Search results for " Isomerization"

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…

Conformational preferences and synthesis of isomers Z and E of 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…

Studio teorico della reazione di idroisomerizzazione del cis-butene su cluster di palladio supportato

2008

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 …

Selective isomerization of a trans -butanediacetal derivative of tartaric acid with differentiating substituents at C-2 and C-3

2017

Abstract A trans-disubstituted butanediacetal derivative with two different substituents (ester and thioester) – methyl (2R,3R,5R,6R)-3-ethylsulfanylcarbonyl-5,6-dimethoxy-5,6-dimethyl-1,4-dioxane-2-carboxylate, was selectively converted to the cis derivative – methyl (2S,3R,5R,6R)-3-ethylsulfanylcarbonyl-5,6-dimethoxy-5,6-dimethyl-1,4-dioxane-2-carboxylate in high yield on a multigram scale. The product of this reaction offers the possibility for selective modification of one of the substituents, which was demonstrated by Fukuyama reduction of the thioester group.

Temperature and light sensitive copolymers containing azobenzene moieties prepared via a polymer analogous reaction

2009

Abstract Four different series of polyacrylamides containing different amounts of azobenzene moieties have been synthesized via a polymer analogous reaction of poly(pentafluorophenylacrylate) (PPFPA). All copolymers were designed to exhibit a lower critical solution temperature (LCST) in aqueous solution, which was dependent on (i) the amount of incorporated chromophoric azobenzene groups and (ii) the isomerization state of the respective azobenzene group. Higher LCST values were measured for UV-irradiated solutions of the copolymers in comparison to the non-irradiated copolymer solutions. A maximum difference in the LCST of up to 7 °C was found for the copolymer poly(N,N-dimethylacrylamide…

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.