Hydrolysis of bis(chloromethyl)phosphonic acid p-nitroanilide in aqueous micellar surfactant solutions

The hydrolysis of bis(chloromethyl)phosphonic acid p-nitroanilide has been studied in the pH range 6.86–13.0 and the effects of ionic surfactant micelles on this process have also been examined. The nature of the micellar effects of cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) on this reaction lead us to conclude that both the neutral and anionic forms of the substrate are reactive, and that in the range of pH > pK_a hydrolysis of the ionic form of the anilide predominates, while at pH < pK_a the reaction of the neutral form is predominant. The binding constants for both the neutral and anionic forms of bis(chloromethyl)phosphonic acid p-nitroanilide in micellar CTAB and SDS solutions have been determined using a kinetic method, as well as by measuring the changes in the acid-base properties of the substrate resulting from the influence of micelles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1718–1722, August, 1990.     

Synthesis of bifunctional derivatives of nitroxyl radicals of imidazoline

3-Imidazoline derivatives that contain a substituent with a functional group in the 2 position of the heteroring were obtained by the reaction of 1,2-hydroxyamino ketones with functionally substituted ketones and ammonia. The use of the reactivity of the endocyclic imino group makes it possible to accomplish the synthesis of a number of bifunctional derivatives of nitroxyl radicals of imidazoline and imidazolidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 772–778, June, 1990.     

Kinetics of the metal-exchange reaction of deuteroporphyrin and gematoporphyrin cadmium complexes with cobalt chloride in acetonitrile

The metal-exchange reaction of cadmium deuteroporphyrin (CdDP) and cadmium gematoporphyrin (CdGP) with cobalt chloride in acetonitrile is studied spectrophotometrically. The stoichiometry of the metal-exchange reaction is determined. The results are compared with the exchange reaction of cadmium mesoporphyrin and cadmium protoporphyrin with cobalt acetate in acetonitrile. Substituents in the 2,4-positions of cadmium complexes of protoporphyrins are shown to influence the rate of the metal-exchange reaction. The increasing order of the rates of the metal-exchange reaction between protoporphyrins and cobalt chloride in acetonitrile is established.     

Self-association of daunomycin antibiotic in various buffer solutions

The self-association of an antitumor antibiotic, daunomycin (DAU), in various buffer solutions, including water-salt solutions, phosphate buffer, HEPES, and TRIS, was studied by 1D and 2D ¹H NMR spectroscopy at 500 MHz. The two-dimensional NOESY spectra and the concentration and temperature dependences of the chemical shifts of antibiotic protons in the solvents studied showed that the self-association parameters of DAU were independent of the type of buffer solutions. The most probable two spatial structures of the dimer of DAU in solution were constructed by the method of molecular mechanics. The mutual orientation of the chromophores was parallel in one structure and antiparallel in the other.     

N,N-dimethyl-N-(methylferrocenyl)amine as a bifunctional component of initiating systems for free-radical polymerization of methyl methacrylate

The specific features of free-radical polymerization of methyl methacrylate in the presence of a new initiating system, benzoyl peroxide-N,N-dimethyl-N-(methylferrocenyl)amine, are studied. Mutual influence of the ferrocene and amino groups on the kinetic parameters of polymerization and on the microstructure of the resulting polymers is revealed. The polymer formed in the presence of this initiating system is shown to have a predominantly syndiotactic structure.     

Isolation,purification, and characterization of two forms of lipase from the fungusMucor miehei

Two forms of lipases (A and B) have been isolated from the fungusMucor miehei UzLT-3 and purified to the homogeneous state, and molecular masses of 43 and 40 kDa have been established for them from the results of disk electrophoresis and gel filtration. The isoelectric points of the lipases are 4.7 for form A and 4.9 for form B. Institute of Microbiology, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax 41 71 29. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 673–676, September–October, 1994.     

Preparation and crystal structure of the La2Ni12P5 and isotypic ternary lanthanoid—Nickel phosphides

The new ternary phosphide La₂Ni₁₂P₅ has been prepared by direct arc melting of the components as pure metals and red phosphorus. The crystal structure has been determined using X-ray single crystal diffraction data. The compound exhibits a new type of crystal structure, P2₁/m with lattice parameters a = 10.911(3), b = 3.696(2), c = 13.174(4) Å, β = 108.02(2)°, V = 505,2(6) ų, Z = 2. Atomic parameters least squares refinement of 116 independent variables (anisotropic approximation for thermal vibrations) employed 1 284 independent I_o(hkl); R_F = 0.0278 and R_W = 0.0287. The crystal structure is characterized by trigonal prismatic arrangement of phosphorus atoms stacking variant of infinite (with phosphorus centered) columns built by metal trigonal prisms ‖ [010]. Two or three such columns are connected through common edges (lanthanum atoms). The compounds RE₂Ni₁₂P₅ (where RE = Ce, Pr, Nd and Eu) display the same with La₂Ni₁₂P₅ crystal structure. Lattice parameters of these compounds have been refined using powder diffraction data.