Polarographic separation of cobalt from nickel

Summary The polarographic behaviour of nickel and cobalt in the mixed base electrolytes, urea-pyridine and urea-hydrazine has been studied. The effect of p_H, concentration of supporting electrolyte and the presence of various other ions was investigated. Well defined polarograms for both the elements were obtained at p_H 6.0 and 5.0 respectively. Attempts were made to utilize these observations in the separation of the two cations. While the difference in E _1/2 of the ions in urea-pyridine was greater than –0.3 volts that in urea-hydrazine was about –0.2 volts or slightly less even under the optimum conditions. In a mixed solution the waves for Co and Ni were therefore well developed and separated in the former base electrolyte. The polarograms in urea-hydrazine were, however, of little analytical use because of the washing away of the Ni wave due to the presence of even small amounts of cobalt.

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Zusammenfassung Das polarographische Verhalten von Nickel und Kobalt in Harnstoff-Pyridin- und Harnstoff-Hydrazinlösung wurde untersucht und der Einfluß des p_H-Wertes, der Leitsalzkonzentration sowie der Gegenwart verschiedener anderer Ionen festgestellt. Bei p_H 6,0 bzw. 5,0 wurden für beide Elemente gut ausgebildete Polarogramme erhalten. Es wurde versucht, die erhaltenen Ergebnisse zur Trennung der beiden Ionen zu benutzen. In Harnstoff-Pyridinlösung beträgt der Unterschied der beiden Halbstufenpotentiale mehr als –0,3 V und man erhält gut ausgebildete und voneinander getrennte Stufen. In Harnstoff-Hydrazinlösung dagegen beträgt der Unterschied nur –0,2 V oder etwas weniger, selbst unter optimaler Bedingungen, und die Ni-Stufe wird schon durch kleine Kobaltmengen beeinträchtigt.

     

Electric field gradients in various chemical environments of133Ba by the sum peak method

The sum peak at 437 keV (356+81 keV) has been measured in various chemical and physico-chemical environments. The fact that the intensity ratio of the sum peak to its single peak changes with the circumstances in which the radioactive source is placed is used to observe the effect of the chemical environment on directional correlation coefficients of 351–81 keV cascade in¹³³Ba−¹³³Cs decay and to detect the variations in the electric field gradient in different barium compounds. The sum peak method has been found to be useful in describing the chemical influences onG ₂₂ parameters and hence in the study of electric field gradients.     

Über die Herstellung von Äther der enantio-14, 15-Dinorlabdan-Reihe aus Eperusäure

The Conversion of Eperuic Acid into Ethers of the enantio-14, 15-Dinorlabdane Series 5 and 6 are strongly odiferous substances of the ambra-type. Their enantiomers 7 and 8 , hitherto unknown, have been synthesized from eperuic acid (4) and their olfactory properties compared with those of 5 and 6 . 4 was esterified by CH₂N₂ and dehydrogenated with (C₆H₅Se)₂/H₂O₂ to the α,β-unsaturated ester 9 (61%). Oxidation by KMnO₄ in acetone yielded the ketone 3 (60%). Epoxidation followed by treatment with acid converted 3 into the acetals 7 (61%) and 8 (14%). 7 and 8 differ from 5 and 6 in odor intensity, and 6 and 8 show slightly different odor quality.     

Application of the sum peak method to study changes in the K-capture probability to the 1086 keV level and perturbed angular correlation parameters in the decay of152Eu

The sum peak method has been applied to electron capture probability changes to the 1086 keV level in the decay of¹⁵²Eu in the different environments, e.g. ethylenediaminetetraacetic acid (EDTA), bovine serum albumin (BSA) and hydrochloric acid (HCl). An attempt is also made to determine the effect of chemical environment on the directional correlation coefficient of the 1409–122 keV - cascade in¹⁵²Eu ¹⁵²Sm decay. A change of G₂₂ is found in the different chemical forms.     

Kinetic studies of nonaqueous polymerization of methyl methacrylate initiated by ferric laurate–n-hexyl amine system

The polymerization of methyl methacrylate was studied in carbon tetrachloride medium with ferric laurate, a metal soap, in combination with n-hexyl amine as the initiator system at 60°C. The rate of polymerization was found to be linear with the monomer concentration and proportional to the square root of both ferric ion and amine concentration. A reaction scheme involving initial complex formation between ferric ion and amine and subsequent reaction of the complex with the solvent molecule to produce free radicals responsible for initiation of polymerization has been postulated to account for the observed results.     

Enantioselective synthesis of (−)-α-conhydrine via cyclic sulfate methodology

An asymmetric synthesis of (−)-α-conhydrine is described using the Sharpless asymmetric dihydroxylation and the regiospecific nucleophilic opening of a cyclic sulfate as the key steps.     

Electrospray tandem mass spectrometric analysis of zeaxanthin and its oxidation products

Carotenoids have been implicated in protection of the eye from light-mediated photo-toxicity caused by free radicals. Under conditions of normal oxidative stress the carotenoids serve as protective antioxidants; however, when the oxidative stress exceeds the antioxidant capacity, carotenoids can be oxidized into numerous cleavage products. The determination and identification of oxidized carotenoids in biological samples remains a major challenge due to the small sample size and low stability of these compounds. We investigated the reaction of various zeaxanthin cleavage products with O-ethyl hydroxylamine to evaluate their levels in a biological sample. For this, a sensitive and specific electrospray tandem mass spectrometry (ESI-MS/MS) was developed, avoiding the classical lower sensitive and specific HPLC-UV and fluorescence absorption methods. Protonated molecules [M + H](+) of carotenoids upon collision-induced dissociation produced a number of structurally characteristic product ions. A series of complicated clusters of product ions differing in 14 (CH(2))and 26 (C(2)H(2))Da was characteristic of the polyene chain of intact carotenoids. All carotenoid ethyl oximes of zeaxanthin cleavage products were characterized by the losses of 60 and 61 Da in their MS/MS spectra. Through the application of the LC/MS/MS method, we identified two oxime derivatives of 3-hydroxy-beta-ionone and 3-hydroxy-14'-apocarotenal with protonated molecules at m/z 252 and m/z 370 respectively, in a human eye sample.     

On a new partitioning of the Hamiltonian in many-body calculation of pair-correlation energies in closed-shell systems

We introduce here a new partitioning of the Hamiltonian in calculating pair-correlation energies using many-body perturbation theory, by which we are able to eliminate the off-diagonal particle–hole (p–h) ladders exactly to all orders in the perturbation expansion. In this formulation, the particle states turn out to be different for each distinct pair of hole states in the correlation energy calculation. We have also included the contributions of the diagonal particle–particle (p–p) and hole–hole ladders exactly to all orders. The effect of the off-diagonal p–p ladders has been estimated for each pair by computing the third-, foruth- and fifth-order energies. For highly symmetric systems the present partitioning yields in general symmetry-broken orbitals. Here one may use an average kind of partitioning for all the partners of the degenerate sets, which restores the symmetry and at the same time ensures cancellation of the p–h ladders exactly at the lowest order and approximately at the higher orders. Results are presented for a selection of 6π-electron conjugated systems. The correlation energy for each pair is in excellent agreement with that obtained from a partial CI calculation involving all double excitations from this pair. The advantages of implementing the present scheme in larger systems has been discussed.