A rapid and highly selective method for the estimation of pyro-,tri- and orthophosphates

A rapid, highly selective and simple method has been developed for the quantitative determination of pyro-, tri- and orthophosphates. The method is based on the formation of a solid complex of bis(ethylenediamine)cobalt(III) species with pyrophosphate at pH 4.2-4.3, with triphosphate at pH 2.0-2.1 and with orthophosphate at pH 8.2-8.6. The proposed method for pyro- and triphosphates differs from the available method, which is based on the formation of an adduct with tris(ethylenediamine)cobalt(III) species. The complexes have the composition [Co(en)(2)HP2O7]4H(2)O and [Co(en)(2)H2P3O10]2H(2)O, respectively. The precipitation is instantaneous and quantitative under the recommended optimum conditions giving 99.5% gravimetric yield in both cases. There is no interferences from orthophosphate, trimetaphosphate and pyrophosphate species in the triphosphate estimation up to 5% of each component. The efficacy of the method has been established by determining pyrophosphate and triphosphate contents in various matrices. In the case of orthophosphate, the proposed method differs from the available methods such as ammonium phosphomolybdate, vanadophosphomolybdate and quinoline phosphomolybdate, which are based on the formation of a precipitate, followed by either titrimetry or gravimetry. The precipitation is instantaneous and the method is simple. Under the recommended pH and other reaction conditions, gravimetric yields of 99.6-100% are obtainable. The method is applicable to orthophosphoric acid and a variety of phosphate salts.

Phase relations and dielectric properties of BaTi03 ceramics heavily substituted with neodymium

Investigations on the phase relations and dielectric properties of (1 -x)BaTiO3 + xNd2/3TiO 3 (BNT) ceramics sintered in air below 1650 K have been carried out. X-ray powder diffraction studies indicate apparent phase singularity for compositions with x < 0.3. Nd2Ti207 is detected at higher neodymium concentrations. The unit cell parameter changes continuously with neodymium content, and BaTiO3 is completely cubic at room temperature with x -- 0.0525, whereas electron diffraction studies indicate that the air-sintered BNT ceramics with x > 0.08 contain additional phases that are partly amorphous even to an electron beam. SEM observations reveal that BaTiO3 grains are mostly covered by a molten intergranular phase, and show the presence of randomly distributed Nd2Ti207 grains. Energy dispersive X-ray analysis shows the Ba-Nd-Ti ternary composition of the intergranular phase. Differential thermal analysis studies support the formation of a partial melt involving dissolution-precipitation of boundary layers of BaTiO3 grains. These complex phase relations are accounted for in terms of the phase instability of BaTiO3 with large cation-vacancy concentration as a result of heavy Nd 3+ substitution. The absence of structural intergrowth in (1 - x)BaTiO3 + xNd2/3TiO3 under oxidative conditions leads to a separation of phases wherein the new phases undergo melting and remain X-ray amorphous. BNT ceramics with 0.1 < x < 0.3 have ~eff >~ 104 with tan 6 < 0.1 and nearly flat temperature capacitance characteristics. The grain-size dependence of ee,, variations of ~eff and tan 6 with the measuring frequency, the non-ohmic resistivities, and the non-linear leakage currents at higher field-strengths which are accompanied by the decrease in eeff and rise in tan 3, are explained on the basis of an intergranular (internal boundary layer) dielectric characteristic of these ceramics.

Distribution of phosphorus and oxygen between liquid steel and basic oxygen steelmaking slag

The efficiency of dephosphorisation is governed by the thermodynamic behaviour of phosphorus and oxygen in molten metal, and P2O5 and FeO in slag. The equilibrium distribution of phosphorus and oxygen, for a wide range of chemical compositions simulating the evolution of slag composition during a typical BOF blow, has been experimentally determined. A mathematical model for estimation of the activity coefficients, as a function of the chemical composition, was also attempted.

X-ray Studies on Crystalline Complexes Involving Amino Acids and Peptides. XIII. Effect of Chirality on Molecular Aggregation: The Crystal Structures of L-Arginine D-Aspartate and L-Arginine D-Glutamate Trihydrate

The crystal structures of (1) L-arginine D-asparate, C6HIsN40~.C4H6NO4 [triclinic, P1, a=5.239(1), b=9.544(1), c=14.064(2)A, a=85"58(1), /3=88.73 (1), ~/=84.35 (1) °, Z=2] and (2) L-arginine D-glutamate trihydrate, C6H15N40~-.CsHsNO4.3H20 [monoclinic, P2~, a=9.968(2), b=4.652(1), c=19.930 (2) A, fl = 101.20 (1) °, Z = 2] have been determined using direct methods. They have been refined to R =0.042 and 0.048 for 2829 and 2035 unique reflections respectively [I>2cr(I)]. The conformations of the two arginine molecules in the aspartate complex are different from those observed so far in the crystal structures of arginine, its salts and complexes. In both complexes, the molecules are organized into double layers stacked along the longest axis. The core of each double layer consists of two parallel sheets made up of main-chain atoms, each involving both types of molecules. The hydrogen bonds within each sheet and those that interconnect the two sheets give rise to EL-, DD- and DE-type head-to-tail sequences. Adjacent double layers in (1) are held together by side-chain-side-chain interactions whereas those in (2) are interconnected through an extensive network of water molecules which interact with sidechain guanidyl and carboxylate groups. The aggregation pattern observed in the two LD complexes is fundamentally different from that found in the corresponding EL complexes.

Microbial transformation of a fungicide-derived amine, dimethyl-p-phenylene diamine by Alcaligenes DM4

Abstract Microbial transformation of N, N-dimethyl-p-phenylene diamine (DMPDA), a microbial product formed from the fungicide fenaminosulf (p-dimethylaminobenzenediazo sodium sulfonate) was studied by enriching microbes in soils treated with the amine. Microorganisms isolated from DMPDA-treated soil belonged to the genera of Micrococcus, Alcaligenes, and Corynebacterium. Of the various isolates, Alcaligenes DM4 showed maximal growth on DMPDA utilizing it as sources of carbon and nitrogen. When grown in mineral salts basal medium containing 0.05% DMPDA to serve as carbon and nitrogen sources, Alcaligenes DM4 grew exponentially up to 18 h. Even though the characterization of the complete pathway of microbial degradation of DMPDA could not be carried out due to the auto-oxidation of the compound, the initial transformation product of DMPDA by Alcaligenes DM4 has been identified as a dimer. The dimer is generated into the culture medium presumably by the extra-cellular oxidase of Alcaligenes DM4. It is suggested that the risk-benefit evaluation on the use of fenaminosulf is to be made taking into consideration the microbial transformations of the fungicide.

A new synthetic procedure for the preparation of pyridinium tetrafluoroborate and hexafluorosilicate

Pyridinium tetrafluoroborate (C5H5NHBF4) and pyridinium hexafluorosilicate [(C5H5NH)2SiF6] have been prepared in good yields and high purity by the reaction of pyridinium poly(hydrogen fluoride) with oxides and acids of boron and silicon respectively. The salts have been characterised by melting points, IR, 1H and 19F NMR spectroscopy and chemical analysis.

Bile Acid Derived PET-Based Cation Sensors: Molecular Structure Dependence of their Sensitivity

A number of bile acid derived photoinduced electron transfer (PET) based sensors for metal ions are prepared. A general strategy for designing the sensor with a modular nature allows for making different molecules capable of sensing different metal ions by a change in the fluorophore and receptor unit. Keeping the basic molecular structure the same, different bile acid base fluoroionophores were prepared inorder to achieve the highest sensitivity toward the metal ions. Thesensors showed similar binding constants for the same metal ion, but the degree Of fluorescence enhancement upon addition of the metal salts were different. The sensitivities of the sensors towards a certain metal were determined from the observed fluorescence enhancement upon addition of the metal salt.

In vitro propagation of Eucalyptus grandis L. by tissue culture

Multiple shoots were induced from nodal segments of five year old trees of Eucalyptus grandis L. on solid medium containing Murashige and Skoog's (MS) Basal medium supplemented with additional thiamine, BAP and NAA. Rooting could be achieved from shoot culture on half strength MS salts or white's medium supplemented with low auxins like IAA, IBA and NAA.

An elegant direct route for the preparation of pyridinium, ammonium and alkali metal hexafluorotitanates (IV)

Pyridinium hexafluorotitanate (IV) has been prepared by a one step procedure. Addition of titanium tetrachloride to pyridinium poly(hydrogen fluoride) yields nearly quantitative amounts of pyridinium hexafluorotitanate(IV). Making use of pyridinium hexafluorotitanate as precursor, ammonium and alkali metal (Na, K, Rb, and Cs) hexafluorotitanates have been prepared in good yields. These salts have been characterised by IR, N.M.R. (1H, 13C and 19F), X-ray powder diffraction data and chemical analysis.

Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes

Metal hydrazine nitrate complexes of the type M(N2H4)Nn (NO3)2 where M = Mg, n = 2; M = Mn, Fe, Co, Ni, Zn and Cd and n = 3; metal dihydrazine azide complexes of the type M(N2H4)2 (N3)2 where M = Mg, Co, Ni and Zn; and Mg(N2H4)2 (C1O4)2 have been prepared by dissolving the respective metal powders in the solution of corresponding ammonium salts (NO3, N3 and C1O4) in hydrazine hydrate. These hydrazine complexes were also prepared by the conventional method involving the addition of alcoholic hydrazine hydrate to the aqueous solution of metal salts. The hydrazine complexes have been characterised by chemical analysis, infrared spectra and differential thermal analysis (DTA). Impact sensitivities of hydrazine complexes were determined by the drop weight method. The reactivity of these hydrazine complexes does not change with the method of preparation.

Preparation, characterisation and thermal properties of hydrazinium derivatives. Part III

Hydrazinium acetate, metavanadate, sulfite, sulphamate and thiocyanate have been prepared by the reaction of corresponding ammonium salts with hydrazine hydrate. The compounds were characterised by chemical analysis and infrared spectra. Thermal behaviour of these hydrazinium derivatives have been investigated using thermogravimetry and differential thermal analysis.

Preparation of cast aluminium alloy-mica particle composites

The optimum conditions for producing cast aluminium alloy-mica particle composites, by stirring mica particles (40 to 120 mgrm) in molten aluminium alloys (above their liquidus temperatures), followed by casting in permanent moulds, are described. Addition of magnesium either as pieces along with mica particles on the surface of the melts or as a previously added alloying element was found to be necessary to disperse appreciable quantities (1.5 to 2 wt.%) of mica particles in the melts and retain them as uniform dispersions in castings under the conditions of present investigation. These castings can be remelted and degassed with nitrogen at least once with the retention of about 80% mica particles in the castings. Electron probe micro-analysis of these cast composites showed that magnesium added to the surface of the melt along with mica has a tendency to segregate around the mica particles, apparently improving the dispersability for mica particles in liquid aluminium alloys. The mechanical properties of the aluminium alloy-mica particle composite decrease with an increase in mica content, however, even at 2.2% the composite has a tensile strength of 14.22 kg mm–2 with 1.1% elongation, a compression strength of 42.61 kg mm–2, and an impact strength of 0.30 kgm cm–2. The properties are adequate for certain bearing applications, and the aluminium-mica composite bearings were found to run under boundary lubrication, semi-dry and dry friction conditions whereas the matrix alloy (without mica) bearings seized or showed stick slip under the same conditions.

Synthesis of Thioesters from Carboxylic Acids via Acyloxyphosphonium Intermediates with Benzyltriethylammonium Tetrathiomolybdate as the Sulfur Transfer Reagent

An efficient protocol is reported for the synthesis of thioesters from carboxylic acids with use of acyloxy phosphonium salts as intermediates and benzyltriethylammonium tetrathiomolybdate as the sulfur transfer reagent.

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

Stability and structural transitions of tomato aspermy virus and cucumber mosaic virus

The properties of the S-strain of cucumber mosaic virus (S-CMV) and the B-strain of tomato aspermy virus (B-TAV) have been studied with respect to their (i) size and sedimentation behavior, (ii) requirement of divalent metal ions for stability, (iii) sensitivity towards chloride salts and the anionic detergent sodium dodecyl sulfate, (iv) solubility in ammonium sulfate-containing buffers, and (v) pH-dependent structural transitions. The results indicate that the coat protein of B-TAV is more hydrophobic than the other well-studied strains of TAV and CMV. Circular dichroism and uv absorption studies reveal pH-dependent structural transitions, although these do not result in particle swelling. These transitions appear to alter the strength of protein-nucleic acid interactions in these viruses.