in catalysis.

  16. The synthesis, lipophilicity and cytotoxic effects of new ruthenium(II) arene complexes with chromone derivatives. (United States)

    Pastuszko, Adam; Majchrzak, Kinga; Czyz, Malgorzata; Kupcewicz, Bogumiła; Budzisz, Elzbieta


    A series of arene ruthenium(II) complexes with the general formula [(η(6)-arene)Ru(L)X2] (where arene=p-cymene, benzene, hexamethylbenzene or mesitylene, L=aminoflavone or aminochromone derivatives and X=Cl, I) were synthesized and characterized by elemental analysis, MS, IR and (1)H NMR spectroscopy. The stability of the selected complexes was assessed by UV-Vis spectroscopy in 24-hour period. The lipophilicity of the synthesized complexes was determined by the shake-flask method, and their cytotoxicity evaluated in vitro on patient-derived melanoma populations. The most active complexes against melanoma cells contain 7-aminoflavone and 6-aminoflavone as a ligand. The relationship between the cytotoxicity of all the obtained compounds and their logP values was determined and briefly analyzed with two different patterns observed. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Design and safety aspects of the Cornell cold neutron source

    International Nuclear Information System (INIS)

    Ouellet, Carol G.; Clark, David D.


    The cold neutron beam facility at the Cornell University TRIGA Mark II reactor will begin operational testing in early 1993. It is designed to provide a low background subthermal neutron beam that is as free as possible of fast neutrons and gamma rays for applied research and graduate-level instruction. The Cornell cold neutron source differs from the more conventional types of cold sources in that it is inherently safer because it uses a safe handling material (mesitylene) as the moderator instead of hydrogen or methane, avoids the circulation of cryogenic fluids by removing heat from the system by conduction through a 99.99% pure copper rod attached to a cryogenic refrigerator, and is much smaller in its size and loads. The design details and potential hazards are described, where it is concluded that no credible accident involving the cold source could cause damage to the reactor or personnel, or cause release of radioactivity. (author)

  18. Retention models and interaction mechanisms of benzene and other aromatic molecules with an amylose-based sorbent. (United States)

    Hsieh, Han-Yu; Wu, Shyuan-Guey; Tsui, Hung-Wei


    Stoichiometric displacement models have been widely used for understanding the adsorption mechanisms of solutes in chromatography systems. Such models are used for interpreting plots of solute retention factor versus concentrations of polar modifier in an inert solvent. However, these models often assume that dispersion forces are negligible and they are unable to account for solutes with significant aromatic interactions. In this study, a systematic investigation of the relationship between retention behavior and aromatic groups was performed using five simple aromatic molecules-benzene, naphthalene, mesitylene, durene, and toluene-with a commercially available amylose tris(3,5-dimethylphenylcarbamate)-based sorbent. The enthalpy changes of adsorption, determined from van't Hoff plots, were obtained separately in pure n-hexane and in pure isopropanol (IPA). In pure n-hexane, the solute adsorptions were driven by electrostatic interactions, favoring a T-shaped binding configuration (edge-to-face π-π interaction). The order of enthalpy change indicated the amount of effective T-shaped π-interactions. In pure IPA, solute adsorption was dominated by dispersion forces, favoring a sandwich binding configuration (face-to-face π-π interaction). The adsorption isotherms of toluene revealed that in pure IPA and in pure n-hexane, the isotherms were linear. The results suggested that the high solvent strength of IPA weakened the interactions between aromatic molecules. The retention behavior of the benzene, naphthalene, mesitylene, and durene as a function of IPA concentration was investigated. U-shaped retention curves were found for all aromatic solutes. A new retention model for monovalent aromatic solutes was developed for describing the U-shaped curves. Three key dimensionless groups were revealed to control the retention behavior. The models suggested that solvophobic interactions should be accounted for in the retention models used to investigate the retention

  19. Synthesis and Characterization of New Trinuclear Copper Complexes (United States)

    Ghiladi, Reza A.; Rheingold, Arnold L.; Siegler, Maxime A.; Karlin, Kenneth D.


    This report describes our approach towards modelling the copper cluster active sites of nitrous oxide reductase and the multicopper oxidases/oxygenases. We have synthesized two mesitylene-based trinucleating ligands, MesPY1 and MesPY2, which employ bis(2-picolyl)amine (PY1) and bis(2-pyridylethyl)amine (PY2) tridentate copper chelates, respectively. Addition of cuprous salts to these ligands leads to the isolation of tricopper(I) complexes [(Mes-PY1)CuI3(CH3CN)3](ClO4)3·0.25Et2O (1) and [(Mes-PY2)CuI3](PF6)3 (3) Each of the three copper centers in 1 is most likely four-coordinate, with ligated acetonitrile as the fourth ligand; by contrast, the copper centers in 3 are three-coordinate, as determined by X-ray crystallography The synthesis of [(Mes-PY1)CuII3(CH3CN)2(CH3OH)2](ClO4)6·(CH3OH) (2) was accomplished by addition of three equivalents of the copper(II) salt, Cu(ClO4)2·6H2O, to the ligand. The structure of 2 shows that two of the copper centers are tetracoordinate (with MeCN solvent ligation), but have additional weak axial (fifth ligand) interactions with the perchlorate anions; the third copper is unique in that it is coordinated by two MeOH solvent molecules, making it overall five-coordinate. For complexes 2 and 3, one copper ion center is located on the opposite side of the mesitylene plane as the other two. These observations, although in the solid state, must be taken into account for future studies where intramolecular tricopper(I)/O2 (or other small molecules of interest) interactions in solution are desirable. PMID:22773847

  20. Osmium pyme complexes for fast hydrogenation and asymmetric transfer hydrogenation of ketones. (United States)

    Baratta, Walter; Ballico, Maurizio; Del Zotto, Alessandro; Siega, Katia; Magnolia, Santo; Rigo, Pierluigi


    The osmium compound trans,cis-[OsCl2(PPh3)2(Pyme)] (1) (Pyme=1-(pyridin-2-yl)methanamine), obtained from [OsCl2(PPh3)3] and Pyme, thermally isomerizes to cis,cis-[OsCl2(PPh3)(2)(Pyme)] (2) in mesitylene at 150 degrees C. Reaction of [OsCl2(PPh3)3] with Ph2P(CH2)(4)PPh2 (dppb) and Pyme in mesitylene (150 degrees C, 4 h) leads to a mixture of trans-[OsCl2(dppb)(Pyme)] (3) and cis-[OsCl2(dppb)(Pyme)] (4) in about an 1:3 molar ratio. The complex trans-[OsCl2(dppb)(Pyet)] (5) (Pyet=2-(pyridin-2-yl)ethanamine) is formed by reaction of [OsCl2(PPh3)3] with dppb and Pyet in toluene at reflux. Compounds 1, 2, 5 and the mixture of isomers 3/4 efficiently catalyze the transfer hydrogenation (TH) of different ketones in refluxing 2-propanol and in the presence of NaOiPr (2.0 mol %). Interestingly, 3/4 has been proven to reduce different ketones (even bulky) by means of TH with a remarkably high turnover frequency (TOF up to 5.7 x 10(5) h(-1)) and at very low loading (0.05-0.001 mol %). The system 3/4 also efficiently catalyzes the hydrogenation of many ketones (H2, 5.0 atm) in ethanol with KOtBu (2.0 mol %) at 70 degrees C (TOF up to 1.5 x 10(4) h(-1)). The in-situ-generated catalysts prepared by the reaction of [OsCl2(PPh3)3] with Josiphos diphosphanes and (+/-)-1-alkyl-substituted Pyme ligands, promote the enantioselective TH of different ketones with 91-96 % ee (ee=enantiomeric excess) and with a TOF of up to 1.9 x 10(4) h(-1) at 60 degrees C.

  1. Identification of chemical compounds of Nardostachys Jatamansi essence available in Iran

    Directory of Open Access Journals (Sweden)

    Ghassemi-Dehkordi Nasrolah


    Full Text Available Introduction: With regard to using drugs with plant origin and with the aim of suitable use of these types of drugs and preventing them to be abused, it is necessary to determine the standards of these plants. The aim of the present study was to identify and study chemical compounds of Nardostachys Jatamansi essence in Iran and define monograph of this plant for the Iranian plant pharmacopeia. Methods: In an experimental study the Nardostachys Jatamansi specimen was prepared from the market in Iran. The essence of the plant was prepared by the hydro-distillation in Clevenger apparatus. Essence was obtained as a greenish yellow oil layer with the 0.07 % yield. The essence compounds were identified quantitatively by Gas Chromatography-Mass Spectroscopy (GC/MS method. Results: Totally, 29 compounds were identified in Nardostachys Jatamansi essence. The retention indexes (RI were only similar with overall standard values in two compounds like mesitylene and P-cymene. In this line the RI values about three compounds of valerenic acid, palmitic acid, and valerenyl isovalerate were determined significantly higher than standard values of RI. Conclusion: The essence prepared from the Nardostachys Jatamansi plant in Iran was different in terms of some compounds and components including valerenic acid, palmitic acid, and valerenyl isovalerate and so it is necessary to identify and register quality and quantity characteristics of compounds available in this plat in the Iranian medicinal plants pharmacopeia.

  2. Formation of highly oxygenated organic molecules from aromatic compounds

    Directory of Open Access Journals (Sweden)

    U. Molteni


    Full Text Available Anthropogenic volatile organic compounds (AVOCs often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs, such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene and ethylbenzene, as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl. We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

  3. Diluent and extractant effects on the enthalpy of extraction of uranium(VI) and americium(III) nitrates by trialkyl phosphates

    International Nuclear Information System (INIS)

    Srinivasan, T.G.; Vasudeva Rao, P.R.; Sood, D.D.


    The effect of various diluents such as n-hexane, n-heptane n-octane, isooctane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, benzene, toluene, p-xylene, mesitylene and o-dichlorobenzene on the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate (TAP) over the temperature range 283 K--333 K has been studied. The results indicate that the enthalpy of extraction does not vary significantly with the diluents studied. Also enthalpies of extraction of uranyl nitrate and americium(III) nitrate by neutral organo phosphorous extractants such as tri-n-butyl phosphate (TBP), tri-n-amyl phosphate (TAP), tri-sec-butyl phosphate (TsBP), tri-isoamyl phosphate (TiAP) and tri-n-hexyl phosphate (THP) have been studied. An attempt has been made to explain the trends, on the basis of the nature of the solvate formed and the different terms which contribute to the overall enthalpy change

  4. Alkaline membrane water electrolysis with non-noble catalysts

    DEFF Research Database (Denmark)

    Kraglund, Mikkel Rykær

    . This, combined with better gas separation properties and a higher operating flexibility, have the prospects of significantly reducing the capex and opex of electrolysis systems, and the cost of green hydrogen. Towards this goal, membranes based on poly(2,2’-(mphenylene)-5,5’-bibenzimidazole) (m......-PBI) as well as poly(2,2’-(m-mesitylene)-5,5’-bibenzimidazole) (mes-PBI) were investigated as electrolyte for alkaline electrolysis cells. PBI membranes were equilibrated with aqueous KOH and applied as separator, and polarization data from cells at 20-25 wt% KOH using these membranes showed improved ohmic...... behaviour over cells with conventional porous separators. This was strikingly clear when combined with active electrodes with Raney-nickel-based coatings. With thin 40 μm m-PBI membranes, Raney-nickelmolybdenum cathodes and nickel anodes, cells operated at 80◦C with 24 wt% KOH (aq) achieved 1000 mA cm-2...

  5. The University of Texas Cold Neutron Source

    International Nuclear Information System (INIS)

    Uenlue, Kenan; Rios-Martinez, Carlos; Wehring, B.W.


    A cold neutron source has been designed, constructed, and tested by the Nuclear Engineering Teaching Laboratory (NETL) at The University of Texas at Austin. The Texas Cold Neutron Source (TCNS) is located in one of the beam ports of the NETL 1-MW TRIGA Mark II research reactor. The main components of the TCNS are a cooled moderator, a heat pipe, a cryogenic refrigerator, and a neutron guide. 80 ml of mesitylene moderator are maintained at about 30 K in a chamber within the reactor graphite reflector by the heat pipe and cryogenic refrigerator. The heat pipe is a 3-m long aluminum tube that contains neon as the working fluid. The cold neutrons obtained from the moderator are transported by a curved 6-m long neutron guide. This neutron guide has a radius of curvature of 300 m, a 50x15 mm cross-section, 58 Ni coating, and is separated into three channels. The TCNS will provide a low-background subthermal neutron beam for neutron capture and scattering research. After the installation of the external portion of the neutron guide, a neutron focusing system and a Prompt Gamma Activation Analysis facility will be set up at the TCNS. ((orig.))

  6. A three-dimensional metal–organic framework for selective sensing of nitroaromatic compounds

    Directory of Open Access Journals (Sweden)

    Dan Tian


    Full Text Available A 3D metal–organic framework [NH2(CH32][Cd6(L4(DMF6(HCOO](DMF = N,N-dimethylformamide (1 has been synthesized using a tripodal ligand H3L (2,4,6-tris[1-(3-carboxylphenoxyylmethyl]mesitylene. The obtained complex exhibits a 3D framework containing hexanuclear {Cd6} building units formed by two trinuclear {Cd3} clusters that are connected via HCOO− anions. For complex 1, the participation of the fluorescent ligand H3L not only gives rise to a strong photoluminescence emission as expected, but more interestingly, that ligand originated characteristic band could be quenched selectively by nitrobenzene with a low detection limit, showing its potential as a highly sensitive and selective sensor for nitrobenzene. Based on an electron transfer quenching mechanism, the fluorescence sensing ability of 1 is also applicable for other electron-deficient nitroaromatic compounds with high selectivity and sensitivity, i.e., 1,4-dinitrobenzene, 1,3-dinitrobenzene, 2,4-dinitrotoluene, and 4-nitrotoluene, suggesting 1 a promising fluorescence sensor for detecting and recognizing the same kind of chemicals.

  7. Formation of highly oxygenated organic molecules from aromatic compounds (United States)

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


    Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

  8. Chemical Composition and Aroma Evaluation of Essential Oils from Skunk Cabbage (Symplocarpus foetidus). (United States)

    Miyazawa, Mitsuo; Nakahashi, Hiroshi; Kashima, Yusei; Motooka, Ryota; Hara, Nobuyuki; Nakagawa, Hiroki; Yoshii, Takashi; Usami, Atsushi; Marumoto, Shinsuke


    Two sample preparation methods, namely hydrodistillation (HD) and solvent-assisted flavor evaporation (SAFE), have been used to investigate the essential oils of the aerial parts (leaves and stems) of Symplocarpus foetidus, a plant with a characteristic odor, by gas chromatography mass spectrometry (GC-MS). Characteristic aroma-active compounds in the oils were detected by GC-Olfactometry (GC-O) and aroma extract dilution analysis (AEDA). From the HD method, the main compounds in the oil were found to be p-vinyl-guaiacol (15.5%), 2-pentyl-furan (13.4%), and (Z)-ligustilide (9.5%). From the SAFE method, the main compounds were 2-butoxy-ethanol (49.6%), ethyl-pentanoate (4.5%), and mesitylene (4.0%). In HD oil, the most intense aroma-active compounds were 2-pentyl-furan (flavor dilution factor (FD) = 32, odor activity value (OAV) = 57), p-vinyl-guaiacol (FD = 16, OAV = 41), and dimethyl disulfide (FD = 16, OAV = 41). In SAFE oil, the main aroma-active compounds were 2-butoxy ethanol (FD = 32, OAV = 16), and 2-methoxy thiazole (FD = 32, OAV = 25).

  9. Patent application for a process for production of unsaturated compounds

    Energy Technology Data Exchange (ETDEWEB)


    This patent application concerned primarily the use of catalysts consisting of solid acids carried on synthetic resins in the dehydration of substances containing hydroxyl groups to produce unsaturated compounds. These catalysts fell under the general name of Wofatites, and their principal previous usage had been in hydrogen ion exchange reactions. The catalyst was effective in dehydrating straight-chain and cyclic alcohols to corresponding unsaturated compounds (olefins, etc.). Some other examples of such transformations were diacetone alcohol changed to mesitylene oxide, ethylene cyanhydrin changed to acrylonitrile, malic acid changed to fumaric acid, and glycols changed to diolefins. The use of the catalyst mentioned above allowed the use of somewhat lower temperatures than did the use of previous catalysts such as aluminum oxide, chromium oxide, tungsten oxide, thorium oxide, zinc chloride, phosphoric acid, arsenic acid, sodium bisulfate, or potassium bisulfate. Operating temperatures could be held to the range 80/sup 0/ to 180/sup 0/. One particular catalyst whose preparation was described was formed by condensing phenol, a cresol-sulfonic acid, and formaldehyde, treating the resulting substance with dilute hydrochloric acid, washing with distilled water, treating with 10% hydrochloric acid, and washing again with distilled water.

  10. Effect of the Amide Bond Diamine Structure on the CO 2 , H 2 S, and CH 4 Transport Properties of a Series of Novel 6FDA-Based Polyamide–Imides for Natural Gas Purification

    KAUST Repository

    Vaughn, J.


    A series of higher permeability polyamide-imides based on 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride with comparable plasticization resistance to Torlon were synthesized and formed into dense film membranes. Polymers possessing 2,4-diamino mesitylene (DAM) were stable up to 56 atm of pure CO 2, which is due to enhanced charge transfer complex formation compared to polymers containing 4,4′- (hexafluoroisopropylidene) dianiline (6FpDA) and 2,3,5,6-tetramethyl-1,4- phenylenediamine (TmPDA). The new polymers containing DAM and TmPDA showed ideal CO 2/CH 4 selectivities of near 50 with CO 2 and H 2S permeabilities over an order of magnitude higher than Torlon. CO 2 and CH 4 sorption in the DAM- and TmPDA-based materials was reduced, whereas H 2S sorption was enhanced relative to membranes containing fluorinated 6FpDA. Consequently, DAM- and TmPDA-based membranes showed increased stability toward high pressure CO 2 but lower plasticization resistance toward pure H 2S. These results highlight the differences between CO 2 and H 2S that challenge the rational design of materials targeting simultaneous separation of both contaminants. © 2012 American Chemical Society.

  11. Comparative reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): impact of ancillary ligand l on activation of carbon-hydrogen bonds including catalytic hydroarylation and hydrovinylation/oligomerization of ethylene. (United States)

    Foley, Nicholas A; Lail, Marty; Lee, John P; Gunnoe, T Brent; Cundari, Thomas R; Petersen, Jeffrey L


    Complexes of the type TpRu(L)(NCMe)R [L = CO or PMe3; R = Ph or Me; Tp = hydridotris(pyrazolyl)borate] initiate C-H activation of benzene. Kinetic studies, isotopic labeling, and other experimental evidence suggest that the mechanism of benzene C-H activation involves reversible dissociation of acetonitrile, reversible benzene coordination, and rate-determining C-H activation of coordinated benzene. TpRu(PMe3)(NCMe)Ph initiates C-D activation of C6D6 at rates that are approximately 2-3 times more rapid than that for TpRu(CO)(NCMe)Ph (depending on substrate concentration); however, the catalytic hydrophenylation of ethylene using TpRu(PMe3)(NCMe)Ph is substantially less efficient than catalysis with TpRu(CO)(NCMe)Ph. For TpRu(PMe3)(NCMe)Ph, C-H activation of ethylene, to ultimately produce TpRu(PMe3)(eta3-C4H7), is found to kinetically compete with catalytic ethylene hydrophenylation. In THF solutions containing ethylene, TpRu(PMe3)(NCMe)Ph and TpRu(CO)(NCMe)Ph separately convert to TpRu(L)(eta3-C4H7) (L = PMe3 or CO, respectively) via initial Ru-mediated ethylene C-H activation. Heating mesitylene solutions of TpRu(L)(eta3-C4H7) under ethylene pressure results in the catalytic production of butenes (i.e., ethylene hydrovinylation) and hexenes.

  12. Novel eclipsed 2D cadmium(II) coordination polymers with open-channel structure constructed from terephthalate and 3-(2-pyridyl)pyrazole: crystal structures, emission properties, and inclusion of guest molecules. (United States)

    Zou, Ru-Qiang; Bu, Xian-He; Zhang, Ruo-Hua


    Five new eclipsed two-dimensional (2D) coordination polymers, [[Cd(2)(TPT)(2)L(2)](GM(1))(3/2)(H(2)O)](infinity) (1) (TPT = terephthalate, L = 3-(2-pyridyl)pyrazole, GM(1) = terephthalic acid), [[Cd(TPT)L](GM(2))(H(2)O)(2)]( infinity) (2) (GM(2) = L = 3-(2-pyridyl)pyrazole), [[Cd(TPT)L](GM(3))(1/2)(H(2)O)](infinity) (3) (GM(3) = mesitylene), [[Cd(4)(TPT)(4)L(4)](GM(4))(7/2)](infinity) (4) (GM(4) = tetramethylbenzene), and [[Cd(TPT)L](GM(5))(1/2)](infinity) (5) (GM(5) = naphthalene), have been synthesized and characterized by X-ray diffraction. All the five complexes take the similar eclipsed 2D open-channel framework with different guest molecules included in the cavities of their channels. TGA analysis indicates that the eclipsed open-channel frameworks are thermally stable up to 300 degrees C. The porous property of the 2D framework of 5 was also investigated by the XRPD technique, which indicated that the guest molecules included in the open-channel frameworks are removable and the framework is maintained after the removal of the guest molecules. Moreover, complexes 1-5 also display strong blue emission in the solid state.

  13. Air and biological monitoring of solvent exposure during graffiti removal. (United States)

    Anundi, H; Langworth, S; Johanson, G; Lind, M L; Akesson, B; Friis, L; Itkes, N; Söderman, E; Jönsson, B A; Edling, C


    The principal aim of the study was to estimate the level of exposure to organic solvents of graffiti removers, and to identify the chemicals used in different cleaning agents. A secondary objective was to inform about the toxicity of various products and to optimise working procedures. Exposure to organic solvents was determined by active air sampling and biological monitoring among 38 graffiti removers during an 8-h work shift in the Stockholm underground system. The air samples and biological samples were analysed by gas chromatography. Exposure to organic solvents was also assessed by a questionnaire and interviews. Solvents identified were N-methylpyrrolidone (NMP), dipropylene glycol monomethyl ether (DPGME), propylene glycol monomethyl ether (PGME), diethylene glycol monoethyl ether (DEGEE), toluene, xylene, pseudocumene, hemimellitine, mesitylene, ethylbenzene, limonene, nonane, decane, undecane, hexandecane and gamma-butyrolactone. The 8-h average exposures [time-weighted average (TWA)] were below 20% of the Swedish permissible exposure limit value (PEL) for all solvents identified. In poorly ventilated spaces, e.g. in elevators etc., the short-term exposures exceeded occasionally the Swedish short-term exposure limit values (STEL). The blood and urine concentrations of NMP and its metabolites were low. Glycol ethers and their metabolites (2-methoxypropionic acid (MPA), ethoxy acetic acid (EAA), butoxy acetic acid (BAA), and 2-(2-methoxyethoxy) acetic acid (MEAA)) were found in low concentrations in urine. There were significant correlation between the concentrations of NMP in air and levels of NMP and its metabolites in blood and urine. The use of personal protective equipment, i.e. gloves and respirators, was generally high. Many different cleaning agents were used. The average exposure to solvents was low, but some working tasks included relatively high short-term exposure. To prevent adverse health effects, it is important to inform workers about the

  14. Synthesis and structures of doubly-bridged dicyclopentadienyl dinuclear rhenium complexes, and their photochemical reactions with aromatic halides in benzene. (United States)

    Zhu, Bolin; Huang, Xinwei; Hao, Xiaoting


    Reaction of the doubly-bridged biscyclopentadienes (C5H4(EMe2))(C5H4(SiMe2)) (E = Si(1a), or C(1b)) with Re2(CO)10 in refluxing mesitylene gave the corresponding dirhenium carbonyl complexes [(η(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)3]2 (trans-2a,b and cis-2a,b), and the desilylated products [(η(5)-C5H4)2(EMe2)][Re(CO)3]2 (3a,b). Photolysis of trans-2a,b with a series of aryl halides in benzene results in the formation of biphenyl, together with the corresponding rhenium dihalide complexes trans-[(η(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)3][Re(CO)2X2] (X = Cl, Br, I) (4, 6, 8, or 10) and trans-[(η(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)2X2]2 (5, 7, or 9). Additional experiments indicate that one phenyl ring in the resulting biphenyl comes from aryl halides and the other phenyl ring comes from the solvent benzene. However, photolysis of trans-2a with benzyl chloride and n-hexyl chloride in benzene afforded the corresponding bibenzyl and n-dodecane, as well as the rhenium dichlorides 8 and 9. In addition, complex trans-2a can also activate the C-F bond on C6F6 to form the pentafluorophenyl rhenium fluoride trans-[(η(5)-C5H3)2(SiMe2)2][Re(CO)3][Re(CO)2(C6F5)F] (11). Molecular structures of cis-2a, cis-2b, trans-2b, 3b, 6, 7, 8, 11, and 12 determined by X-ray diffraction are also presented.

  15. Core-Shell Diamond as a Support for Solid-Phase Extraction and High-Performance Liquid Chromatography

    International Nuclear Information System (INIS)

    Saini, Gaurav; Jensen, David S.; Wiest, Landon A.; Vail, Michael A.; Dadson, Andrew; Lee, Milton L.; Shutthanandan, V.; Linford, Matthew R.


    We report the formation of core-shell diamond particles for solid phase extraction (SPE) and high performance liquid chromatography (HPLC) made by layer-by-layer (LbL) deposition. Their synthesis begins with the amine functionalization of microdiamond by its immersion in an aqueous solution of a primary amine-containing polymer (polyallylamine (PAAm)). The amine-terminated microdiamond is then immersed in an aqueous suspension of nanodiamond, which leads to adsorption of the nanodiamond. Alternating (self-limiting) immersions in the solutions of the amine-containing polymer and the suspension of nanodiamond are continued until the desired number of nanodiamond layers is formed around the microdiamond. Finally, the core-shell particles are cross-linked with 1,2,5,6-diepoxycyclooctane or reacted with 1,2-epoxyoctadecane. Layer-by-layer deposition of PAAm and nanodiamond is also studied on planar Si/SiO2 surfaces, which were characterized by SEM, Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). Core-shell particles are characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), environmental scanning electron microscopy (ESEM), and Brunauer Emmett Teller (BET) surface area and pore size measurements. Larger (ca. 50 ?m) core-shell diamond particles have much higher surface areas, and analyte loading capacities in SPE than nonporous solid diamond particles. Smaller (ca. 3 ?m), normal and reversed phase, core-shell diamond particles have been used for HPLC, with 36,300 plates per meter for mesitylene in a separation of benzene and alkyl benzenes on a C18 adsorbent, and 54,800 plates per meter for diazinon in a similar separation of two pesticides.

  16. Chemical and electrochemical oxidation of small organic molecules (United States)

    Smart, Marshall C.

    Direct oxidation fuel cells using proton-exchange membrane electrolytes have long been recognized as being an attractive mode of power generation. The current work addresses the electro-oxidation characteristics of a number of potential fuels on Pt-based electrodes which can be used in direct oxidation fuel cells, including hydrocarbons and oxygenated molecules, such as alcohols, formates, ethers, and acetals. Promising alternative fuels which were identified, such as trimethoxymethane and dimethoxymethane, were then investigated in liquid-feed PEM-based fuel cells. In addition to investigating the nature of the anodic electro-oxidation of organic fuels, effort was also devoted to developing novel polymer electrolyte membranes which have low permeability to organic molecules, such as methanol. This research was initiated with the expectation of reducing the extent of fuel crossover from the anode to the cathode in the liquid-feed design fuel cell which results in lower fuel efficiency and performance. Other work involving efforts to improve the performance of direct oxidation fuel cell includes research focused upon improving the kinetics of oxygen reduction. There is continued interest in the identification of new, safe, non-toxic, and inexpensive reagents which can be used in the oxidation of organic compounds. Urea-hydrogen peroxide (UHP), a hydrogen bonded adduct, has been shown to serve as a valuable source of hydrogen peroxide in a range of reactions. UHP has been shown to be ideal for the monohydroxylation of aromatics, including toluene, ethylbenzene, p-xylene, m-xylene, and mesitylene, as well as benzene, in the presence of trifluoromethanesulfonic acid. It was also found that aniline was converted to a mixture containing primarily azobenzene, azoxybenzene and nitrobenzene when reacted with UHP in glacial acetic acid. A number of aniline derivatives have been investigated and it was observed that the corresponding azoxybenzene derivatives could be

  17. Ruthenium(0) nanoclusters stabilized by a Nanozeolite framework: isolable, reusable, and green catalyst for the hydrogenation of neat aromatics under mild conditions with the unprecedented catalytic activity and lifetime. (United States)

    Zahmakiran, Mehmet; Tonbul, Yalçin; Ozkar, Saim


    The hydrogenation of aromatics is a ubiquitous chemical transformation used in both the petrochemical and specialty industry and is important for the generation of clean diesel fuels. Reported herein is the discovery of a superior heterogeneous catalyst, superior in terms of catalytic activity, selectivity, and lifetime in the hydrogenation of aromatics in the solvent-free system under mild conditions (at 25 degrees C and 42 +/- 1 psig initial H(2) pressure). Ruthenium(0) nanoclusters stabilized by a nanozeolite framework as a new catalytic material is reproducibly prepared from the borohydride reduction of a colloidal solution of ruthenium(III)-exchanged nanozeolites at room temperature and characterized by using ICP-OES, XRD, XPS, DLS, TEM, HRTEM, TEM/EDX, mid-IR, far-IR, and Raman spectroscopy. The resultant ruthenium(0) nanoclusters hydrogenate neat benzene to cyclohexane with 100% conversion under mild conditions (at 25 degrees C and 42 +/- 1 psig initial H(2) pressure) with record catalytic activity (initial TOF = 5430 h(-1)) and lifetime (TTO = 177 200). They provide exceptional catalytic activity not only in the hydrogenation of neat benzene but also in the solvent-free hydrogenation of methyl substituted aromatics such as toluene, o-xylene, and mesitylene under otherwise identical conditions. Moreover, they are an isolable, bottleable, and reusable catalyst in the hydrogenation of neat aromatics. When the isolated ruthenium(0) nanoclusters are reused, they retain 92% of their initial catalytic activity even for the third run in the hydrogenation of neat benzene under the same conditions as those of the first run. The work reported here also includes (i) far-infrared spectroscopic investigation of nanozeolite, ruthenium(III)-exchanged-nanozeolite, and ruthenium(0) nanoclusters stabilized by a nanozeolite framework, indicating that the host framework remains intact after the formation of a nanozeolite framework stabilized ruthenium(0) nanoclusters; (ii) the

  18. Copper(I) and silver(I) bis(trifluoromethanesulfonyl)imide and their interaction with an arene, diverse olefins, and an NTf2(-)-based ionic liquid. (United States)

    Stricker, Marion; Oelkers, Benjamin; Rosenau, Carl Philipp; Sundermeyer, Jörg


    The chemistry of coinage metal bis(triflyl)imides of technological interest, CuNTf(2) and AgNTf(2), their synthesis and complexes with excess of comparatively weakly coordinating NTf(2)(-) as well as with ether, olefins, and the arene mesitylene are described. The existence of the solvent-free pure phase [CuNTf(2)](∞) has not been evidenced so far. Contrary to the literature, in which the preparation of [CuNTf(2)](∞) is supposed to be carried out by reacting mesityl copper, [Cu(Mes)](5), and HNTf(2), we found that in fact this reaction leads reproducibly to the interesting copper diarene sandwich complex [Cu(η(3)-MesH)(2)][Cu(NTf(2))(2)] (1) (MesH = 1,3,5-trimethylbenzene). The unexpectedly stable molecular etherate [Cu(Et(2)O)(NTf(2))] (2) turned out to be the best precursor for CuNTf(2) having only an inert and easily exchangeable solvent ligand. The coordination mode of NTf(2)(-) in 1 and 2 as well as in the hitherto unknown crystalline phase of [AgNTf(2)](∞) (3) is described. The complex formation, which takes place when dissolving 2 or 3 in the room temperature ionic liquid (RTIL) [emim]NTf(2) ([emim](+) = 1-ethyl-3-methylimidazolium), has been studied. Furthermore, the reaction of 1-3 towards the diolefins 1,5-cyclooctadiene (COD), 2,5-norbornadiene (NBD) and isoprene (2-methylbuta-1,3-diene) and towards ethylene has been investigated. The products 4-13 of these conversions have been isolated and fully characterized by NMR- and IR spectroscopies, mass spectrometry, and elemental- and XRD analyses. The potential of [Cu(η(3)-MesH)(2)][Cu(NTf(2))(2)] (1), [Cu(Et(2)O)(NTf(2))] (2) and [AgNTf(2)](∞) (3) as well as of [emim][M(NTf(2))(2)] (M = Cu 4, Ag 5) as chemisorbers for ethylene was studied by NMR spectroscopy. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Selective Complexation of Cyanide and Fluoride Ions with Ammonium Boranes: A Theoretical Study on Sensing Mechanism Involving Intramolecular Charge Transfer and Configurational Changes. (United States)

    Bhat, Haamid R; Jha, Prakash C


    The anion binding selectivity and the recognition mechanism of two isomeric boranes, namely, 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 1, where "Mes" represents mesitylene and "Me" represents methyl) and 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 2) has been investigated using density functional theory (DFT) and time dependent-density functional theory (TD-DFT) methods. Natural population analysis indicates that the central boron atoms in 1 and 2 are the most active centers for nucleophilic addition of anions. The negative magnitude of free energy changes (ΔG) reveals that out of CN - , F - , Cl - , Br - , NO 3 - , and HSO 4 - only the binding of CN - and F - with 1 and 2 is thermodynamically feasible and spontaneous. In addition, the calculated binding energies reveal that the CN - is showing lesser binding affinity than F - both with 1 and 2, while other ions, viz. NO 3 - , HSO 4 - , Br - , and Cl - , either do not bind at all or show very insignificant binding energy. The first excited states (S 1 ) of 1 and 2 are shown to be the local excited states with π → σ* transition by frontier molecular orbital analysis, whereas fourth excited states (S 4 ) of 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline cyanide ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] CN, 1CN, the cyano form of 1) and 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 1F, the fluoro form of 1) and fifth excited state (S 5 ) of 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 2F, the fluoro form of 2) are charge separation states that are found to be responsible for the intramolecular charge transfer (ICT) process. The synergistic effect of ICT and partial configuration changes induce fluorescence quenching in 1CN, 1F, and 2F after a significant internal conversion (IC) from S 4 and

  20. The liquid phase hydrogenation of nitrobenzene over supported copper catalysts

    International Nuclear Information System (INIS)

    Anderson, David Scott


    via an alkylation reaction which occurred between the hydrogenation product, aniline, and the solvent itself, hexan-1-ol. A preliminary investigation of this side reaction was conducted, revealing the sequential formation of N-hexylenebenzenamine and N-hexylaniline. It is believed that the alkylation reaction occurs on the silica support, whilst the hydrogenation step occurs on the metal crystallites; in the presence of nitrobenzene the hydrogenation of the nitro group is favoured over that of N-hexylenebenzenamine. During the assessment of t-butyl benzene as a solvent it was found that its history bore marked effect on catalyst activity. It was established that the presence of sulphur within different batches of t-butyl benzene was responsible for an observed enhancement of catalyst performance. The overall concentration of sulphur within the solvent samples was determined, and it was found that five different sulphur species were present. A conclusive assignment of their identities, however, did not prove possible. Dodecane, ethyl benzene and mesitylene were also found to be unsuitable as solvents for this reaction. n-Butyl benzene was ultimately adopted as the reaction medium. Comprehensive testing with n-butyl benzene did reveal the existence of two minor reactions involving this solvent, but these were not found to affect the major reaction. The optimised technique, 'benchmarked' against a platinum/silica catalyst, allowed the behaviour of the different copper catalysts to be evaluated with reproducible results. The Cu(N)/Cab catalyst had the greatest activity and the highest metal surface area, which was attributed to the combination of the copper nitrate salt and powdered Cab-O-Sil support used in its preparation. No by-products were observed from the reaction of nitrobenzene; all of the copper catalysts showed complete selectivity to aniline. Following complete consumption of the nitrobenzene, however, it was apparent that the concentration of aniline in