Search results for "Cis trans isomerization"
showing 10 items of 16 documents
Chiral Polyisocyanates from an Azomonomer with a Very High Chiral Induction
2001
The synthesis of new chiral polyisocyanates is described. For this purpose a new chiral azobenzene containing monomer with the chiral center in α-position to the isocyanate group was synthesized. The anionic copolymerization was carried out in THF as solvent with potassium cyanide that was complexed by 18-crown-6 as initiator. This allowed a better control of the reaction and thereby the synthesis of polyisocyanates with a fairly low polydispersity. The copolymers show an extremely high transfer of chirality from the chiral side groups to the helical backbone in dilute solution. Copolymers with only 1.6 mol % of chiral side groups show nearly the full optical rotation and exist predominantl…
Interplay of Chiral Side Chains and Helical Main Chains in Polyisocyanates
1996
Here we describe the synthesis of seven new copolymer series prepared by copolymerization of hexyl isocyanate with seven new chiral azo chromophores with an isocyano functionality. The resulting copolyisocyanates (Nylon 1) possess a helical polymer conformation. In the cases in which the chiral group and polymer chain are linked to the same phenyl ring (copolymer series VI-IX) a transfer of chirality to the polymer chain is possible. I.e. one helical twist sense is preferred in this case. By variation of the chiral center, polymers with preferable right- or left-handed helical conformation are accessible. The photochemical isomerization of the azo chromophore (trans → cis) is possible in hi…
The reduction mechanism of the CO group.
2001
A detailed study of the electrochemical reduction of benzil in aqueous medium between H0=−5 and pH 11 is presented. A global 2e−, 3H+ or 2e−, 2H+ surface reaction leads to cis and trans endiols. Analysis, using the theory of the square schemes with protonations at equilibrium, shows that in all the pH range the reaction is controlled by the second electron uptake, the paths being successively H+, e− and e−, H+. The electrochemical reaction is followed by surface isomerizations whose rate constants vary from 7 to 200 s−1 for the trans/cis and from 1 to 2000 s−1 for the cis/trans transformations.
Heterocyclic photorearrangements. Photoinduced rearrangement of 3-styryl-1,2,4-oxadiazoles
1990
The photochemical behaviour of 3-styryl-5-phenyl-(5-methyl)-1,2,4-oxadiazoles in methanol at 254 nm has been investigated. A photoinduced rearrangement to the quinoline system has been pointed out and explained as proceeding through an initial photolysis of the ring ON bond, followed by a six membered ring closure reaction involving the styryl moiety.
cis- and trans-1,2-diphenylaziridines: induction of xenobiotic-metabolizing enzymes in rat liver and mutagenicity in Salmonella typhimurium.
1986
trans-Stilbene imine (trans-1,2-diphenylaziridine) is the nitrogen analog of trans-stilbene oxide, a potent inducer of several microsomal and cytosolic xenobiotic-metabolizing enzymes. Although the acute toxicity of cis- and trans-stilbene imines prevents their application at the usual dose for trans-stilbene oxide (400 mg/kg/day), it is apparent that the imines nevertheless potently induce several xenobiotic-metabolizing enzymes in rat liver. The IP administration of trans-stilbene imine resulted in statistically significant increases in the activities of aminopyrine N-demethylase, microsomal epoxide hydrolase, glutathione transferase (toward 1-chloro-2,4-dinitrobenzene, 1,2-dichloro-4-nit…
Thecis-transisomerization ofN-methyl-α,β-dehydroamino acids
2012
Dehydroamino acids with the methylated N-terminal peptide group occur in natural small cyclic peptides. The structural analysis was used to investigate the cis-trans isomerization of the N-terminal tertiary amide group of diamides: Ac-(Z)-Δ(Me)Abu-NHMe (1), Ac-(Z)-Δ(Me)Phe-NHMe (2), Ac-(E)-Δ(Me)Phe-NHMe (3), Ac-Δ(Me)Ala-NHMe (4), and Ac-(Me)Ala-NHMe (5). The compounds were analyzed in the solid state by an X-ray crystallography (1-3), and in the solution by FTIR (MeCN and CHCl(3) ) and NMR (DMSO-d6 and CDCl(3) ) methods (1-5). In the solid state, the studied compounds adopt the cis configuration of N-terminal amide. In solution, this configuration also prevails for the dehydroamino acids 1-…
Gold nanoparticle catalysis of the cis-trans isomerization of azobenzene
2013
Ablated, “pseudo-naked” gold nanoparticles (AuNPs) catalyze the cis–trans isomerization of substituted azobenzenes. para-Substitution was found to affect the rate of isomerization, suggesting the participation of AuNP-mediated electron transfer in the isomerization mechanism. Fil: Hallet Tapley, Geniece. University of Ottawa; Canadá Fil: D'Alfonso, Claudio. University of Ottawa; Canadá. Universita Di Roma; Italia Fil: Pacioni, Natalia Lorena. University of Ottawa; Canadá Fil: McTiernan, Cristopher D.. University of Ottawa; Canadá Fil: Gonzalez Bejar, Maria. University of Ottawa; Canadá. Universidad de Valencia; España Fil: Lanzalunga, Osvaldo. Universita Di Roma; Italia Fil: Alarcon, Emilio…
Conformational preferences and synthesis of isomersZandEof oxazole-dehydrophenylalanine
2016
Dehydrophenylalanine, ΔPhe, is the most commonly studied α,β-dehydroamino acid. In nature, further modifications of the α,β-dehydroamino acids were found, for example, replacement of the C-terminal amide group by oxazole ring. The conformational properties of oxazole-dehydrophenylalanine residue (ΔPhe-Ozl), both isomers Z and E, were investigated. To determine all possible conformations, theoretical calculations were performed using Ac-(Z/E)-ΔPhe-Ozl(4-Me) model compounds at M06-2X/6-31++G(d,p) level of theory. Ac-(Z/E)-ΔPhe-Ozl-4-COOEt compounds were synthesized and the conformational preferences of each isomer, Z and E, were investigated using FTIR and NMR-NOE in solutions of increasing p…
Manipulation of the ferroelectricity in LC polymers via photomechanical isomerization of azobenzene moieties
1996
We report the synthesis and characterization of a new ferroelectric liquid crystalline side chain copolymer containing photoisomerizable chromophores and non-photoisomerizable mesogenic units. On illumination with UV-light a suppression of the polar order is obtained as indicated by a substantial drop of the spontaneous polarization (Ps) compared to the dark state. We interpret this as the phase order being disrupted by the cis-isomer of the chromophore. After illumination with VIS-light only the major part of Ps is restored. The photochemical cis-trans back-isomerization (restoration of the phase) leads to a different stationary state than the dark state of the material. The thermal reisom…
Switch in Relative Stability between cis and trans 2-Butene on Pt(111) as a Function of Experimental Conditions: A Density Functional Theory Study
2018
International audience; The adsorption of cis and trans 2-butenes on Pt(111) has been studied as a function of hydrogen coverage OH by means of calculations based on density functional theory (DFT) with the inclusion of dispersion forces. All hydrogen coverages have been considered, from 0 to 1.00 monolayer (ML). For each case, the di-sigma and pi adsorption geometries of the olefins have been compared at a surface coverage of theta(C4H8) = 0.11 ML. Calculations of the Gibbs free energies of these systems have identified the most stable 2-butene isomer (cis or trans) as a function of coverage, temperature, and pressure. In particular, focus was placed on two sets of conditions, namely, one …