Gradient elution capillary electrochromatography and hyphenation with nuclear magnetic resonance

Coupling of gradient capillary electrochromatography (gradient CEC) and capillary zone electrophoresis (CZE) with nuclear magnetic resonance spectroscopy (NMR) was performed using a recently developed capillary NMR interface. This technique was applied for the analysis of pharmaceuticals and food. An analgesic was investigated using isocratic and gradient continuous-flow CEC-NMR. Comparison of the results demonstrated the superiority of gradient CEC over isocratic CEC. Aspartame and caffeine, both ingredients of soft beverages, were separated and analyzed by continuous flow CZE-NMR. The order of elution could be reversed by altering the pH. This reversal led to an increased sample concentration in the NMR detection cell, thus allowing the acquisition of a totally correlated spectroscopy (TOCSY) two-dimensional (2-D) spectrum of the synthetic peptide aspartame.     

Crystal structures and Mössbauer spectroscopic studies of oxo-centered trinuclear chloroacetate complexes

The crystal structures of oxo-centered trineclear cobalt-iron chloroacetate complex [Co^IIFe ₂ ^III O(CH₂ClCO₂)₆(H₂O)₃]·3H₂O (1) was compared with that of previously reported trinuclear iron complex [Fe^IIFe ₂ ^III O(CH₂ClCO₂)₆(H₂O)₃]·3H₂O (2) which has an isomorphous structure to 1. Compound 1 crystallizes in space group P2₁/n with Z=4 in a unit cell of a=14.826 (4) Å, b=4.536 (8) Å, c=14.000 (4) Å, =100.32 (2)⁰ and V=2968 (11) ų. The structure was refined to R=0.75 and R_w=0.82. The coordination geometries of the three iron atoms are observed equivalent in 1 indicating a static disorder of the position among cobalt and iron atoms. Two distinct Fe^III doublets observed in Mössbauer spectra of 1 become an indistinguishable broad doublet by dehydration of crystal water. On the other hand, no significant line-broadening is observed after the dehydration in complex 2. The results indicate that the dehydration in 2 induces a local environmental change reordering of an electronic configuration around iron atoms, whereas the remaining disordering is reflected in Mössbauer spectrum after the dehydration in 1.     

Carbonylation reaction Communication 11. Carbonylation of amino alcohols and some cyclic amines with carbon monoxide in the presence of mercuric acetate

Conclusions Primary amino alcohols react with CO in the presence of mercuric acetate at 100–200° and a pressure of 100–150 atm to give the corresponding N-(hydroxyalkyl)formamides in a yield of 1.4–2.5 M/M of reacted Hg(OCOCH₂)₃. Morpholine under analogous conditions forms the corresponding formyl derivative and the urea derivative in a 1.2–51 ratio, while cyclohexylamine forms the same derivatives in an 0.7 1 ratio.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1533–1536, July, 1973.     

Hydrolysis of dimethyl 1-acetoxy-2,2,2-trichloroethyl phosphonate

Conclusions The hydrolysis of chloroacetophos in water includes the parallel cleavage of acetic acid, hydrochloric acid and methanol. The ratio of the products, formed in the parallel steps, was determined, and we also determined the total rate constant for the hydrolysis of chloroacetophos.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2336–2338, October, 1971.     

Co-Pt bimetallic catalysts for the selective oxidation of carbon monoxide in hydrogen-containing mixtures

The performance of a Co-Pt powder and of Co-Pt catalysts supported on γ-Al₂O₃ and on the graphite-like carbon material Sibunit in selective CO oxidation in hydrogen-containing mixtures is considered. Fine particles of metal-metal solid solutions and intermetallides were obtained by the decomposition of a Co- and Pt-containing double complex salt in a hydrogen atmosphere at ～400°C. As compared to their Pt and Co monometallic counterparts, the bimetallic catalysts are more active and allow the CO concentration in hydrogen-containing mixtures to be reduced from 1 to 10^?3 vol %. This effect is likely due to the formation of bimetallic particles of a Co-Pt solid solution on the support surface.     

Determination of cadmium by substoichiometric thermal neutron activation analysis

A rapid and selective method has been developed for the determination of cadmium in environmental samples by thermal neutron activation analysis, employing substoichiometric solvent extraction technique. Alcoholic solution of 2-mercaptobenzothiazole /2-HMBT/ has been used for the substoichiometric extraction of Cd/II/ from an aqueous solution of pH 7.0 into methyl iso-butyl ketone /MIBK/.