Search results for "Bond"
showing 10 items of 3527 documents
Manganese(III)-mediated oxidative carbon-carbon bond cleavage of the 1,10-phenanthroline-5,6-dione ligand
1999
[EN] A new manganese(III)-1,10-phenanthroline-5,6-dione (phendione) complex possessing a putative Mn-2(mu-O) (mu-O2CMe)(2) core has been found to undergo a Ligand-based oxidative cleavage of the C(5)-C(6) bond in weak acid aqueous MeOH under aerobic conditions at room temperature to yield 2,2'-bipyridyl-3,3'-dicarboxylate with co-reduction to the corresponding Mn-II-phendione species.
Antimicrobial activity of methylene blue and toluidine blue O covalently bound to a modified silicone polymer surface
2009
Methylene Blue or Toluidine Blue O were covalently bound to an activated silicone polymer by means of an amide condensation reaction. UV-visible absorption spectra confirmed that the dye was surface bound. The new polymers with covalently attached dye display significant bactericidal activity against Escherichia coli and Staphylococcus epidermidis with a 99.999% reduction in viable bacteria after four minutes exposure to a low power laser.
Separation of lanthanides and actinides using magnetic silica particles bearing covalently attached tetra-CMPO-calix[4]arenes
2004
Calix[4]arene tetraethers in the cone conformation bearing four –NH–CO–CH2–P(O)Ph2 (= CMPO) residues on their wide rim and one, two or four ω-amino alkyl residues of various lengths at the narrow rim were synthesized. Reaction with dichlorotriazinyl (DCT) functionalized magnetic particles led to complete coverage of the available surface by covalently linked CMPO-calix[4]arenes in all cases. Magnetically assisted removal of Eu(III) and Am(III) from acidic solutions was distinctly more efficient with these particles in comparison to analogous particles bearing the same amount of analogous single-chain CMPO-functions. The best result, an increase of the extraction efficiency by a factor of 14…
Enhancing reactivity of carbonyl compounds via hydrogen-bond formation. A DFT study of the hetero-Diels-Alder reaction between butadiene derivative a…
2003
To examine how hydrogen-bond (HB) formation involving chloroform solvent molecules influences the chemical reactivity of ketones, the hetero-Diels-Alder reaction of N,N-dimethyl-1-amino-3-methoxy-1,3-butadiene and acetone has been studied by using density functional theory (DFT) at the B3LYP/6-31G level. The effects of the chloroform on the activation energies have been modeled by means of discrete-continuum models. In the gas phase, the formation of specific HB between acetone and one and two chloroform molecules decreases the activation barriers from 19.3 to 13.6 and 8.5 kcal/mol, respectively. Inclusion of solvent effects by means of combined discrete and polarizable continuum models yie…
Theoretical study of the OH addition to the endocyclic and exocyclic double bonds of the d-limonene
2005
Abstract The initial step of the d-limonene + OH gas-phase reaction mechanism was investigated by means of ab initio calculations. We have considered eight different possibilities for the OH addition, corresponding to the two C–C double bonds, the two C atoms of each double bond, and the syn or anti orientation, with respect to the isopropenyl group (endocyclic attack) or the ring cycle (exocyclic attack). Activation energies calculated at the QCISD(T)/6-31G(d)//UMP2/6-31G(d) level, show that there are preferred orientations for the OH addition under atmospheric conditions of temperature and pressure.
Studien zum Vorgang der Wasserstoffübertragung, 68. Die reduktive Überführung aromatischer Säurechloride in Diarylacetylene mit Lithiumamalgam in ein…
1983
Endioldiester A, die durch “Acylierende reduktive Dimerisierung” mit Lithiumamalgam (Li/Hg) nach (1) zuganglich sind, werden mit zwei weiteren Reduktionsaquivalenten nach (2) durch “Reduktive Eliminierung” in Acetylenderivate ubergefuhrt. Hierbei hat sich praparativ das Eintopfverfahren in der Zweistufenarbeitsweise bewahrt. Auch mit Natriumamalgam (Na/Hg) und Kaliumamalgam (K/Hg) gelingt die reduktive Eliminierung nach (2) sowohl von cis- als auch von trans-Endiol-diestern zu Acetylenverbindungen mit guten Ausbeuten. Voraussetzung fur den erfolgreichen Ablauf der Reaktion (2) ist die direkte Verknupfung von zwei Aromaten mit der C C-Doppelbindung in den Endiol-diestern. Endiol-diester mit …
An ELF analysis of the C–C bond formation step in the N-heterocyclic carbene-catalyzed hydroacylation of unactivated C–C double bonds
2012
The changes in electron-density along the C–C bond-formation step in the N-heterocyclic carbene-catalyzed hydroacylation of unactivated double bonds has been studied by an electron localization function (ELF) analysis at the B3LYP/6-31G** level in order to characterize the reaction mechanism. Analysis of DFT reactivity indices and the natural bond orbital and ELF analysis at the most relevant points of the intrinsic reaction coordinate indicate that the reaction path takes place through a two-stage one-step mechanism with non-polar character. In the first stage a hydrogen atom is transferred from the hydroxyl group of Breslow intermediate 12 to the terminal olefinic carbon atom, to yield a …
The skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite
2001
The complete mechanism for the skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite was investigated theoretically by means of DFT calculations, and the influence of the local geometry of the active site and of electrostatic effects on the geometries of the species involved and on activation and reaction energies were analyzed. It was found that whereas the geometry and stability of alkoxide intermediates are strongly influenced by the local geometry of the active site, the ionic transition states are mainly stabilized by electrostatic effects. Both aspects result in a lowering of the activation energies of the elementary steps that form the mechanism and therefore in enhanced r…
Formation of covalent di-tyrosine dimers in recombinant α-synuclein
2015
Parkinson's disease is associated with fibril deposition in the diseased brain. Misfolding events of the intrinsically disordered synaptic protein α-synuclein are suggested to lead to the formation of transient oligomeric and cytotoxic species. The etiology of Parkinson's disease is further associated with mitochondrial dysfunction and formation of reactive oxygen species. Oxidative stress causes chemical modification of native α-synuclein, plausibly further influencing misfolding events. Here, we present evidence for the spontaneous formation of covalent di-tyrosine α-synuclein dimers in standard recombinant protein preparations, induced without extrinsic oxidative or nitrative agents. The…
N-[Glycyl-(Z)-α,β-dehydrophenylalanylglycyl-(Z)-α,β-dehydrophenylalanyl]glycine trifluoroacetate methanol solvate
2007
The molecular conformation of the title dehydropeptide, H+-Gly1–ΔZPhe2–Gly3–ΔZPhe4–Gly5-OH·CF3COO−·CH3OH or C24H26N5O6+·CF3COO−·CH3OH, is characterized by the presence of two intramolecular N—H⋯O hydrogen bonds that stabilize two type III β-turns, at the ΔZPhe2 (ΔZPhe is the Z isomer of the α,β-dehydrophenylalanine residue) and Gly3, and Gly3 and ΔZPhe4 residues. As a result, the pentapeptide adopts a right-handed 310-helical conformation. All peptide units are linked trans to each other.