Interaction of metal ions with nucleic acids and related compounds. II. Studies on Au(III)-nucleic acid system

The nature of interaction of Au(III) with nucleic acids was studied by using methods such as uv and ir spectrophotometry, viscometry, pH titrations, and melting-temperature measurements. Au(III) is found to interact slowly with nucleic acids over a period of several hours. The uv spectra of native calf-thymus DNA 9pH 5.6 acetate buffer containing (0.01M NaCIO4) showed a shift in λ max to high wavelengths and an increase in optical density at 260 nm. There was a fourfold decrease in viscosity (expressed as ηsp/c). The reaction was faster at pH 4.0 and also with denatured DNA (pH 5.6) and whole yeast RNA (pH 5.6). The order of preference of Au(III) (as deduced from the time of completion of reaction) for the nucleic acids in RNA > denatured DNA > DNA. The reaction was found to be completely reversible with respect KCN. Infrared spectra of DNA-Au(III) complexes showed binding to both the phosphate and bases of DNA. The same conclusions were also arrived at by melting-temperature studies of Au(III)-DNA system. pH titrations showed liberation of two hydroxylions at r = 0.12 [r = moles of HAuCl4 added per mole of DNA-(P)] and one hydrogen ion at r = 0.5. The probable binding sites could be N(1)/N(7) of adenine, N(7) and/or C(6)O of guanine, N(3) of cytosine and N(3) of thymine. DNAs differing in their (G = C)-contents [Clostridium perfingens DNA(G = C, 29%), salmon sperm DNA (G + C, 42%) and Micrococcus lysodeikticus DNA(G + C, 29%), salmon sperm DNA (G = C, 72%)] behaved differently toward Au(III). The hyperchromicity observed for DNAs differing in (G + C)-content and cyanide reversal titrations indicate selectivity toward ( A + T)-rich DNA at lw values of r. Chemical analysis and job's continuous variation studies indicated the existence of possible complexes above and below r = 1. The results indicate that Au(III) ions probably bind to hte phosphate group in the initial stages of the reaction, particularly at low values of r, and participation of the base interaction also increases. Cross-linking of the two strands by Au(III) may take place, but a complete collapse of the doulbe helix is not envisaged. It is probable that tilting of the bases or rotaiton of the bases around the glucosidic bond, resulting in a significant distrotion of the double helix, might take place due to binding of Au(III) to DNA.

Laser-fused refractory oxides for optical coatings

Laser sintering was carried out using a high power continuous-wave CO2 laser to prepare pellets of zirconia (ZrO2), hafnia (HfO2) and yttria (Y2O3) mixed oxides as starting materials in the deposition of optical coatings. Hardened recrystallized pellets appeared to have been formed during laser treatment. X-ray diffraction analysis revealed a monoclinic-to-tetragonal phase transformation in the binary system while the ternary system was found to have a mixture of two crystalline phases. Cross-sectional scanning electron microscopy showed two isothermal crystalline regions in the ternary system. The optical inhomogeneity was low in the films deposited from the laser-fused pellets, but the absorption at a wavelength of 351 nm increased with increasing HfO2 content. The films deposited from laser-fused pellets were analysed by electron spectroscopy for chemical analysis and found to be stoichiometric and homogeneous.

Preparation and characterization of hydrazine derivatives. Part-II: Reaction of transition metal ammonium double sulphates with hydrazine hydrate

Transition metal ammonium double sulphates (NH4)2M(SO4)2· 6H2O, where M = Fe, Co and Ni react with hydrazine hydrate in air giving crystalline compounds of the general formula (N2H5) [M(N2H3COO)3] H2O. The reaction proceeds through (N2H5)2 M(SO4)2, · 3N2H4, (N2H5)2 [M(OH)4 · (N2H4)2], M(N2H3COO)2 · (N2H4)2 and N2H5 [M(N2 H3 COO)3] intermediates. The reaction sequence is followed by chemical analysis and infrared spectra. A possible reaction mechanism has been suggested.

Thermal decomposition of zirconyl oxalates I. Barium zirconyl oxalate

Conditions for the preparation of stoichiometric barium zirconyl oxalate heptahydrate (BZO) have been standardized. The thermal decomposition of BZO has been investigated employing TG, DTG and DTA techniques and chemical and gas analysis. The decomposition proceeds through four steps and is not affected much by the surrounding gas atmosphere. Both dehydration and oxalate decomposition take place in two steps. The formation of a transient intermediate containing both oxalate and carbonate groups is inferred. The decomposition of oxalate groups results in a carbonate of composition Ba2Zr2OsCO3, which decomposes between 600 and 800 ~ and yields barium zirconate. Chemical analysis, IR spectra and X-ray powder diffraction data support the identity of the intermediate as a separate entity.

Thermal decomposition of zirconyl oxalates I. Barium zirconyl oxalate

Conditions for the preparation of stoichiometric barium zirconyl oxalate heptahydrate (BZO) have been standardized. The thermal decomposition of BZO has been investigated employing TG, DTG and DTA techniques and chemical and gas analysis. The decomposition proceeds through four steps and is not affected much by the surrounding gas atmosphere. Both dehydration and oxalate decomposition take place in two steps. The formation of a transient intermediate containing both oxalate and carbonate groups is inferred. The decomposition of oxalate groups results in a carbonate of composition Ba2Zr2O5CO3, which decomposes between 600 and 800° and yields barium zirconate. Chemical analysis, IR spectra and X-ray powder diffraction data support the identity of the intermediate as a separate entity.Die Bedingungen für die Herstellung von stöchiometrischem Barium-zirconyl-oxalat Heptahydrat (BZO) wurden standardisiert. Die thermische Zersetzung von BZO wurde unter Einsatz der TG-, DTG- und DTA, sowie der chemischen und Gasanalyse untersucht. Die Zersetzung verläuft über vier Stufen und wird von der umgebenden Gasathmosphäre nicht besonders beeinflusst. Sowohl die Dehydratisierung als auch die Oxalatzersetzung erfolgt in zwei Stufen. Die Bildung einer intermediären Übergangsverbindung mit sowohl Oxalat- als auch Carbonatgruppen wirken hierbei mit. Die Zersetzung der Oxalatgruppen ergibt ein Carbonat der Zusammensetzung Ba2Zr2O5CO3, das zwischen 600 und 800° zersetzt wird und Bariumzirconat ergibt. Die Angaben der chemischen Analyse, der IR-Spekren und der Röntgen-Pulver-Diffraktion unterstützen die Identität der Intermediärverbindung als eine separate Einheit.On a standardisé les conditions de préparation de l'oxalate heptahydraté de zirconyle et de baryum (BZO) stoechiométrique. On a étudié la décomposition thermique de BZO par TG, TGD et ATD ainsi que par analyses chimiques et analyses des gaz. La décomposition a lieu en quatre étapes et n'est pas trop influencée par l'atmosphère ambiante. La déshydratation et la décomposition de l'oxalate ont lieu en deux étapes. Il se forme un composé intermédiaire de transition contenant à la fois les groupes oxalate et carbonate. La décomposition des groupes oxalate fournit un carbonate de composition Ba2Zr2O5CO3 qui se décompose entre 600 et 800° pour fournir du zirconate de baryum. L'analyse chimique, les spectres IR et la diffraction des rayons X sur poudre, apportent les preuves de l'existence d'un composé intermédiaire comme entité séparée.

Mixed ligand cobalt(III) complexes of tetradentate N,N′-ethylenebis(acetylacetonimine) and flexidentate isonitroso-β-diketones and isonitrosomonoketones

A series of mixed ligand cobalt(III) complexes having the general formula Co(EA)X [where EA = dianion of N,N′-ethylenebis(acetylacetonimine) and X = anion of isonitroso-acetylacetone, IAA; isonitrosobenzoylacetone, IBA; isonitrosodibenzoylmethane, IDBM; isonitrosoethylacetoacetate, IEA; isonitrosoacetoacetanillide, IAN; isonitrosoethylmethylketone, IEMK; isonitrosobenzylmethylketone, IBMK and isonitrosopropiophenone, IPP] have been synthesised and characterised. A facial-cis-β structure (cis with respect to the coordinated two oxygen atoms of EA) with N,N,N,O,O,O ligational environment has been assigned for the complexes. The characterisation of the complexes has been based upon chemical analysis, electrical conductivity, magnetic moment, IR, PMR and electronic spectra.

Lanthanide perchlorate complexes of o,o' diisopropyl, n(-4-antipyryl) phosphoramidate

Five new complexes of lanthanide perchlorates with a new ligand O,O' diisopropyl N(-4-antipyryl) phosphoramidate (DIAP) of the general formula Ln(DIAP)4(ClO4)3 where Ln = La, Pr, Nd, Sm and Gd, have been synthesised and characterized by chemical analysis, IR(200–4000cm−1) and electronic spectra and electrical conductance data. Infrared spectral data indicate the coordination of the ligand to the metal ions in a bidentate fashion, through the C=O oxygen of the antipyrine group and the P=O group. IR and conductance values show that the three perchlorate groups are ionic. Electronic spectrum of the Nd3+ complex in the visible region, indicates reasonable covalency in the metal-ligand bond. The available data point to an eight coordinate geometry around the metal ions, with each ligand behaving in a bidentate ‘00’ fashion.

Synthesis, infrared spectra and thermoanalytical properties of transition metal sulfite hydrazine hydrates

Transition metal sulfite hydrazine hydrates, MSO3·xN2H4·yH2O whereM=Mn, Fe, Co, Ni and Zn have been prepared and characterized by chemical analysis, infrared spectra, thermoanalytical and combustion studies. The colours,x andy parameters of the complexes varied depending upon the preparation conditions. Thermal decomposition characteristics differ from metal to metal yielding metal oxides at relatively low temperatures.Mittels chemischer Analyse, IR-Spektren, thermoanalytischen und Verbrennungsstudien wurden die Hydrazinhydrate der hergestellten Übergangsmetallsulfite MSO3·xN2H4·yH2O mitM=Mn, Fe, Co, Ni und Zn beschrieben. Farbe sowie die Parameterx undy der Komplexe hängen von den Herstellungsbedingungen ab. Die thermische Zersetzung, bei der bei relativ niedrigen Temperaturen Metalloxide entstehen, ist von Metall zu Metall verschieden.

Reactivity of pyridinium poly(hydrogen fluoride) towards silicon tetrachloride, trichlorosilane and tris(amino)silanes

The reaction of silicon tetrachloride (SiCl4), trichlorosilane (HSiCl3) and tris(amino)silanes[(R2N)3SiH] with pyridinium poly(hydrogen fluoride) (PPHF) gives rise to hexafluorosilicatesalts in good yields. They have been characterized as pyridinium hexafluorosilicate(C5H5NH)2SiF6 (in the case of SiCl4 and HSiCl3) and the corresponding dialkyl ammoniumhexafluorosilicate (R2NH2)2SiF6 salts [for tris(amino)silanes] (where R2N=pyrrolidino,piperidino, hexamethyleneimino, morpholino, N-methylpiperazino and diethylamino). Theinteresting features of these reactions are the cleavage of Si---Cl, Si---H and Si---N bondsat room temperature by PPHF and fluorination of the silicon moiety to a hexa-coordinateddoubly charged anionic species. These compounds have been characterized by NMR (1H,29Si, 19F) and IR spectroscopy, and by chemical analysis.

Studies on pyridinium hexafluorostannate and its derivatives

Pyridinium hexafluorostannate, (C5H5NH)2SnF6, has been prepared by the reaction of stannous chloride or tin metal with pyridinium poly(hydrogen fluoride), PPHF, and identified by chemical analysis, IR and NMR (H-1, F-19, C-13). Making use of (C5H5NH)2SnF6 as a precursor, the following important hexafluorostannate salts have been synthesized in high yields at room temperature by ionic exchange: M2SnF6 (M = NH4, Na, K, Rb, Cs) and BaSnF6. These salts have been characterised by chemical analysis and infrared spectroscopy. Indexed powder X-ray diffraction data for Na2SnF6, Rb2SnF6 and Cs2SnF6 have been reported.

Synthesis and studies on pyridinium pentafluorozirconate and pyridinium oxotetrafluoroniobate

Pyridinium pentafluorozirconate, (C5H5NH)ZrF5, and pyridinium oxotetrafluoroniobate, (CH5NH)NbOF4, have been synthesised by the reaction of pyridinium poly(hydrogen fluoride), PPHF, with ZrOCl2 and Nb2O5, respectively. These new complexes have been characterised by chemical analysis, thermal analysis, X-ray diffraction and infrared spectra.

Sputter deposited LiPON thin films from powder target as electrolyte for thin film battery applications

Lithium phosphorus oxynitride (LiPON) thin films as solid electrolytes were prepared by reactive radio frequency (rf) magnetron sputtering from Li3PO4 powder compact target. High deposition rates and ease of manufacturing powder target compared with conventional ceramic Li3PO4 targets offer flexibility in handling and reduce the cost associated. Rf power density varied from 1.7 Wcm(-2) to 3 Wcm(-2) and N-2 flow from 10 to 30 sccm for a fixed substrate to target distance of 4 cm for best ionic conductivity. The surface chemical analysis done by X-ray photoelectron spectroscopy showed incorporation of nitrogen into the film as both triply, NE and doubly. Nd coordinated form. With increased presence of NE, ionic conductivity of LiPON was found to be increasing. The electrochemical impedance spectroscopy of LiPON films confirmed an ionic conductivity of 1.1 x 10(-6) Scm(-1) for optimum rf power and N-2 flow conditions. (C) 2011 Elsevier B.V. All rights reserved.

Low temperature synthesis of ferromagnetic (LaK)MnO3 from KCl, KBr and KI fluxes

Potassium doped lanthanum manganites have been synthesized from KCl, KBr and KI fluxes at 900, 850 and 750 °C respectively. While all the flux-grown oxides are ferromagnetic metals (Tc=290–330 K), the oxides grown from KCl and KBr fluxes crystallize in the rhombohedral structure and that synthesized from KI flux adopts the cubic structure. The enhancement in Tc correlates with the increasing tendency of the flux to get oxidized and decreasing melting points of the flux. Nearly stoichiometric (LaK)MnO3 with 33 % of Mn4+ concentration could be prepared at temperature as low as 750 °C. Composition of all the phases have been obtained from the chemical analysis of the elements present.

An investigation of carbon nanotubes obtained from the decomposition of methane over reduced Mg1− xM xAl2O4 spinel catalysts

Carbon nanotubes produced by the treatment of Mg1−xMxAl2O4 (M = Fe, Co, or Ni; x = 0.1, 0.2, 0.3, or 0.4) spinels with an H2–CH4 mixture at 1070 °C have been investigated systematically. The grains of the oxide-metal composite particles are uniformly covered by a weblike network of carbon nanotube bundles, several tens of micrometers long, made up of single-wall nanotubes with a diameter close to 4 nm. Only the smallest metal particles (<5 nm) are involved in the formation of the nanotubes. A macroscopic characterization method involving surface area measurements and chemical analysis has been developed in order to compare the different nanotube specimens. An increase in the transition metal content of the catalyst yields more carbon nanotubes (up to a metal content of 10.0 wt% or x = 0.3), but causes a decrease in carbon quality. The best compromise is to use 6.7 wt% of metal (x = 0.2) in the catalyst. Co gives superior results with respect to both the quantity and quality of the nanotubes. In the case of Fe, the quality is notably hampered by the formation of Fe3C particles.

Thermodynamic properties of Fe3O4 FeAl2O4 spinel solid solution

The Gibbs energy of mixing for the system Fe3O4-FeAl2O4 was determined at 1573 K using a gas-metal-oxide equilibration technique. Oxide solid solution samples were equilibrated with Pt foils under controlled CO+CO2 gas streams. The equilibrium iron concentration in the foil was determined by chemical analysis. The cation distribution between tetrahedral and octahedral sites in the spinel crystal can be calculated from site-preference energies and used as an alternate method of determining some thermodynamic properties, including the Gibbs energy of mixing. The solvus occurring at low temperatures in the system Fe3C4-FeAl2C4 was used to derive the effect of lattice distortion due to cation size difference on the enthalpy of mixing and to obtain a better approximation to the measured thermodynamic quantities.