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Thiocyanate
Kinds of Thiocyanate Terms modified by Thiocyanate Selected AbstractsDinuclear Complexes of MII Thiocyanate (M = Ni and Cu) Containing a Tridentate Schiff-Base Ligand: Synthesis, Structural Diversity and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005Suparna Banerjee Abstract A dinuclear NiII complex, [Ni2(L)2(H2O)(NCS)2]·3H2O (1) in which the metal atoms are bridged by one water molecule and two ,2 -phenolate ions, and a thiocyanato-bridged dimeric CuII complex, [Cu(L)NCS]2 (2) [L = tridentate Schiff-base ligand, N -(3-aminopropyl)salicylaldimine, derived from 1:1 condensation of salicylaldehyde and 1,3-diaminopropane], have been synthesized and characterized by IR and UV/Vis spectroscopy, cyclic voltammetry and single-crystal X-ray diffraction studies. The structure of 1 consists of dinuclear units with crystallographic C2 symmetry in which each NiII atom is in a distorted octahedral environment. The Ni,O distance and the Ni,O,Ni angle, through the bridged water molecule, are 2.240(11) Å and 82.5(5)°, respectively. The structure of 2 consists of dinuclear units bridged asymmetrically by di-,1,3 -NCS ions; each CuII ion is in a square-pyramidal environment with , = 0.25. Variable-temperature magnetic susceptibility studies indicate the presence of dominant ferromagnetic exchange coupling in complex 1 with J = 3.1 cm,1, whereas complex 2 exhibits weak antiferromagnetic coupling between the CuII centers with J = ,1.7 cm,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] New Molecular Charge-Transfer Salts of TM-TTF and BMDT-TTF with Thiocyanate and Selenocyanate Complex Anions [TMTTF = Tetramethyltetrathiafulvalene; BMDT-TTF = Bis(methylenedithio)tetrathiafulvalene]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2003Marta Mas-Torrent Abstract Three new charge-transfer salts of tetrathiafulvalene (TTF)-based donors with thiocyanato- or selenocyanato-metal complex anions have been synthesised. The salts isolated were [BMDT-TTF]4[Cr(NCS)6] (1), [TM-TTF]4[Cr(NCS)6]·2CH3CN (2) and [TM-TTF]4[Cr(NCSe)6]·2CH3CN (3) [BMDT-TTF = bis(methylenedithio)tetrathiafulvalene and TM-TTF = tetramethyltetrathiafulvalene]. Single crystals of compound 1 crystallise in the monoclinic C2/c space group with a = 37.286(3), b = 10.0539(6), c = 21.069(2) Å, , = 124.348(4)°, V = 6520.9(9) Å3 and Z = 4. Compound 3 was also suitable for an X-ray diffraction study, however the anionic part, [Cr(NCSe)6], was highly disordered and the best solution gave a final R factor of 16.4%. A solution was found for the monoclinic space group C2/m with a = 13.787(3), b = 19.507(3), c = 14.735(5) Å, , = 102.90(3)°, V = 3862.9(17) Å3 and Z = 2. For compound 1 there are several S···S close atomic contacts between the donors and acceptors, but there is no discernible magnetic exchange between ions. Such an interaction was previously observed in related salts such as [TTF][Cr(NCS)4(phenanthroline)2] and [donor][M(NCS)4(isoquinoline)2] [M = Cr, Fe and donor = TTF, BEDT-TTF or TM-TTF (tetramethyltetrathiafulvalene)]. Compounds 1 to 3 are all paramagnetic semiconductors in which the magnetic susceptibility is dominated by the Cr-containing anions. The structure-function relationship, along with a comparison with related compounds, indicates that there is no long-range magnetic order because there are no ,-stacking interactions between donor and acceptor; these types of interactions are seen in all of the bulk magnets of this type in which the donor spin is magnetically coupled to the anion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Synthesis of Some Novel Thioxanthenone-Fused Azacrown Ethers, and Their Use as New Catalysts in the Efficient, Mild, and Regioselective Conversion of Epoxides to , -Hydroxy Thiocyanates with Ammonium ThiocyanateHELVETICA CHIMICA ACTA, Issue 7 2007Hashem Sharghi Abstract The regioselective ring-opening reactions of some epoxides with ammonium thiocyanate in the presence of a series of new 9H -thioxanthen-9-one-fused azacrown ethers, i.e., 7,11 (Scheme,1), and also of dibenzo[18]crown-6 (12), Kryptofix®22 (13), and benzo[15]crown-5 (14) were studied (Tables 1 and 2). The epoxides were subjected to cleavage by NH4SCN in the presence of these catalysts under mild conditions in various aprotic solvents. Reagents and conditions were identified for the synthesis of individual , -hydroxy thiocyanates in high yield and with more than 90% regioselectivity. The results can be discussed in terms of a four-step mechanism (Scheme,2): 1) formation of a complex between catalyst and NH4SCN, 2) release of SCN, from the complex, 3) reaction of the released SCN, at the sterically less hindered site of the epoxide, and 4) regeneration of the catalyst. The major advantages of this method are the high regioselectivity, the simple regeneration of the catalyst, the reuse of it through several cycles without a decrease of activity, and the ease of workup of the reaction mixtures. [source] Thiocyanate overload and thyroid diseaseBIOFACTORS, Issue 3-4 2003Murat Faik Erdo Abstract Thiocyanate [SCN,] is a complex anion which is a potent inhibitor of iodide transport. It is the detoxification product of cyanide and can easily be measured in body fluids. Consumption of naturally occurring goitrogens, certain environmental toxins and cigarette smoke can significantly increase SCN, concentrations to levels potentially capable of affecting the thyroid gland. Goiter endemics were reported to develop when the critical urinary iodine/ SCN, ratio decreases below 3 ,g iodine per mg SCN,. Iodine supplementation completely reverses the goitrogenic influence of SCN,. SCN, is also generated from cigarette smoking as a detoxifying product of cyanide. During the past two decades many reports dealt with the possible effects of cigarette smoking on thyroid hormone synthesis, thyroid gland size and thyroid autoimmunity including infiltrative ophtalmopathy of Graves' disease. In this mini-review, issues regarding thiocyanate overload and thyroid disease will be summarized. [source] ChemInform Abstract: Novel Antitumor Acetamide, Pyrrole, Pyrrolopyrimidine, Thiocyanate, Hydrazone, Pyrazole, Isothiocyanate and Thiophene Derivatives Containing a Biologically Active Pyrazole Moiety.CHEMINFORM, Issue 16 2010Saleh I. Alqasoumi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Mechanism of Criss-Cross Reaction of Aromatic Glyoxalimines with Potassium Cyanate and Thiocyanate.CHEMINFORM, Issue 32 2007Jiri Hanusek Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] ChemInform Abstract: Thiocyanogen as an Intermediate in the Oxidation of Thiocyanate by Hydrogen Peroxide in Acidic Aqueous Solution.CHEMINFORM, Issue 6 2001James N. Figlar Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Dynamical Complexity in Electrochemical Oxidations of ThiocyanateCHINESE JOURNAL OF CHEMISTRY, Issue 4 2009Li LIU Abstract Kinetics and mechanism of the electrochemical oxidation of thiocyanate on a Pt electrode were investigated by using various electrochemical methods, in which both current and potential oscillations have been observed. Cyclic voltammetry measurements illustrate that the oxidation process consists of two steps. In addition to the oscillatory behavior, the system also exhibits bistability, in which the oxidation could be switched between a high and a low current density states with a temporal potential perturbation. The presence of inert ions with stronger absorption also induces transitions from oscillatory to steady reactions in the thiocyanate system. [source] Synthesis of Some Novel Thioxanthenone-Fused Azacrown Ethers, and Their Use as New Catalysts in the Efficient, Mild, and Regioselective Conversion of Epoxides to , -Hydroxy Thiocyanates with Ammonium ThiocyanateHELVETICA CHIMICA ACTA, Issue 7 2007Hashem Sharghi Abstract The regioselective ring-opening reactions of some epoxides with ammonium thiocyanate in the presence of a series of new 9H -thioxanthen-9-one-fused azacrown ethers, i.e., 7,11 (Scheme,1), and also of dibenzo[18]crown-6 (12), Kryptofix®22 (13), and benzo[15]crown-5 (14) were studied (Tables 1 and 2). The epoxides were subjected to cleavage by NH4SCN in the presence of these catalysts under mild conditions in various aprotic solvents. Reagents and conditions were identified for the synthesis of individual , -hydroxy thiocyanates in high yield and with more than 90% regioselectivity. The results can be discussed in terms of a four-step mechanism (Scheme,2): 1) formation of a complex between catalyst and NH4SCN, 2) release of SCN, from the complex, 3) reaction of the released SCN, at the sterically less hindered site of the epoxide, and 4) regeneration of the catalyst. The major advantages of this method are the high regioselectivity, the simple regeneration of the catalyst, the reuse of it through several cycles without a decrease of activity, and the ease of workup of the reaction mixtures. [source] ChemInform Abstract: Reaction of Ammonium Ylides with Alkyl Thiocyanates in Aqueous and Non-aqueous Media.CHEMINFORM, Issue 38 2010Ebrahim Kianmehr Abstract Reactions of ammonium ylides, derived from phenacyl bromides and DABCO in organic solvents or thiolate anions, generated in aqueous medium, with alkyl thiocyanates lead to thio-substituted acetophenones. [source] ChemInform Abstract: A Facile and Convenient Method for the Synthesis of Alkyl Thiocyanates under Homogeneous Phase Transfer Catalyst Conditions.CHEMINFORM, Issue 21 2009Ali Reza Kiasat Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] A Task-Specific Ionic Liquid [bmim]SCN for the Conversion of Alkyl Halides to Alkyl Thiocyanates at Room Temperature.CHEMINFORM, Issue 25 2005Ahmed Kamal Abstract For Abstract see ChemInform Abstract in Full Text. [source] Preparation of Alkyl Nitrates, Nitriles and Thiocyanates from Alcohols Utilizing Trichloroisocyanuric Acid with Triphenylphosphine.CHEMINFORM, Issue 47 2004Gene A. Hiegel No abstract is available for this article. [source] Conversion of Alcohols, Thiols, Carboxylic Acids, Trimethylsilyl Ethers, and Carboxylates to Thiocyanates with Triphenylphosphine/Diethylazodicarboxylate/NH4SCN.CHEMINFORM, Issue 18 2004Nasser Iranpoor Abstract For Abstract see ChemInform Abstract in Full Text. [source] ChemInform Abstract: BaClSCN and Na4Mg(SCN)6: Two New Thiocyanates of the Alkaline Earth Metals.CHEMINFORM, Issue 38 2001Claudia Wickleder Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Improved Procedure to Aryl Thiocyanates: A New Synthetic Application of Dry Arenediazonium o-Benzenedisulfonimides.CHEMINFORM, Issue 28 2001Margherita Barbero Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Nucleation kinetics and growth of nonlinear optical bis (dimethyl sulfoxide) manganese mercury thiocyanate single crystalsCRYSTAL RESEARCH AND TECHNOLOGY, Issue 10 2008C. M. Raghavan Abstract Nonlinear optical (NLO) material of bis (dimethyl sulfoxide) manganese mercury thiocyanate (MMTD) was synthesized by two step reaction method. The solubility and metastable zonewidth were experimentally determined in order to optimize the growth parameters. Bulk crystals of MMTD were grown by slow cooling and slow evaporation methods. The structure of the grown crystal was confirmed by X-ray diffraction analysis. Presence of functional groups and the coordination of Lewis base ligand of dimethyl sulfoxide (DMSO) were confirmed by FT-IR analysis. Optical transparency of the grown crystals was studied by UV-Vis spectroscopy. Nonlinear optical property of the grown crystal was confirmed by Kurtz powder method. Etching studies reveal the formation of triangular hillock etch patterns, indicative of 2D nucleation mechanism. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Electrochemical Sensing of Thiocyanate Using Gold Electrodes Modified with an Underpotentially Deposited Silver MonolayerELECTROANALYSIS, Issue 2 2010Christopher Abstract Gold electrodes modified by underpotential deposition to expose a layer of silver atoms on their surfaces were used to measure thiocyanate concentrations in aqueous solutions. When exposed to thiocyanate, the ion adsorbs onto the modified electrode and causes changes in the electrochemical properties of the silver adlayer. Coulometric measurement of the fraction of the silver adlayer that remains in its original state provides a means for determining thiocyanate concentrations. The adsorption of thiocyanate onto the electrode follows a first-order process with a rate constant of ca. 440,L/mol s that defines its concentration/time response. [source] Estimation of Ion-Pairing Constants in Plasticized Poly(vinyl chloride) Membranes Using Segmented Sandwich Membranes TechniqueELECTROANALYSIS, Issue 17-18 2009Vladimir Abstract Segmented sandwich membrane method was used to determine ion-pairing constants for four cationic sites: tris-(2,3,4-dodecyloxy)benzenetrimethylammonium, tris-(2,3,4-dodecyloxy)benzenedimethyloctylammonium, tris-(2,3,4-dodecyloxy)benzenemethyldioctylammonium, and dimethyldioctadecylammonium with chloride, bromide, nitrate, benzene sulfonate, trichloroacetate, thiocyanate, perchlorate and picrate, as well as ion-pairing constants for two anionic sites: tetraphenylborate and tris-(2,3,4-octyloxy)benzenesulfonate with dimedrol, quinine, anapriline, and amantadine cations in poly(vinyl chloride) membranes plasticized with 2-nitrophenyl octyl ether. Ion association constants of anions with quaternary ammonium sites regularly increase from picrate to chloride along with reduction of the anion radius and with improvement of site exchanger center steric accessibility. Ion association constants of amine cations with tris-(2,3,4-octyloxy)benzenesulfonate are several orders higher than those with tetraphenylborate and regularly increase from tertiary amine to primary one. [source] Aluminum(III) Porphyrins as Ionophores for Fluoride Selective Polymeric Membrane ElectrodesELECTROANALYSIS, Issue 6 2006Jeremy Abstract Aluminum(III) porphyrins are examined as potential fluoride selective ionophores in polymeric membrane type ion-selective electrodes. Membranes formulated with Al(III) tetraphenyl (TPP) or octaethyl (OEP) porphyrins are shown to exhibit enhanced potentiometric selectivity for fluoride over more lipophilic anions, including perchlorate and thiocyanate. However, such membrane electrodes display undesirable super-Nernstian behavior, with concomitant slow response and recovery times. By employing a sterically hindered Al(III) picket fence porphyrin (PFP) complex as the membrane active species, fully reversible and Nernstian response toward fluoride is achieved. This finding suggests that the super-Nernstian behavior observed with the nonpicket fence metalloporphyrins is due to the formation of aggregate porphyrin species (likely dimers) within the membrane phase. The steric hindrance of the PFP ligand structure eliminates such chemistry, thus leading to theoretical response slopes toward fluoride. Addition of lipophilic anionic sites into the organic membranes enhances response and selectivity, indicating that the Al(III) porphyrin ionophores function as charged carrier type ionophores. Optimized membranes formulated with Al(III)-PFP in an o -nitrophenyloctyl ether plasticized PVC film exhibit fast response to fluoride down to 40,,M, with very high selectivity over SCN,, ClO4,, Cl,, Br, and NO3, (kpot<10,3 for all anions tested). With further refinements in the membrane chemistry, it is anticipated that Al(III) porphyrin-based membrane electrodes can exhibit potentiometric fluoride response and selectivity that approaches that of the classical solid-state LaF3 crystal-based fluoride sensor. [source] Ion-Selective Electrodes for Thiocyanate Based on the Dinuclear Zinc(II) Complex of a Bis- N,O -bidentate Schiff BaseELECTROANALYSIS, Issue 12 2004Philippe Bühlmann Abstract An ion selective electrode based on the dinuclear complex formed by two zinc(II) ions and two molecules of the bis- N,O -bidentate Schiff base 2,2,-[methylenebis(4,1-phenylenenitrilomethylidyne)]bisphenol exhibits thiocyanate selectivity with a good discrimination of nitrite, nitrate, and azide. The selectivities of electrode membranes with various compositions indicate that this potentiometric selectivity is based on the formation of a 1,:,1 complex between the thiocyanate anion and the dinuclear ionophore. The 2,:,1 ratio of thiocyanate ions and the dinuclear ionophore that results from higher ratios of cationic sites and ionophore worsens the selectivity, suggesting that binding of a thiocyanate to both zinc(II) centers of the dinuclear ionophore is not favorable. Interestingly, the selectivity patterns of these electrodes differ radically from that of a highly sulfate selective electrode based on a compound reported previously to be the analogous mononuclear 1,:,1 complex of zinc(II) and the same Schiff base. It is suggested that the previously reported 1,:,1 complex with zinc(II) may indeed have been a polymer of the same elemental composition. [source] Indirect laser-induced fluorescence detection for capillary electrophoresis using a frequency-doubled diode laserELECTROPHORESIS, Issue 3 2003Natalia Ragozina Abstract A blue (452 nm) frequency-doubled diode laser with a quasi-cw optical output power of 10 ,W is used for indirect laser-induced fluorescence detection in combination with the capillary electrophoretic separation of inorganic anions. As fluorescing probe ion the anion of 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS) was selected having an absorption maximum of 454 nm in alkaline medium. Employing a capillary coated with linear acrylamide, baseline separation of eight inorganic anions was possible within 5 min. With a separation buffer containing 50 ,mol·L -1 HPTS and 10 mmol·L -1 lysine the limits of detection for sulfate, nitrite, nitrate, azide, thiocyanate, and chlorate were between 0.9 and 4.7 ,mol·L -1. Separation of chloride and sulfate was achieved by adding 0.25 mmol·L -1 calcium hydroxide to the separation buffer. Inorganic anions in several mineral and tap water samples have been determined with the technique developed and results are compared to data obtained by ion chromatography in combination with conductivity detection after conductivity suppression. [source] Hydration of exercised Standardbred racehorses assessed noninvasively using multi-frequency bioelectrical impedance analysisEQUINE VETERINARY JOURNAL, Issue S36 2006A. WALLER Summary Reasons for performing study: In human and animal clinical practice, multi-frequency bioelectrical impedance analysis (MF-BIA) is increasingly used as a diagnostic tool to assess hydration of intra-and extracellular fluid compartments. Accurate determination of changes in hydration status within individuals over time has remained problematic due to the requirement for complete impedance-frequency relationships at the time points of interest. Objectives: To use MF-BIA in 13 Standardbred racehorses and 7 ,endurance' research horses to determine if MF-BIA could be used to track changes in total body water (TBW), intracellular fluid volume (ICFV) and extracellular fluid volume (ECFV) resulting from exercise. Methods: Jugular venous blood was sampled at rest and for 2,13 h following exercise. TBW, ECFV and plasma volume (PV) were measured at rest using indicator dilution techniques (D2O, thiocyanate and Evans Blue, respectively). TBW, ECFV, ICFV and PV were correlated to impedance measures and predictive equations used to determine hydration status from MF-BIA measures. Results: TBW loss continued throughout the recovery period, and was primarily borne by the ECF compartment at 90 min of recovery. Conclusions: MF-BIA predictions of compartmental hydration status were significantly correlated to measured/calculated decreases in these compartments. Potential relevance: Practical applications for MF-BIA in horses include monitoring of hydration status during transport and competition, assessment of body compostion, clinical health assessment and critical care management. [source] Monomeric and Dimeric Copper(II) Complexes of a Pyrrole-Containing Tridentate Schiff-Base LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2009Rongqing Li Abstract Three copper(II) complexes of (L1),, [CuL1Cl] (1), [CuL1Br]n (2) and [Cu2(L1)2(,1,3 -NCS)2] (3), and two copper(II) complexes of HL1, [Cu(HL1)X2] (X = Cl,, 4; X = Br,, 5), have been prepared and characterised [where HL1 is the Schiff-base ligand derived from pyrrole-2-carbaldehyde and 2-aminomethylpyridine]. The removal of a chloride ion and deprotonation of [Cu(HL1)Cl2] (4) to form [CuL1Cl] (1) worked well. However, attempts to protonate [CuL1Cl] with HCl to re-form [Cu(HL1)Cl2] were not successful. X-ray structure determinations revealed that 1 is a N3Cl-coordinated square-planar copper(II) monomer [CuL1Cl], whereas 3 is a doubly end-to-end thiocyanate-bridged square-pyramidal copper(II) dimer [Cu2(L1)2(,1,3 -NCS)2]. The structure determinations on 4 and 5 showed that in both cases the copper(II) ion is in a distorted square-planar N2X2 environment, with the pyrrole NH remaining non-deprotonated and uncoordinated. Variable-temperature magnetic susceptibility investigations carried out on the end-to-end thiocyanate doubly bridged square-pyramidal copper(II) dimer 3 showed that no magnetic coupling occurs between the two copper(II) ions; it exhibits Curie-like magnetic behaviour.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Tripyrrinatocadmium Complexes: Enforcing Supramolecular Aggregation by a Large IonEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2007Martin Bröring Abstract A newly developed method for the preparation of free base tripyrrin ligands HTrpy by cyanide-promoted demetalation of nickel chelates TrpyNiNCO was used in order to explore the chemistry of cadmium tripyrrins TrpyCdX with a variety of anionic co-ligands X. The introduction of the large CdII ion into the tripyrrin N3 coordination site was accomplished by the use of cadmium acetate as the metal precursor. Ligand exchange experiments using sodium salts of different anions disclose a marked tendency for pentacoordination, which is achieved either by the formation of chelates or of 1D coordination polymers that form as a consequence of the size of the central metal. The attempted introduction of chlorido, iodido, or cyanato ligands thus leads mainly to decomposed material, while the use of 1,1,1-trifluoracetylacetonate, salicylate, and acetate ligands results in stable, pentacoordinate and monomeric complexes with the external ligand bound as a four- or six-membered O,O -chelate ring. With the pseudohalogenido ligands thiocyanate, selenocyanate, and azide as well as with the weakly coordinating trifluoroacetate 1D coordination polymers with a variety of chain structures were obtained and investigated by X-ray diffraction studies. Interestingly TrpyCdN3 is present in the crystal as a coordinatively and hydrogen-bonded methanol adduct with a dimeric repeating subunit. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] EPR Insensitivity of the Metal-Nitrosyl Spin-Bearing Moiety in Complexes [LnRuII -NO·]kEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2004Stéphanie Frantz Abstract A survey of 18 paramagnetic species [LnRu(NO)]k, including seven new examples studied by in situ electrolysis, reveals a surprisingly narrow range of EPR parameters despite a wide variety of ligands such as pyridine, polypyridines, imines, amines, nitriles, phosphanes, carbonyl, cyclopentadienides, halides, hydride, hydroxide, thiocyanate or cyanide: g1 = 2.015 ± 0.02, g2 = 1.990 ± 0.015, g3 = 1.892 ± 0.03, gav = 1.968 ± 0.02, ,g = g1 , g3 = 0.122 ± 0.037, A2(14N) = 3.3 ± 0.5 mT. This rather small variability, smaller still if the organometallic compounds are excluded, differs from the wider range of EPR data reported for nitrosyliron species with S = 1/2; apparently, the {RuNO}7 configuration involves a rather invariant and relatively covalent metal,NO interaction. DFT calculations were employed for [(NC)5Ru(NO)]3, to reproduce the EPR data, to evaluate the spin distribution (58% spin density on NO), and to reveal structural changes on reduction such as the Ru,N,O bending and Ru,NO bond lengthening. In addition, the possibility of staggered and eclipsed conformations is discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Sodium Hydro(isothiocyanato)borates: Synthesis and StructuresEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2004Heinrich Nöth Abstract Sodium thiocyanate reacts in THF solution with 18-crown-6 to give the molecular compound Na(18-crown-6)(THF)NCS (3) with the N atom of the NCS anion oriented towards Na+. The same reaction with 15-crown-5 yields the ion pair Na(15-crown-5)NCS (4). In contrast, Na(NCS)(py)4, obtained by treating a solution of Na(H3BNCS) in THF with pyridine, yields Na(py)4(NCS) (5), which has a chain structure with hexacoordinate Na atoms coordinated to five N atoms and an S atom. Na(NCS) in THF adds 1 equiv. of BH3 to give Na(H3BNCS)·nTHF. Addition of 18-crown-6 to this solution yields crystals of the salt [Na(18-crown-6)(THF)2][H3BNCS] (1), as shown by X-ray crystallography. Both the cation and the anion show site disorder. However, when 15-crown-5 is used for complexation, the salt [Na(15-crown-5)(THF)][H3BNCS] (2) can be isolated. Its anion shows an almost linear B,N,C,S unit. Only a mixture of (catecholato)(isothiocyanato)borates results on treating Na(NCS) in THF with catecholborane. However, the borate Na[catB(NCS)2] is readily formed by adding Na(NCS) to B -(isothiocyanato)catecholborane. Single crystals of this compound were obtained as the salt [Na(18-crown-6)(THF)2][catB(NCS)2] (6). On the other hand, the reaction of Na(NCS) with 9-borabicyclo[3.3.1]nonane (9-BBN) in THF yields Na[(9-BBN)NCS)]·nTHF, and, on addition of 18-crown-6, the complex [Na(18-crown-6)(THF)2][(9-BBN)NCS] was isolated. Suitable crystals for X-ray structure determination were, however, only obtained by crystallization from tetrahydropyran. This solvate has the rather unusual structure [Na(18-crown-6)(thp)2][{(9-BBN)NCS}2Na(thp)4] (8). The sodiate anion has an Na atom coordinated by two S and four O atoms. DFT calculations support these experimental results: The (isothiocyanato)borates are more stable than the thiocyanato isomers. For the latter a bent structure of the B,S,C,N unit with a B,S,C bond angle of 105.7° is predicted. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Sulfide : quinone oxidoreductase (SQR) from the lugworm Arenicola marina shows cyanide- and thioredoxin-dependent activityFEBS JOURNAL, Issue 6 2008Ursula Theissen The lugworm Arenicola marina inhabits marine sediments in which sulfide concentrations can reach up to 2 mm. Although sulfide is a potent toxin for humans and most animals, because it inhibits mitochondrial cytochrome c oxidase at micromolar concentrations, A. marina can use electrons from sulfide for mitochondrial ATP production. In bacteria, electron transfer from sulfide to quinone is catalyzed by the membrane-bound flavoprotein sulfide : quinone oxidoreductase (SQR). A cDNA from A. marina was isolated and expressed in Saccharomyces cerevisiae, which lacks endogenous SQR. The heterologous enzyme was active in mitochondrial membranes. After affinity purification, Arenicola SQR isolated from yeast mitochondria reduced decyl-ubiquinone (Km = 6.4 ,m) after the addition of sulfide (Km = 23 ,m) only in the presence of cyanide (Km = 2.6 mm). The end product of the reaction was thiocyanate. When cyanide was substituted by Escherichia coli thioredoxin and sulfite, SQR exhibited one-tenth of the cyanide-dependent activity. Six amino acids known to be essential for bacterial SQR were exchanged by site-directed mutagenesis. None of the mutant enzymes was active after expression in yeast, implicating these amino acids in the catalytic mechanism of the eukaryotic enzyme. [source] Presence of a Na+ -stimulated P-type ATPase in the plasma membrane of the alkaliphilic halotolerant cyanobacterium Aphanothece halophyticaFEMS MICROBIOLOGY LETTERS, Issue 1 2007Kanjana Wiangnon Abstract Aphanothece cells could take up Na+ and this uptake was strongly inhibited by the protonophore, carbonyl cyanide m -chlorophenylhydrazone (CCCP). Cells preloaded with Na+ exhibited Na+ extrusion ability upon energizing with glucose. Na+ was also taken up by the plasma membranes supplied with ATP and the uptake was abolished by gramicidin D, monensin or Na+ -ionophore. Orthovanadate and CCCP strongly inhibited Na+ uptake, whereas N, N, -dicyclohexylcarbodiimide (DCCD) slightly inhibited the uptake. Plasma membranes could hydrolyse ATP in the presence of Na+ but not with K+, Ca2+ and Li+. The Km values for ATP and Na+ were 1.66±0.12 and 25.0±1.8 mM, respectively, whereas the Vmax value was 0.66±0.05 ,mol min,1 mg,1. Mg2+ was required for ATPase activity whose optimal pH was 7.5. The ATPase was insensitive to N -ethylmaleimide, nitrate, thiocyanate, azide and ouabain, but was substantially inhibited by orthovanadate and DCCD. Amiloride, a Na+/H+ antiporter inhibitor, and CCCP showed little or no effect. Gramicidin D and monensin stimulated ATPase activity. All these results suggest the existence of a P-type Na+ -stimulated ATPase in Aphanothece halophytica. Plasma membranes from cells grown under salt stress condition showed higher ATPase activity than those from cells grown under nonstress condition. [source] GC,MS analysis of volatile hydrolysis products from glucosinolates in Farsetia aegyptia var. ovalisFLAVOUR AND FRAGRANCE JOURNAL, Issue 2 2003A. A. Al-Gendy Abstract Twenty-two volatile glucosinolate hydrolysis products from seeds and leaves of Farsetia aegyptia var. ovalis were identi,ed and quanti,ed using both natural autolysis and exogenous myrosinase, followed by GC,MS. The 22 isothiocyanate thiocyanate, epithioalkane nitrile and nitrile hydrolysis products identi,ed can be rationalized, assuming 13 glucosinolates in the seeds and 12 in the leaves. Among the volatile hydrolysis products observed, those derived from allylglucosinolates and 3-methylsulphinylpropylglucosinolate (glucoiberin) were prominent. 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