Preparation and electrochemical behavior of ordered rh adlayers on Pt(100) electrodes

Rhodium adlayers on Pt(100) substrates have been prepared by electrodeposition from dilute Rh(III) acidic solutions. The initially disordered layer is electrochemically annealed by applying a polarization program consisting of high-sweep-rate multicycle sequences between 0.05 and 0.78 V(RHE) in 0.1 M H(2)SO(4). In this way, a pseudomorphic Rh monolayer can be prepared on Pt(100) substrates. The degree of order of the electrochemically annealed layer has been evidenced not only through voltammetric experiments but also by means of scanning tunneling microscopy with atomic resolution for iodine-protected adlayers, which show a c(2 x 2) structure. The electrochemically induced ordering of the Rh adlayer appears to be a consequence of the repeated cycles of adsorption/desorption of H and, especially, oxygenated species. Voltammetry in sulfuric acid solutions permits examination of the energetics of H/anions and OH/O adsorption as a function of the Rh coverage. The first monolayer adsorbs both hydrogen and oxygenated species more strongly than the second one. This can be explained through an electronic effect caused by the underlying Pt(100) substrate.     

2-Diphenylphosphinoyloxybenzaldehyde 4-Nitrophenyl-, 4-Phenyl-1-phthalazinyl-, and Aroylhydrazones and Thiosemicarbazone

Condensation of aryl- and aroylhydrazines and thiosemicarbazide with 2-diphenylphosphinoyloxybenzaldehyde results in formation of the corresponding hydrazones and thiosemicarbazone. The products give rise to conformational equilibrium between rotational and Z,E isomers, which is strongly displaced toward the E,E',Z' isomer and is determined by the nature of substituent in the hydrazine fragment.     

Mechanical analysis on rocket propellants

The mechanical properties of solid rocket propellants are very important for good functioning of rocket motors. During use and storage the mechanical properties of rocket propellants are changing, due to chemical and mechanical influences such as thermal reactions, oxidation reactions or vibrations. These influences can result in malfunctioning, leading to an unwanted explosion of the rocket motor. Most of modern rocket propellants consist of a polymer matrix (i.e. HTPB) filled with a crystalline material (i.e. AP, AN). However, the more conventional double base propellants consist of a solid gel matrix with additives, such as stabilizers. Both materials show a mechanical behaviour, quite similar to that of general polymers. To describe the material behaviour of both propellants a linear visco-elastic theory is often used to describe the mechanical behaviour for small deformations. Because the time-temperature dependency is also valid for these materials a mastercurve can be constituted. With this mastercurve the response properties (stiffness) under extreme conditions can be determined. At TNO-PML a mastercurve of a double base propellant was constituted using dynamical mechanical analysis (DMA) and compared with a mastercurve reduced from conventional (static) stress relaxation tests. The mechanical properties of this double base propellant determined by DMA were compared with conventional (quasi-static) tensile test results. This revised version was published online in July 2006 with corrections to the Cover Date.     

Highly sensitive method for the determination of a new anthracycline: Pirarubicin

Summary A new and highly sensitive HPLC method for the simultaneous determination of pirarubicine (THP-doxorubicin) and its metabolites, adriamycin and adriamycinol, in human plasma, is described. Samples were treated by liquid-liquid extraction, the organic phase removed and the residue dissolved in methanol. Separation was on a Lichrocart Supersher RP 8 column, (250×4 mm) 4 m, with a mobile phase of acetonitrile/methanol/formate-buffer.     

Catalytic nitrobenzene oxidation of lignins

Alkaline nitrobenzene oxidation of hardwood and softwood lignins in the presence of redox and phase-transfer catalysts was studied. The selectivity of oxidation of lignins increased by 1.7 to 1.9 times. A possible mechanism of catalysis is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 3004–3007, December, 1996.     

Clathrate formation in water-cyclic ether systems at high pressures

Experimental data on the investigation of the water-trimethyleneoxide system,P, t, x phase diagram (up to 6 kbar) are presented. The results are compared with those on water systems with ethyleneoxide, 1,3- and 1,4-dioxane, 1,3-dioxolane and tetrahydrofuran, on the basis of which a summarizedP, t, x diagram is plotted for water-cyclic ether systems. It is shown that in all the systems in which a cubic structure II hydrate forms at 1 bar, it eventually turns to cubic structure I under pressure. The nature of high pressure hydrates is discussed.Dedicated to the memory of D. W. Davidson.     

Thermal coefficient of linear expansion of non-crystalline chalcogenides in the As-S-Se-Te-I system

The object of the paper is an investigation of the glasses of the (As₂S₃)_x(AsSe_0.5Te_0.5I)_100-x. type for 65≤;x≤;95, using methods of thermomechanical analysis. Values of the thermal coefficients of linear expansion in solid and visco-plastic phase were determined. it was shown that introducing arsenic-sulfide in glass-matrix AsChI, i.e. (AsSe_0.5Te_0.5I), leads to an increasing stability of these glasses. The characteristic temperatures of softening Tg and the temperature of the beginning of deformation t_w increase by increasing content of As₂S₃. The analytical forms of dependence of four significant physical values α_g, α_l, Tg, Tw, as a function of As₂S₃ content in the structure of glasses were fitted. This revised version was published online in July 2006 with corrections to the Cover Date.     

Aufbau und Zunderverhalten von Niob-Bor-Silicium-Legierungen

Zusammenfassung Der Aufbau des Dreistoffes Niob-Bor-Silicium wird bei 1600° C mit Hilfe röntgenographischer und mikroskopischer Methoden ermittelt. Die T 2-Phase sowie die ternäre D 8₈-Phase besitzen einen ausgedehnten homogenen Bereich. Während Silicium in T 2 durch Bor bis annähernd Nb₅SiB₂ substituiert wird, besteht beim D 8₈-Typ eine Gitterauffüllung gemäß Nb₅Si₃B. Oxydationsversuche im Bereich von 400 bis 1200° C zeigen vor allem die Selektivität, indem Nb–Mk bzw. die Nb-Boride bevorzugt in Pentoxyd übergehen. Silicium übt einen stabilisierenden Einfluß auch auf das Bestehen von -Nb₂O₅ aus. -Nb₂O₅ tritt als Mischphase mit Anionendefekt auf, wodurch die sogenannte scharfe und diffuse Form erklärt wird. Die Umwandlungstemperatur - wird teilweise erheblich oberhalb der vonGoldschmidt angegebenen beobachtet. Die -Form wird als M-Modifikation nachBrauer identifiziert und relativ häufig nachgewiesen. Die -Form erweist sich alsBrauersche H-Modifikation und entsteht offensichtlich stufenweise (fast kontinuierlich) aus -Nb-Oxyd. Auf die Anionendefekt-Bildung wird nachdrücklich hingewiesen.Mit 3 Abbildungen     

Structurization and Optical Activity in Cellulose Triacetate Modified with Trifluoroacetic Acid Vapor

Structurization in cellulose triacetate modified with trifluoroacetic acid vapor and its effect on the optical activity are studied.     

2,3-Diphenylthiazolo[3,2-a]pyrimidinium salts

The corresponding 2,3-diphenyl[3,2-a]pyrimidinium salts were obtained by the condensation of 4,5-diphenyl-2-aminothiazole perchlorate with -diketones, -chlorovinyl ketones, -chlorovinyl aldehydes, and 1,1,3,3-tetraethoxypropane. The PMR spectra were used to prove the structures of the compounds obtained, particularly to select the structures of the isomeric salts obtained in the condensation with unsymmetrical -diketones, -chlorovinyl ketones, and -chlorovinyl aldehydes. As a rule, the latter give one isomer — the -unsubstituted (relative to the bridge nitrogen atom) derivative.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 629–631, May, 1972.