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Showing papers on "Acetonitrile published in 1982"



Journal ArticleDOI
TL;DR: A new enzyme, aliphatic nitrile hydratase, which hydrates acetonitrile to form acetamide was purified from the cell-free extract of acetonijile-grown Arthrobacter sp.
Abstract: A new enzyme, aliphatic nitrile hydratase, which hydrates acetonitrile to form acetamide was purified from the cell-free extract of acetonitrile-grown Arthrobacter sp. J-1. The overall purification was about 290-fold with a yield of 10%. The purified enzyme was homogeneous as judged by ultracentrifugation and disc gel electrophoresis. The enzyme catalyzed the stoichiometric hydration of acetonitrile to form acetamide according to the following scheme: CH3CN + H2O →. CH3CONH2. The enzyme was inducibly formed and then amidase which hydrolyzed acetamide was formed. The molecular weight of the enzyme was determined to be about 420,000 by gel filtration. The enzyme was composed of two kinds of subunits, of which the molecular weights were 24,000 and 27,000. The isoelectric point was 3.6. The enzyme was active toward low molecular weight aliphatic nitriles of 2 to 5 carbon atoms. The Km value for acetonitrile was determined to be 5.78 mM. The enzyme was inactivated by sulfhydryl reagents. The enzyme was competi...

158 citations


Journal ArticleDOI
TL;DR: In this article, a polythiophene perchlorate was prepared electrochemically in an electrolyte of 0.5 M AgClO4 and 0.2 M thiophene in acetonitrile.
Abstract: Poly-thiophene perchlorate is prepared electrochemically in an electrolyte of 0.5 M AgClO4 and 0.2 M thiophene in acetonitrile. Dark greenish film with the complex of ca. [C4H2S(ClO4)0.26]x is obtained. The electrical conductivity along the film surface is about 0.6 Ω-1cm-1.

121 citations


Journal ArticleDOI
TL;DR: In this article, a model of the stationary phase consisting of solvent molecules absorbed to both the bonded organic moiety and residual silanols on the silica surface is presented, and the authors show that the formation of stationary phase is dependent on two mechanisms.

105 citations


Journal ArticleDOI
TL;DR: In this paper, the effects of using different sources of precursor poly(ethylene oxide) and acetonitrile solvent on the physical and electrochemical properties of lithium salt-PEO polymer electrolytes were investigated.

79 citations


Journal ArticleDOI
TL;DR: Toxic expression of aliphatic nitriles depends not only upon cyanide release but also on their degree of unsaturation, which plays a minimal role in their toxicity.

67 citations




Journal ArticleDOI
TL;DR: The cathodic behavior of acetonitrile at a platinum electrode is strongly dependent on the cation of the supporting electrolyte, and contamination by moisture as mentioned in this paper, and the results are consistent with the formation of hydride ion at the platinum surface.

45 citations


Journal ArticleDOI
E. Klei1, J.H. Teuben1, H.J. de Liefde Meijer1, E.J. Kwak1, A.P. Bruins1 
TL;DR: In this article, the insertion products of Cp 2 Tiη 3 -allyl and Cp2 Ti-3 -1-methylallyl with carbon dioxide, phenylisocyanate, benzalaniline, acetone and acetonitrile were formed via allyl migration.

45 citations


Journal ArticleDOI
TL;DR: In this paper, experimentelle Ergebnisse für the beiden Selbstdiffusionskoeffizienten and den einen gegenseitigen Diffusionskoesffizienen für die vier binären wäßrigen Mischungen with Methanol, Ethanol, Acetonitril' and Dimethylformamid bei 25°C mitgeteilt.
Abstract: Es werden experimentelle Ergebnisse für die beiden Selbstdiffusionskoeffizienten und den einen gegenseitigen Diffusionskoeffizienten für die vier binären wäßrigen Mischungen mit Methanol, Ethanol, Acetonitril' und Dimethylformamid bei 25°C mitgeteilt. Die benutzte Methode war teilweise die NMR-Spin-Echo-Technik und teilweise das Diaphragmaverfahren, verbunden mit Tracer-Aktivitäts-, Dichteoder Brechungsindexmessungen. Aus den Diffusionsdaten wurde dann für jedes System ein Satz von Geschwindigkeitskorrelationskoeffizienten hergeleitet. Der herausragende Effekt, der sich für die Wasser— Wasser-Korrelationskoeffizienten ergab, war deren positives Vorzeichen in drei Fällen; dies deutet auf Wasser—WasserAssoziation hin. Es ergaben sich geringfügige gleichfalls positive Effekte für Geschwindigkeitskorrelationen zwischen den gelösten Teilchen.

Journal ArticleDOI
TL;DR: A series of 29 substituted 1,4-dihydropyridines has been studied in acetonitrile by means of voltammetric methods at a platinum electrode as mentioned in this paper.

Journal ArticleDOI
TL;DR: In this article, the interaction of typical polar solvents and electrolytes at electrodes having Pt(111) or Pt(100) single-crystal surfaces was investigated and the results indicated that these typical electrochemical materials adsorb strongly to the clean Pt surface but once adsorbed tend not to react with each other.

Journal ArticleDOI
TL;DR: In this paper, the compounds (M(NO)/sub 2/(CH/sub 3/CN)/sub 4/), (BF/sub 4)/sub 1/ ), (2, M = Mo; 3, W = W) were synthesized through reactions of the corresponding metal hexacarbonyls with 2 equiv of NOBF/Sub 4/ in acetonitrile.


Journal ArticleDOI
TL;DR: In this paper, the results obtained are discussed in terms of the mixture model of water and they are compared with results obtained from Raman spectral studies of aqueous electrolytes, and it is proposed that water structure breaking and the formation of solute-solvent complexes when organic solutes are added to water can account for these results.
Abstract: Raman spectra of aqueous solutions of dimethylsulfoxide, dimethylsulfoxide-d6, acetone and acetonitrile are reported in the OH stretching region, and in the stretching regions of the functional groups of these solutes. Raman intensities and frequency shifts of these bands show definite trends with varying concentrations of the solutions. The results obtained are discussed in terms of the mixture model of water, and they are compared with results obtained from Raman spectral studies of aqueous electrolytes. It is proposed that water structure breaking and the formation of solute-solvent complexes when organic solutes are added to water can account for these results.

Journal ArticleDOI
TL;DR: In this paper, the authors show that the metallurgically important oxidations of copper, silver, CuS and Cu2 with CuSO4 in water are strongly favored in an enthalpic and free energy sense by the addition of acetonitrile.
Abstract: Free energies and Walden products show that the Cu+ and Ag+ ions are specifically solvated by acetonitrile (AN), 2-hydroxycyanoethane (HAN), and by pyridine (Py) whereas Na+ is specifically solvated by water, in mixtures of these organics with water. The Cu2+ ion is specifically solvated by pyridine in pyridine-water mixtures, but by water in acetonitrile-water mixtures. Ion-solvent, coordinated solvent-bulk solvent, and solvent-solvent interactions produce large entropy losses in the order Cu+≫Ag+>Na+ for transfer of these ions from water to dilute acetonitrile-water. The metallurgically important oxidations of copper, silver, CuS and Cu2 with CuSO4 in water are strongly favored in an enthalpic and free energy sense by the addition of acetonitrile, but addition of acetonitrile also produces a large loss of entropy for the reactions.

Journal ArticleDOI
TL;DR: In this article, the fluorescence properties of a covalently-linked porphyrin-quinone complex and its zinc derivative were studied in a variety of organic solvents.
Abstract: — The fluorescence properties of a covalently-linked porphyrin-quinone complex and its zinc derivative were studied in a variety of organic solvents The kinetics of fluorescence decay for both the quinone and hydroquinone oxidation states were measured in acetonitrile, dichloromethane, dimethyl-formamide, and pentane The fluorescence yield and kinetics of decay at room temperature were little affected in the porphyrin or zinc porphyrin complexes when the attached quinone was reduced However, for these complexes the fluorescence yield and lifetimes were both substantially decreased in acetonitrile and dichloromethane when the quinone was in its oxidized state These latter decay kinetics were not explainable by a process having a single exponential decay On the other hand, little fluorescence quenching or lifetime shortening was observed in dimethylformamide or pentane, indicating unique solvent dependencies for the quenching process Evidence was obtained for photoproduced charge separation from EPR measurements on the covalently-linked zinc porphyrin-quinone complex The EPR data showed equivalent concentrations of a Zn porphyrin cation radical and a benzoquinone anion radical in acetonitrile or dichloromethane at both room temperature and 77 K The charge separated state rapidly decayed at room temperature (in sub-millisecond times) but was quite stable at 77 K It is concluded that light-induced charge separation in acetonitrile and dichloromethane at room temperature may occur from the excited singlet state with a high quantum efficiency A photoproduced charge separated state also occurred when the covalently-linked complexes were incorporated into egg yolk phosphatidylcholine liposomes The quantum yield for radical formation in this latter system was 01 and the lifetimes of the radical species formed were many minutes

Journal ArticleDOI
TL;DR: In this paper, the structure and microdynamics of the dibenzo-24crown-8 -sodium perchlorate complex have been studied by Na-23 and C-13 nmr.
Abstract: Structure and microdynamics in solution of the dibenzo-24-crown-8 – sodium perchlorate complex have been studied by Na-23 and C-13 nmr. In all solvents (acetone, acetonitrile, pyridine, nitromethane, propylene carbonate, and chloroform-d) and in the binary mixtures acetone/pyridine, acetonitrile/nitromethane, propylene carbonate/methanol, the crown wraps around the sodium cation and expels the conjugate anion and the solvent molecules from the cation coordination sphere. Measurements of Na-23 quadrupolar and C-13 dipole–dipole relaxation times give the effective correlation time of the complex in CDCl3 solution (65 ± 11 ps) and the Na-23 quadrupolar coupling constant in all those solvents and binary mixtures (0.8–1.2 MHz). The sodium coordination shell is completely frozen during a time superior to the reorientational correlation time.

Journal ArticleDOI
TL;DR: A species of Rhodococcus was isolated from garden soil on the basis of its capacity to use acetonitrile as sole C and N source hydrolysed a number of amides and nitriles to ammonia indicating that the enzymes involved in nitrile degradation are subject to induction/repression.
Abstract: SUMMARY: A species of Rhodococcus was isolated from garden soil on the basis of its capacity to use acetonitrile as sole C and N source. Acetonitrile-grown cells hydrolysed a number of amides and nitriles to ammonia. The substrate nitriles, listed in order of decreasing hydrolysis rates, were acetonitrile, acrylonitrile, propionitrile and n-butyronitrile. The corresponding amides were also hydrolysed together with formamide and, to a small extent, nicotinamide. With the exception of acrylonitrile and acrylamide, each compound supported growth as did the non-substrates malonamide, benzamide, α-phenylacetamide and 3-aminopropionitrile. Benzonitrile, phenylacetonitrile (benzyl cyanide), malononitrile and aminoacetonitrile did not support growth. Nicotinamide and benzamide stimulated acetamidase activity but malonamide had no effect. Both the aminonitriles inhibited the acetonitrilase system. Cells grown in succinate (NH4)2SO4 medium did not hydrolyse acetonitrile or acetamide indicating that the enzymes involved in nitrile degradation are subject to induction/repression. Acetamide and acetate appear to be gratuitous inducers of acetonitrilase: acetate also induces the acetamidase.

Journal ArticleDOI
TL;DR: In this paper, the electrochemical reduction of 17 substituted 1, 2, 4, 5-tetrazines and 22 substituted 1-2, 4-triazines in dry acetonitrile has been investigated by cyclic voltammetry at a mercury drop electrode.

Journal ArticleDOI
TL;DR: In this paper, the authors examined trinuclear triangular copper(II) complexes of pyridine•2-carbaldoxime (HPL) and isonitrosoketimine ligands of type RNC(R(R')C(R´NOH)NOH (R = Et, n-Pr,n-Bu, Ph; R'=Me. Ph) have been examined electrochemically.
Abstract: Trinuclear triangular copper(II) complexes of pyridine•2-carbaldoxime (HPL) and isonitrosoketimine ligands of type RNC(R(R')C(R')NOH (R = Et, n-Pr, n-Bu, Ph; R'=Me. Ph) have been examined electrochemically. These strongly antiferromagnetic complexes are of types (Cu30(ligand)3)+ and [Cu3OH(ligand)2+, having Cu30 and Cu30H cores, respectively. The known structure of [Cu3OH(PL)3]2+ provides an authentic reference point for data analysts. Cyclic voltammetry and constant-potential electrolysis (platinum working electrode) show that complexes with a Cu30 ooze uniformly display a one-electron-transfer process characterized by the oxidation-state description CuIIICuII+e-⇌ CuII3 with E°298 in the range 0.3-0.6 V vs. SCE in acetonitrile and dimethylformamide. The species with a Cu3OH core do not have this electrochemical response. On the other hand, such species show a novel one-electron-transfer process of the type CuII3+e-⇌ CuII2CuI with E°298 in the range -0.3 to -0.45 V vs. SCE at a hanging-mercury-drop electrode in acetonitrile. The Cu30 core does not display this process. In effect the electrochemical behaviors of the two cores are complementary: the Cu3O core undergoes oxidation while the Cu3OH core undergoes reduction. Thus the core proton acts in a va/velike fashion in controlling the direction of electron transfer Addition of an acid (HCl04) converts the Cu3O species to the Cu3OH species. Conversely, addition of a base (NEt3) converts Cu3OH to Cu30. The electrochemical responses change accordingly with addition of acid or base The interconversion reactions are also useful at preparative levels.

Journal ArticleDOI
01 Jul 1982-Talanta
TL;DR: The suitability of Raman spectroscopy for studies of the solid-phase complex is demonstrated and limitations in the use of infraredSpectroscopy are discussed.

Journal ArticleDOI
TL;DR: Treatment of trimethylsilylmethanesulfonyl chloride with cesium fluoride in acetonitrile at room temperature has been found to produce sulfene which can be trapped in good yield as mentioned in this paper.

Journal ArticleDOI
TL;DR: In this article, die sich bildenden Hauptspezies bei der Solvolyse von AlCl3 in Acetonitril IR-, RA- sowie 35Cl-and 27AL-NMR-spektroskopisch untersucht.
Abstract: Im molaren CH3CN/AlCl3-Verhaltnisbereich von 5.6-8O werden die sich bildenden Hauptspezies bei der Solvolyse von AlCl3 in Acetonitril IR-, RA- sowie 35Cl- und 27AL-NMR-spektroskopisch untersucht.

Journal ArticleDOI
TL;DR: In this article, rate constants and activation parameters for the reaction of ethyl iodide plus bromide ion in acetonitrile + methanol and NN-dimethylacetamide + methenol mixtures have been determined for single-ion transfer enthalpies for the ions Br−, I−, ClO−4 and (n-Bu)4)B−.
Abstract: Rate constants and activation parameters have been determined for the reaction of ethyl iodide plus bromide ion in acetonitrile + methanol and NN-dimethylacetamide + methanol mixtures. Single-ion transfer enthalpies have also been determined in these two solvent mixtures for the ions Br–, I–, ClO–4 and (n-Bu)4)B– on the basis of tetra-n-butylammonium/tetra-n-butylborate exchange. Experimental analysis and model calculations indicated that the halide-ion solvation enthalpy is a composite of the hydrogen-bonding energy and of the ‘more physical’ interaction energy. The physical meaning of the abnormal coefficient of the extended Bronsted relationships observed for the present reactions is discussed by dissecting anion transfer enthalpies into their constituent terms.


Journal ArticleDOI
TL;DR: N-Trifluoracetyl-1-benzyltetrahydroisoquinolines 1 cyclize on anodic oxidation in acetonitrile to neospirodienones, whilst in methanol/acetonitriles as electrolyte morphinadienones are formed as mentioned in this paper.

Journal ArticleDOI
TL;DR: In this paper, the 1 : 1 complexes of lithium ion in acetonitrile (AN) with DMF, DMSO, DMA, and HMPA were derived.
Abstract: Formation constants of the 1 : 1 complexes of lithium ion in acetonitrile (AN) with DMF, DMSO, DMA, and HMPA and of sodium ion in AN with 15-crown-5 (15C5), 18-crown-6 (18C6), dibenzo-18-crown-6 (D...