Amine-templated metal squarates

Two layered amine-templated cobalt squarates, [C₆N₂H₁₄]₂[Co₂(C₄O₄)₃(H₂O)₄], I, and [C₃N₂H₅]₂[Co₂(C₄O₄)₃(H₂O)₄], II, have been prepared under hydrothermal conditions. Both I and II contain chains formed by dimers comprising two cobalt atoms bound to the squarate units, the chains being connected through hydrogen bond interactions. An amine-templated cobalt squarate of the formula [C₄N₂H₁₂][Co(C₄O₄)₂(H₂O)₄][H₂O]₂, III, as well as its Ni, Zn and Cd analogues have been prepared by room temperature reactions. III has a layered architecture wherein the cobalt-squarate monomers are linked by the amine molecules. Co and Zn analogues of [Ni(C₄O₄)(H₂O)₂(C₃N₂H₄)] with ligating imidazole units have also been prepared and characterized.     

Non-isothermal thermogravimetric pyrolysis kinetics of waste petroleum refinery sludge by isoconversional approach

Pyrolysis of petroleum refinery sludge has received global acclamation as a clean conversion technique for providing solution of sludge disposal as well as efficient resource utilization. This communication reports the kinetics study of pyrolysis of petroleum refinery sludge. Experiments were carried out by means of thermogravimetric analysis at different heating rates of 5, 10 and 20°C min⁻¹. The pyrolytic reaction is significant in the temperature range of 200–350°C and analysis and evaluation of kinetic parameters is done in the 100–500°C region of non-isothermal TG curves obtained in nitrogen atmosphere. The activation energy is calculated by iso-conversional method, then other kinetic parameters are determined by considering single reaction and two reaction global kinetic model. Two-reaction model is found to fit satisfactorily the experimental results.     

High resolution protein separations using affinity ultrafiltration with small charged ligands

Although the feasibility of affinity ultrafiltration was demonstrated more than 20 years ago, commercial applications have not developed due to the high cost and practical limitations of the large macroligands needed for highly selective separations. The objective of this study was to examine the use of small charged affinity ligands for protein purification by exploiting electrostatic interactions between the charged complex and an electrically-charged membrane. Experiments were performed using bovine serum albumin and ovalbumin with Cibacron Blue as the affinity ligand. Negatively charged versions of a composite regenerated cellulose membrane were generated by covalent attachment of a sulfonic acid functionality. Binding experiments were used to identify appropriate conditions for protein separations. The selectivity for the separation of BSA and ovalbumin was a function of the solution conditions, Cibacron Blue concentration, and membrane charge, with the addition of Cibacron Blue causing a 30-fold increase in selectivity. A diafiltration process was performed at the optimal conditions, giving a BSA product with a purification factor of more than 90-fold and a yield greater than 90%. These results clearly demonstrate the potential of using a small charged affinity ligand for high resolution protein separations.     

Preparation and thermal stability of trioxalatocobaltates of bivalent metals KM2+ [Co(C2O4)3]·xH2O

Trioxalatocobaltates of bivalent metals KM²⁺[Co(C₂O₄)₃]·x H₂O, with M²⁺ = Ba, Sr, Ca and Pb, have been prepared, characterized and their thermal behaviour studied. The compounds decompose to yield potassium carbonate, bivalent metal carbonate or oxide and cobalt oxide as final products. The formation of the final products of decomposition is influenced by the surrounding atmosphere. Bivalent metal cobaltites of the types KM²⁺CoO₃ and M²⁺CoO_3—x are not identified among the final products of decomposition. The study brings out the importance of the decomposition mode of the precursor in producing the desired end products.     

Novel simulated moving-bed adsorber for the fractionation of gas mixtures

The separation of propylene-propane mixture is an energy intensive operation commercially practiced using cryogenic distillation. The separation by pressure swing adsorption has been studied as an alternative. A fixed-bed pressure swing adsorption yields the heavy component as a pure product. The product recovery and the productivity are not high. In a moving-bed process, because of the counter-current solid-gas contact, the separation achieved is similar to that of the fractionation by distillation. Although the moving-bed operation offers the upper limit for the performance of a cyclic adsorptive process, due to mechanical complexities in the handling of solids the 'simulated' moving-bed is preferred. By moving the inlet and outlet ports of streams located along the length of the bed, a moving-bed process can be realized in a fixed bed. We describe here a 'moving-port' system which permits injection or withdrawal of the fluid along the axial direction in a fixed bed. A fixed bed embedded with the moving-port systems emulates a simulated moving-bed adsorber. The proposed adsorber can fractionate a binary gas mixture into two product streams with high purities. It is similar to the Sorbex process of UOP but does not have the eluent as an additional separating agent. A parametric study indicates that high purity products and a higher productivity by an order of magnitude can be achieved with simulated moving-beds compared to the fixed beds.     

Synthesis of a novel cis-proline-derived cyclic type VI beta-turn mimic via ring-closing metathesis

A cis-proline derived cyclic mimic of a type VI beta-turn is synthesized via a ring-closing metathesis reaction. The solution NMR conformational study indicates that the major conformer of the cyclic peptide adopts a type VIa beta-turn in CDCl(3) and a type VIb beta-turn in DMSO-d(6).     

Kinetics of the oxidation of oxalic acid by cerium(IV) sulfate in dilute sulfuric acid

The kinetics of the oxidation of oxalic acid by cerium(IV) in sulfuric acid medium has been studied voltammetrically. The specific reaction rate is 132±4.0 M^–1s^–1 at 25.0 °C. The energy of activation is 62.6±3.0 kJ mol^–1. The entropy of activation is –2.7 J mol^–1K^–1. The specific reaction rate is influenced by complexation and also by ionic strength (). The most likely mechanism has been suggested.

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(IV) . 132±4,0 M^–1c^–1 25,0 °C. 62,6±3,0 ·M^–1. –2,7 ·K^–1M^–1. , (). .

     

A Polarographic Study of ϵ-Caprolactam Complexes of Uranium and Tellurium

The polarographic behaviour of uranium and tellurium has been studied in the presence of increasing concentration of complex forming agent viz. ?-caprolactam at pH 4.4 for U(VI) and at pH 10.0 for Te(IV) at μ=0.1 M KNO₃. In both cases the waves have been found to be diffusion controlled and irreversible. The values of kinetic parameters (σπ_a and K°_f,h) have been calculated as a function of the ligand concentration. Method is suitable for the quantitative determination of these metals individually and simultaneously with the effect of diverse ions.     

Decomposition of ores by manganese dioxide: Analysis of chrome ore

Pure manganese dioxide, prepared synthetically, has been used for the oxidative decomposition of chrome ores. The usual constituents of the ores, viz. Cr(2)O(3) FeO, Al(2)O(3), MgO, CaO and SiO(2) have been estimated and the results compare favourably with those obtained by standard methods.