Search results for "isomerization"
showing 10 items of 281 documents
Binding and isomerization energies for the Cu/CN and Cu(I)CN interactions
1993
Abstract Binding and isomerization energies of the CuCN, CuNC, CuCN+, and CuNC+ systems were investigated by means of a multireference CI perturbatively selected, MRCI-PS approach. The inclusion of the main dynamical correlation effects are evaluated. The binding energies for CuCN and CuNC are 4.37 and 4.03 eV, respectively, and those for CuCN+ and CuNC+ are 0.08 and 1.61 eV. Calculated isomerization energies are 7.86 and 35.98 kcal/mol for CuCN and Cu(I)CN isomerizations, respectively.
Isomerization of 9c11t/10t12c CLA in Triacylglycerols
2010
Published version of an article in the journal: Lipids . The original publication is available at Spingerlink. http://dx.doi.org/10.1007/s11745-010-3452-x Isomers of conjugated linoleic acid from 7t9c through 12t14t can be induced by thermal treatment of triacylglycerol samples of 9c11t or 10t12c fatty acids in glass tubes. The formation of conjugated linoleic acids (CLAs) has been observed during thermal induction of the above-mentioned triacylglycerols at 250, 280 and 320A degrees C. The concentrations of isomers formed in the mixture varied depending on the temperature and duration of the heating experiments. The objective of this study was to find a suitable thermal induction temperatur…
The influence of branching isomerization on the product distribution obtained during cracking of n-heptane on acidic zeolites
1985
Abstract The initial selectivities for the primary products occurring during the cracking of n-heptane on a rare-earth (RE)-HY ultrastable zeolite up to 470°C have been calculated. The activation energies for the cracking of n-heptane and its branched isomers in the fraction C4 + C3 have been obtained by molecular orbital calculations, and these values and the predicted product distribution have been compared with those obtained experimentally. It is concluded that the cracking of n-heptane on large-pore zeolites may take place by different parallel routes involving protolytic and β-cracking of n-heptane and β-cracking of the readily formed branched carbenium ions. The relative importance o…
Pumice-supported Cu-Pd catalysts: Influence of copper on the activity and selectivity of palladium in the hydrogenation of phenylacetylene and but-1-…
1999
Abstract Pumice-supported copper–palladium catalysts prepared from organometallic precursor have been tested in the hydrogenation of phenylacetylene and in the hydrogenation/isomerization of the but-1-ene. The structure and catalytic behaviour of the bimetallic catalysts depended on the different temperatures of reduction. The presence of CuO or Cu metal in an alloyed state with Pd influenced the two reactions. The system containing CuO is the most active and selective towards the formation of the monoalkene in the hydrogenation of the highly unsaturated hydrocarbon. The system containing Cu partially alloyed with Pd is more active and selective towards the isomerization of the but-1-ene. T…
Stopped-Flow and DFT Studies of Proton Transfer and Isomerization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine and Its Related Base 2-(5-Amin…
2001
International audience; A complete kinetic study of pH-dependent isomerization of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (HL) and 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L‘-) in the pH range from −0.5 to +13 in aqueous solution, which spans over 7 orders of magnitude for the pseudo-first-order rates (log k from −4.8 to +2.5), has revealed for the first time the existence of the corresponding conjugate species L- and HL‘. The study has allowed the determination of the acid dissociation constants of HL (pKa) and HL‘ (pKa‘), as well as all of the individual forward and reverse isomerization rates of the acidic (HL/HL‘) and basic (L-/L‘-) forms. Although L…
Butene Isomerization and Double-Bond Migration on the H-ZSM-5 Outer Surface: A Density Functional Theory Study
2011
Isomerization of trans-but-2-ene to cis-but-2-ene and double bond migration of trans-but-2-ene to but-1-ene have been investigated by means of density functional theory calculations on a suitable model of H-ZSM-5 surface. The study has been afforded on outer surface sites by considering the hydroxyl group of either a SiO2(OH)2 or a AlO2H(OH)2 moiety. On these outer surface sites, one alkoxide species occurs as a stable intermediate both along the isomerization and double bond migration pathways. The latter process could also occur via a single-step mechanism, which involves a six-center transition state. The energy barriers of the outer surface processes above do not take any advantage by t…
Photoswitchable Smectic Liquid-Crystalline Elastomers
2005
We succeeded in the synthesis of azo side chain containing polysioxanes with broad smectic C* and A phases. In these polymers the phase transition temperatures can be shifted reversibly by up to 17°C by irradiation with UV (cis) or VIS (trans) light. Thin films of these polymers in the smectie phase (both on substrates and as free-standing films) orient perfectly in a homeotropic manner. As a consequence, the aze chromophores do no longer absorb during a perpendicular illumination with light (dichroism). It is thus possible to crosslink these films photochemically to prepare photoswitchable smectic LC elastomers.
One is Enough: Influencing Polymer Properties with a Single Chromophoric Unit
2011
1) Institute for Technical and Macromolecular Chemistry, University of Hamburg, Bundesstrasse 45, D-‐20146 Hamburg, Germany 2) WCU program of C2E2, School of Chemical and Biological, Engineering, College of Engineering, Seoul National University, Seoul, Korea Designing a polymer usually involves the incorporation of multiple functional units into a polymer chain, which mutually determine the polymer properties. By combining various functional units, a myriad of polymer properties can be fine-‐ tuned. Classical polymer chemistry teaches us that a single functional group -‐-‐ in particular the end-‐group of a polymer chain -‐-‐ does not contribute to the polymer properties, as is indee…
Direct Surface Relief Formation in Polymer Films
2013
Due to active development of nanoelectronics, the studies of methods of nanorelief surface formation in different materials, in particular polymers are very important. Organic polymer films in consequence of their dielectric and optical properties have been used as basis of these devices. In this paper, the possibility of UV optical record and electron beam lithography in different type of polymeric films was studied. Mechanisms of molecular structure changes: photoisomerization, destruction, cross-linking and oxidation have been discussed. The results of UV illumination of polyurethanes, polyacrylates, and some block-copolymers were described. The element analysis of polybutadiene block co…
UV optical record and electron beam lithography in polymer films
2012
Possibility of UV optical record and electron beam lithography in different type of organic polymer films was studied. Mechanisms of molecular structure changes: photoisomerization, destruction, cross-linking and oxidation have been discussed. The results of UV illumination of polyurethanes, polyacrilates, and some block-copolymers are described. The element analysis of polyisoprene block copolymer was performed before and after UV illumination, and the changes in transmission spectra of the polymer film were measured. The resolution of electron beam lithography on polymer films was studied. In the polyisoprene block copolymer film the oxidation polymerization was ascertain at UV-illuminati…