Effects of Organic Salts on the Rate of Alkaline Hydrolysis of Phthalimide in the Presence Ofcationic Micelles

Pseudo-first order rate constants (k_obs) for alkaline hydrolysis of phthalimide (PTH), obtained at constant concentration of cetyltrimethylammonium bromide (CTABr) and 35°C, vary with the concentration of organic salts ([MX]) according to the relationship: k_obs = (k₀ + K [MX])/(1 + K [MX]) where and K are empirical parameters. The values of K at 0.01 M CTABr are nearly 2 times larger than the corresponding K values at 0.02 M CTABr for sodium benzoate, disodium phthalate and disodium isophthalate.     

A novel series of materials composed of arrays of vanadium oxide container molecules, [V18O42(X)] (X = H2O,Cl-, Br-): synthesis and characterization of [M2(H2N(CH2)2NH2)5][(M(H2N(CH2)2NH2)2]2V18O42(X)]. 9H2O (M = Zn,Cd)

The synthesis and characterization of the novel systems [Zn(2)(H(2)N(CH(2))(2)NH(2))(5)][(Zn(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(H(2)O)].9H(2)O (1), [Cd(2)(H(2)N(CH(2))(2)NH(2))(5)][(Cd(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(Br)].9H(2)O (2), and [Zn(2)(H(2)N(CH(2))(2)NH(2))(5)][(Zn(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(Cl)].9H(2)O (3) have been described. These materials represent a new class of solids that have been prepared by combining conventional coordination compounds with spherical polyoxovanadate clusters. The isomorphous structures of these hybrid solids consist of two-dimensional arrays of container cluster molecules [V(18)O(42)(X)] (X = H(2)O, Br-, Cl-) interlinked by the transition metal complex moieties [M(H(2)N(CH(2))(2)NH(2))(2)] (M = Zn, Cd). These compounds contain an unprecedented complex cation, [M(2)(H(2)N(CH(2))(2)NH(2))(5)](4+). Crystal data for 1: C(9)H(46)N(9)O(26)V(9)Zn(2), monoclinic space group P2(1)/m (No. 11), a = 12.3723(7) A, b = 20.9837(11) A, c = 15.8379(8) A, beta = 97.3320(10) degrees, Z = 4.     

Estimation of Residual Nickel and Some Heavy Metals in Vanaspati Ghee

To convert vegetable edible oils into vanaspati ghee, nickel is used as a catalyst in the hydrogenation process. A simple and fast method for the trace level determination of nickel in ghee is reported. In this work different methods were applied for the extraction of residual nickel from ghee samples. Using toluene, benzene and carbon tetrachloride as organic solvents, an acid mixture was used for the extraction of nickel. Extracted nickel was quantified with atomic absorption and colorimetric methods. Among the organic solvents, toluene proved to be the best solvent mediating a 95% extraction of nickel from ghee samples. Nickel was extracted and determined in ten different brands of ghee and in all samples its amount was well above the permissible limit of WHO (0.2 μg/g). Other metals like lead, zinc, copper, and cadmium were also determined and their concentrations were found to be much below the WHO permissible limits.     

Oxidation of l-methionine with aqueous chromic acid: a kinetic study

The kinetics of oxidation of l-methionine by chromic acid in acidic medium (pH=0.83–2.2) has been studied spectrophotometrically. The effect of l-methionine and chromium(VI) concentrations on the rate of the reaction was determined. The reaction rate decreases with increasing the pH of the medium. The kinetics of the formation of a chromium(III) complex conform to the rate law:with k1=7.5×10–2s–1 and Kes1=43.85 at constant [H+]=1.9×10–2moldm–3 and [l-methionine]T= 2.0×10–2moldm–3. The same values were found with [l-methionine]T variation at constant [H+]. The reaction proceeds through formation of chromium(VI)-l-methionine ester in a rapid pre-equilibrium step, followed by a slower redox reaction of the ester. The present study provides kinetic evidence for formation of a complex ion (ester). One mole of Cr2O72– oxidizes four moles of l-methionine, which acts as a monodentate ligand and binds to chromium(VI) through the sulfur atom. The coordinated sulfur atom of l-methionine–chromium(VI) ester is responsible for the oxidative degradation (breaking of the C1-C2 bond) of l-methionine. Coordinated oxygen of the carboxylate group inhibits the cleavage of the C1-C2 bond.     

Synthesis, characterization, and reactivity of new copper(II) complexes of 2-methylthio-N-(2-pyridylmethyl)acetamide

Copper(II) complexes were prepared with the new N(2)S(thioether) ligand 2-methylthio-N-(2-pyridylmethyl)acetamide (2-HL(N2S)). [Cu(2-L(N2S))Cl(MeOH)], which formed in the presence of excess triethylamine, is a distorted square pyramidal complex containing the ligand with the amide nitrogen deprotonated. The structurally analogous complex, [Cu(2-HL(N2S))Cl(2)], which formed in the absence of triethylamine, contains 2-HL(N2S) in the tautomeric imidic acid form. Neutral copper(II) N(2)S(thioether)S(thiolate) species were generated by addition of alkyl or aromatic thiolates to [Cu(2-L(N2S))Cl(MeOH)] and an unusual decomposition pathway was discovered.     

Studies with model membranes. IX. Evaluation of thermodynamic parameters from the transition state theory of rate processes for electrolyte diffusion through silver chloride parchment-supported membranes

Diffusion rate of biologically important electrolytes through parchment-supported silver chloride membrane have been determined by the use of Nernst-Planck equation at various temperatures taking into account membrane resistance R_m, membrane potential E_m, etc. The diffusion rates were found to be primarily dependent upon the difference in the hydration energies of the counterion in the external solution. On the basis of Eisenman-Sherry theory the diffusion rate sequence of alkali metal cations point towards the weak field strengths of the fixed charge groups. The various thermodynamic parameters, namely, ΔH^?, ΔF^?, and ΔS^? were evaluated. The values of ΔS^? found to be negative, indicating that the diffusion is taking place with partial immobilization in the membrane phase. A formal relation between ΔH_hydration, ΔF_hydration, and ΔS_hydration of cations with the corresponding values of ΔH^?, ΔF^?, and ΔS^? for diffusion was also found to exist for the investigated system.     

A new method for the extraction of Au/III/ with ethyl thioacetoacetate into chloroform

A method has been developed for rapid and selective extraction of Au/III/ with ethyl thioacetoacetate /HETAcAc/ into chloroform at pH 4. The effect of various parameters on the extraction coefficient values have been studied. The stoichiometry of the extracted species 13 was obtained by the slope ratio method and by the method of substoichiometric extraction.     

Terpenoids ofPinus funebris

The complete chemical composition of the oleoresin of the Chinese pine growing in the Far East has been studied. It has been shown that the main components of the monoterpenes are -pinene, -phellandrene, and -terpineol. The sesquiterpenes contain longifolene and compounds related to it. The oleoresin of the Chinese pine is distinguished by a high content of diterpene cembrane compounds. Among the resin acids, dehydroabietic acid predominates (42.4%).Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 444–448, July–August, 1984.     

Temperature and concentration effects on supramolecular aggregation and phase behavior for poly(propylene oxide)-b-poly(ethylene oxide)- b-poly(propylene oxide) copolymers of different composition in aqueous mixtures, 1

The phase behavior (temperature vs composition) and microstructure for the two binary systems Pluronic 25R4 [(PO)19(EO)33(PO)19]-water and Pluronic 25R2 [(PO)21(EO)14(PO)21]-water have been studied by a combined experimental approach in the whole concentration range and from 5 to 80 degrees C. The general phase behavior has been identified by inspection under polarized light. Precise phase boundaries have been determined by analyzing 2H NMR line shape. The identification and microstructural characterization of the liquid crystalline phases have been achieved using small-angle X-ray scattering (SAXS). The isotropic liquid solution phases have been investigated by self-diffusion measurements (PGSE-NMR method). 25R2 does not form liquid crystals and is miscible with water in the whole concentration range; with increasing temperature, the mixtures split into water-rich and a copolymer-rich solutions in equilibrium. 25R4 shows rich phase behavior, passing, with increasing copolymer concentration, from a water-rich solution to a lamellar and copolymer-rich solution. A small hexagonal phase, completely encircled in the stability region of the water-rich solution, is also present. In water-rich solutions, at low temperatures and low copolymer concentrations, the copolymers are dissolved as independent macromolecules. With increasing copolymer concentrations an interconnected network of micelles is formed in which micellar cores of hydrophobic poly(propylene oxide) are interconnected by poly(ethylene oxide) strands. In copolymer-rich solutions water is molecularly dissolved in the copolymer. The factors influencing the self-aggregation of Pluronic R copolymers (PPO-PEO-PPO sequence) are discussed, and their behavior in water is compared to that of Pluronic copolymers (PEO-PPO-PEO sequence).     

Mass spectrometric fragmentation of saturated six membered heterocyclic systems containing two chalcogen family atoms

The mass spectra of six-membered saturated heterocycles containing oxygen, sulphur, selenium and tellurium in the 1,4-positions have been measured. The differing fragmentation modes have been characterized using high resolution, low voltage and metastable ion scan techniques. The important decomposition reactions of the molecular ions involve elimination of C₂H₄ and CH₂X (X is a chalcogen atom) and formation of [C₂H₄X]⁺ and C₂H₅⁺. The propensities of these reactions vary systematically as a function of the ability of the chalcogen to stabilize a positive charge.