Platinum(II) 1,10-phenanthroline complexes of acetylides containing redox-active groups

The new diimine ligand 3,8-di-n-pentyl-4,7-di(phenylethynyl)-1,10-phenanthroline (1) was used for the synthesis of a range of Pt(II) complexes, viz.[Pt(1)Cl2], [Pt(1)(C triple bond C-Ph)2], [Pt(1)(C triple bond C-Fc)2] and [Pt(1)(C triple bond C-p-C6H4-C triple bond C-Fc)2](Fc = ferrocenyl). Crystal structure analyses were performed for [Pt(1)Cl2] and [Pt(1)(C triple bond C-Ph)2] and revealed that the di(acetylide)pi-tweezer of the latter binds a molecule of chloroform through C-H...pi hydrogen bonds. The redox and optical properties of 1 and its complexes were investigated by (spectro-)electrochemistry, UV-Vis and luminescence spectroscopy, and an energy level diagram was derived for [Pt(1)(C triple bond C-Fc)2] and related compounds on the basis of the data collected. The ferrocenyl-substituted Pt(II) complexes are donor-sensitiser assemblies. Intramolecular quenching of the photoexcited Pt(II) diimine unit leads to very short luminescence lifetimes for [Pt(1)(C triple bond C-p-C(6)H(4)-C triple bond C-Fc)2](2 ns) and [Pt(1)(C triple bond C-Fc)2](0.3 ns), as opposed to [Pt(1)(C triple bond C-Ph)2](0.7 micros). Excimer formation has been observed for [Pt(1)(C triple bond C-Ph)(2)] at room temperature in dichloromethane and at low temperatures in frozen glassy dichloromethane and 2-methyltetrahydrofuran solution, but not in the solid state.     

Glucose utilization by lysine-producing fluoroacetate-sensitive mutants ofCorynebacterium glutamicum

A fluoroacetate-sensitive mutant was isolated fromCorynebacterium glutamicum, ATCC 21513, following mutagenesis with NTG. Batch fermentations show that in terms of growth kinetics, glucose utilization, and lysine formation, there are significant differences between the mutant and the parent. The mutant’s specific growth rate (0.22/h) is lower than that for the parent (0.34/h). Also, the yield expressed as lysine/glucose consumed does not alter as a function of the glucose concentration for the mutant, and is about 0.22, whereas for the parent, this coefficient decreases with increasing glucose concentration. The maximum specific rate of lysine production for the mutant is 1.3 g/L/h that is about two-fold higher than that for the parent.     

Estimates of the supremum of a class of stationary random processes

Under the conditions guaranteeing the uniform convergence of the spectral representations, we obtain estimates for the distribution of its supremum. We obtain estimates for the supremum of a real stationary process for which the corresponding spectral processes belong to the space Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 43, No.12, pp. 1628–1637, December, 1991.     

Manganese doping of In1−xGaxAsyP1-y films in liquid-phase epitaxy

The manganese doping of In_1–xGa_xAs_yP_1-y(0 y 1) films grown by liquid-phase epitaxy has been investigated. A study has been made of the influence of the solid-solution composition and of the method of introducing the manganese into the solution melt on the electrical properties of the films, and also on the surface morphology, the optical absorption edge, and the mismatch of the film and substrate lattice constants. It is shown that the hole density in the films decreases with decreasing y. The reasons for this are the decrease in the distribution coefficient of the acceptor manganese (from 0.3 to 0.001), the increase in the degree of compensation of the acceptors with donors (from 0.2 to 0.9), and the increase in the acceptor ionization energy. The composition of the InGaAsP:Mn film and the morphology of its surface depend on the method of preparation of the melt, this being explained by the strong interaction of the manganese atoms with the other components of the liquid phase.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 26–34, January, 1992.We thank T. G. Druzhinin, Ya. I. Otman, and V. B. Yabzhanov for helping with the experiments.     

Convergence rates of a global optimization algorithm

Second order conditions for the (pseudo-) convexity of a function restricted to an affine subspace are obtained by extending those already known for functions on ⁿ . These results are then used to analyse the (pseudo-) convexity of potential functions of the type introduced by Karmarkar.This research was completed while the first author was on sabbatical leave at the Département d'Informatiques et de Recherche Opérationelle, Université de Montréal, and supported by NSERC (grant Q015807). This research was also supported by NSERC (grants A8312 and A5408) and la Coopération franco-québécoise (project 20-02-13).     

Zur Synthese von Human-Big-Gastrin I

The synthesis of the tetratriacontapeptide amide corresponding to the revised primary structure of human big gastrin I is described. For this purpose the fragments were designed in view of the maximum use of those utilized in our previous synthesis of human big gastrin I according to the first sequence proposal. Consequently the key tripeptide-Pro-Pro-His- (sequence 7–9) was prepared in suitably protected form to be used as amino or carboxyl component for assembly of the segments 1–9 and 1–14, respectively. Final condensation of the latter nona- and tetradecapeptide derivatives with the C-terminal segments 10–34 and 15–34 via the azide and the dicyclohexylcarbodiimide/N-hydroxysuccinimide procedure, respectively, leads to crude fully protected human big gastrin I. Upon deprotection by exposure to trifluoroacetic acid in presence of ethanedithiol-(1,2) as scavanger, ion exchange chromatography and partition chromatography, the desired tetratriacontapeptide amide was isolated in satisfactory yield with a high degree of purity. The identical immunological behaviour of the synthetic material, if compared with that of natural human big gastrin I, represents ulterior strong evidence for the correctness of the newly proposed structure for this putative prohormonal form of the gastrins.

Kurzmitteilung:Wünsch E., Wendlberger G., Mladenova-Orlinova L., Göhring W., Jaeger E., Scharf R., Gregory R. A., Dockray G. J., Hoppe-Seyler's Z. Physiol. Chem.362, 179 (1981).     

Structure of the products of the reaction of 9,10-dimethylacridinium salts with aromatic o-hydroxy aldehydes

The reaction of 9,10-dimethylacridinium methosulfate with aromatic o-hydroxy aldehydes in alcohol in the presence of piperidine gives 10-methyl-4-(10-methyl-9-acridanylidenemethyl)-spiro[acridan-9,2-chromans]. The structure of the compounds obtained was established by means of the PMR, UV, and IR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 539–544, April, 1973.     

Pyrimidotetrathiafulvalenes. 3.* synthesis and properties of cation-radical salts,cation-radical betaines,and complexes of dimethyl[2,4-dioxo(1H,3H)pyrimido]tetrathiafulvalene and its N-alkyl substituted derivatives with iodine

The reaction of dimethyl[2,4-dioxo(1H,3H) pynmido]tetrathiafulvalene and its N-alkyl derivatives with iodine leads to the formation of complexes with various numbers of iodine atoms. Depending on the conditions, the betaine of the cation-radical of dimethyl[2, 4-dioxo(1 H, 3H)pyrimidojtetrathiafulvalene or a complex of the latter with dimethy1[2,4-dioxo(1H,3H)pyrimidoltetrathiafulvalene is formed by the oxidation of the pyrimidotetrathiafulvalene. The cation-radical perchlorates are formed on carrying out the oxidation of dimethyl[2,4-dioxo(1H,3H)pyrimidojtetrathiafulvalene and its N-methyl derivatives in the presence of perchloric acid. The preparation of the cation-radical salts is usually linked with the reaction of the cation-radical betaine with acids.For part 2 see [1].     

Functionalization of 2,3,4,5-Tetrahydro-1,5-benzodiazepin-2(1 H)-ones by Electrophilic Aromatic Substitution

Highly substituted, novel, 8- and 9-nitro-2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones were obtained by direct nitration of the 7-bromo-5-trifluoroacetyl (or formyl)-substituted tetrahydrobenzodiazepinones. Alkaline and acidic hydrolysis of the novel mononitro derivatives was examined. Semiempirical AM1 calculations of aromatic substituents orientation in the nitration products are presented.     

Stability of single-mode oscillations synchronized by an external signal in A multimode cyclotron-resonance maser monotron

Conclusions Premodulation of the electron beam by an external signal and appropriate choice of parameters for a synchronized CRM monotron increase the starting values of the parameters I_s proportional to the beam current and the Q's of competing modes. In maximum-efficiency regimes (for optimal beam current and externalsignal frequency), the stability of single-mode oscillations in a CRM monotron is ensured for any competing-mode Q's, regardless of the values of the parameters,, , X, or n.Scientific-Research Institute of Radio Physics. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 19, No. 3, pp. 453–459, March, 1976.