Search results for "Cyanide"
showing 10 items of 180 documents
Optical sensing of cyanide using hybrid biomolecular films
2006
The selective sensing of cyanide anions in water has been studied using a hybrid biomaterial composed of a mesoporous TiO2 film of crystalline nanoparticles and the protein hemoglobin. The mesoporous structure of the film prevents protein unfolding and also stabilizes the oxidized form of the prosthetic groups. Low-levels of cyanide anions (<0.2 ppm (0.2 mgr/L)) can be detected by monitoring the changes in the optical properties of the hybrid biomolecular films upon cyanide binding to the heme groups.
Computational Analysis of n→π* Back-Bonding in Metallylene-Isocyanide Complexes R2MCNR′ (M = Si, Ge, Sn; R = tBu, Ph; R′ = Me, tBu, Ph)
2013
A detailed computational investigation of orbital interactions in metal–carbon bonds of metallylene–isocyanide adducts of the type R2MCNR′ (M = Si, Ge, Sn; R, R′ = alkyl, aryl) was performed using density functional theory and different methods based on energy decomposition analysis. Similar analyses have not been carried out before for metal complexes of isocyanides, even though the related carbonyl complexes have been under intense investigations throughout the years. The results of our work reveal that the relative importance of π-type back-bonding interactions in these systems increases in the sequence Sn < Ge ≪ Si, and in contrast to some earlier assumptions, the π-component cannot be …
Synthesis of α-aminonitriles using aliphatic nitriles, α-amino acids, and hexacyanoferrate as universally applicable non-toxic cyanide sources
2018
In cyanation reactions, the cyanide source is often directly added to the reaction mixture, which restricts the choice of conditions. The spatial separation of cyanide release and consumption offers higher flexibility instead. Such a setting was used for the cyanation of iminium ions with a variety of different easy-to-handle HCN sources such as hexacyanoferrate, acetonitrile or α-amino acids. The latter substrates were first converted to their corresponding nitriles through oxidative decarboxylation. While glycine directly furnishes HCN in the oxidation step, the aliphatic nitriles derived from α-substituted amino acids can be further converted into the corresponding cyanohydrins in an oxi…
Synthesis of bi- and tricyclic β-lactam libraries in aqueous medium
2007
Water as a solvent is not only inexpensive and environmentally benign, but may allow good reactivity. The present work focuses on the application of a modified Ugi reaction, i.e. the Ugi four-centre three-component reaction (U-4C-3CR), in aqueous medium to construct β-lactam libraries. All the attempted reactions could be successfully performed in water. The reaction conditions under which the precipitation process was effective were investigated; no further work-up or purification was necessary. In several cases when less water-soluble β-amino acids were used, the precipitated products were isolated easily by simple filtration. In other cases, evaporation of the solvent was appropriate for…
Wirkung der Insektizide Allethrin, Lindan und Jacutin-Fogetten-Sublimat auf den photosynthetischen Elektronentransport
1977
Summary During our studies of Hill-reactions of isolated chloroplasts we observed an inhibition of electron transport after an application of the smoke of «Jacutine-Fogetten» in the plant growth chamber. Therefore we tested the influence of the insecticides Lindane (Gammexan), the sublimate formed by the fumigation of «Jacutin Fogetten», and of Allethrin on the photosynthetic electron transport reactions of PS II and PS I. 39 μ M Lindane inhibits the basal, coupled and uncoupled electron transport to ferricyanide of broken chloroplasts isolated from leaves of Pisum sativum up to 35%. A higher inhibitory effect with higher concentrations is limited by the low water solubility of Lindane. On …
Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes
2001
Abstract Three novel compounds formed by the photochromic nitroprusside anion, [Fe(CN)5NO]2−, and the paramagnetic complexes [Cu(C19H18N6)]2+, [Ni(C6H14N2)2]2+ and [Ni(cyclam)]2+ are reported. The structure of [Cu(C19H18N6)][Fe(CN)5NO] (1) comprises binuclear complexes with a [Fe(CN)5NO]2− anion linked to a [Cu(C19H18N6)]2+ cation. The structure of [Ni(C6H14N2)2][Fe(CN)5NO]·6.5H2O (2) and [Ni(cyclam)][Fe(CN)5NO]·4H2O (3) consists of zigzag chains formed by an alternate array of the paramagnetic cations and [Fe(CN)5NO]2− anions. The three compounds are paramagnets; a fourth compound containing [cis-Ni(en)2]2+ cations and [Fe(CN)5NO]− anions does not show a change in the magnetic properties a…
Understanding the high reactivity of carbonyl compounds towards nucleophilic carbenoid intermediates generated from carbene isocyanides
2015
The high reactivity of carbonyl compounds towards the carbenoid intermediate cis-IN, generated in situ by the addition of methyl isocyanide to dimethyl acetylenedicarboxylate (DMAD), has been investigated at the MPWB1K/6-311G(d,p) computational level by using Molecular Electron-Density Theory (MEDT). This multicomponent (MC) reaction is a domino process that comprises two sequential reactions: (i) the formation of a nucleophilic carbenoid intermediate trans-IN; and (ii) the nucleophilic attack of cis-IN on the carbonyl compound, resulting in the formation of the final 2-iminofuran derivative. The present MEDT study establishes that the high nucleophilic character and the electronic structur…
Carbohydrates as chiral templates: Diastereoselective Ugi synthesis of (S)-amino acids using O-acylated D-arabinopyranosylamine as the auxiliary
1989
Abstract Enantiomerically pure (S)-amino acids are synthesized via a highly diastereoselective Ugi reaction using 2,3,4-tri-O-pivaloyl-α-D-arabinopyranosylamine as the chiral template.
Neue extrem deformierte (Biphenylen‐)Kohlenwasserstoff‐Gerüste
1992
New Extremely Deformed (Biphenylene)Hydrocarbon Skeletons The tetracyclic carbon skeleton 2-oxo[3](1,8)biphenylenophane (4) was synthesized by cyclization of a mixture of the bis(bromomethyl) compounds 7a, b with p-tolylsulfonylmethyl isocyanide. 2-Hydroxy[3](1,8)biphenylenophane (5) and the [3](1,8)biphenylenophane hydrocarbon 6 were obtained by reduction of 4 with LiAlH4 and NaBH4, respectively. X-ray analyses of 4 and 6 illustrate the dramatic deformation of bond lengths and angles in these molecules.
Hexacyanocobaltate(III) Anions as Precursors of Co(II)−Ni(II) Cyano-Bridged Multidimensional Assemblies: Hydrothermal Syntheses, Crystal and Powder …
2005
Three novel cyanide-bridged heterobimetallic coordination polymers have been synthesized by hydrothermal routes, in superheated water solutions, by using K3[Co(CN)6], NiCl2.6H2O, and alpha-diimine ligands: [Ni(CN)4Co(phen)] (1; phen = 1,10-phenanthroline), [Ni(CN)4Co(2,2'-bipy)] (2; 2,2'-bipy = 2,2'-bipyiridine), and [Ni(CN)4Co(2,2'-bipy)2] (3). The isostructural compounds 1 and 2 contain a two-dimensional network with Co(II) centers octahedrally coordinated by one chelating 2,2'-bipy ligand and four cyanide groups of four distinct [Ni(CN)4]2-, through crystallographically equivalent, bridging units. Compound 3 contains one-dimensional zigzag chains in which the Co(II) ion is coordinated by…