Die kristallstruktur des trimethylbleiazids,Me3PbN3

Me₃PbN₃ crystallizes as colourless needles in the space group P3₁21 (or P3₂21) with a 664.6 ± 5 pm; c 1378 ± 1 pm; V 527.2 »³; Z = 3; d_c 2.781 g cm^?3. With 122 independent reflections (7 non-observed by I < o(I)) and anisotropic temperature factors for the lead atom the structure was refined to a conventional R-value (without hydrogen atoms) R = 0.042. Planar Me₃Pb groups are linked by linear N₃ groups in a 3₁ (or 3₂) screw, rendering the lead atoms an almost perfect trigonal bipyramidal coordination sphere (PbN 258 pm; PbC 225 pm). The Me₃Pb units are ordered in a skew conformation; since the lead atoms are positioned 65 pm away from the screw axes the packing of the methyl groups is not influenced (Pb·Pb 474 pm).     

Mass spectrometry of dinucleotide analogues containing 6-azauracil moiety

The mass fragmentation of three dinucleotide analogues in which D -ribose phosphodiester linkages were replaced by a three methylene unit chain has been investigated. The fragmentation pathways were proposed on the basis of high resolution data and metastable transitions. These compounds demonstrated a unique fragmentation with the formation of the fragment ion containing nitrogen at the end of the C₃H₆ chain.     

Biodegradable polycarbonates containing side carboxyl groups—synthesis,properties, and degradation study

The main objective of the presented research was to synthesise biodegradable aliphatic polycarbonates containing reactive carboxyl pendant groups and to examine the influence of the copolymer chain microstructure and composition on the process of their hydrolytic degradation and cytocompatibility. The work describes copolymerization of cyclic trimethylene carbonate derivative containing benzyl‐ester pendant group (benzyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate) with trimethylene carbonate. The copolymerization was conducted with the use of zinc (II) and lanthanum (III) acetylacetonates as ring‐opening polymerization coordination initiators. Detailed NMR analysis allowed to define the microstructure of the obtained copolymers, which depended on the composition and type of used initiator. The final tapered chain microstructure of the obtained copolymers was related to huge differences in comonomers reactivity and evidenced low level of transesterification of the main copolymer backbone. Chosen copolymers, with unprotected carbonyl groups, were subjected to in vitro degradation test and cytocompatibility studies. It was found that high concentration of carboxyl groups resulted in copolymers which formed hydrogels and were very prone to hydrolytic degradation; they were also cytotoxic toward osteoblast‐like MG 63 cells. Copolymers with lower content of carboxyl groups were found less susceptible to degradation and cytocompatible with studied cells. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2756–2769     

Reactions and stresses in polycrystalline diamond-metal and diamond-carbide compacts

Abstract

The kind of bonding phase has a significant influence on the microstructure and mechanical properties of diamond compacts. Microstructural studies of diamond with 5% wt. Ti and 5%wt. Tic (and also 30%wt. Tic) were carried out with a Transmission Electron Microscope. The TEM microstructural observations show differences between the metal and metal carbide bonding phase in diamond compacts. The mismatch of thermal expansion coefficients between diamond and the bonding metal or the compound induces significant internal stresses and may generate micro-cracks in polycrystalline diamond compacts. Twins and dislocations are the important details of microstructures in diamond crystals after HPHT sintering. They can appear as a result of residual stress relaxation. Results of measurements of residual stresses on a diamond compact surface by means of the “sin²ψ X-ray diffraction method are reported.     

Role of polyaniline morphology in Pd particles dispersion. Hydrogenation of alkynes in the presence of Pd-polyaniline catalysts

Two polyaniline (PANI) samples of various molecular masses were used for the preparation of palladium catalysts (with 2 mass % of Pd). The physicochemical features of starting polyanilines were found to substantially affect the size and extent of palladium nanoparticles aggregation. Strongly aggregated large palladium particles appeared in the PANI sample of more compact morphology (PANI-H), higher crystallinity and lower specific surface area. Pd nanoparticles of a definitively smaller size were formed in the more amorphous PANI sample of looser morphology (PANI-L) and the extent of particles aggregation was markedly lower. The catalytic properties of Pd/PANI samples were studied in a liquid phase hydrogenation of unsaturated triple bond (C≡C) in alkynes reactants, phenylacetylene, and cyclohexylacetylene. The 2 mass % Pd/PANI-L catalyst prepared using polymer of less compact texture exhibited much higher activity in both reactions. In the presence of the 2 mass % Pd/PANI-L catalyst, alkene products were formed with a high selectivity (approximately 90 %) attained at the almost complete conversion of alkynes. This highly selective hydrogenation of the C≡C to the C=C bond was related to the presence of an electroactive polymer, PANI, in close proximity with Pd active sites. Polyaniline could have a role in a steric effect as well as in a modification of adsorptive properties of Pd centres.     

(Co)polymers of oligo(ethylene glycol) methacrylates—temperature‐induced aggregation in aqueous solution

The synthesis and aggregation behavior of well‐defined thermosensitive (co)polymers of oligo(ethylene glycol) methacrylates (POEGMA) in aqueous solutions were investigated. The cloud points of the POEGMAs solutions were determined by turbidimetry and dynamic light scattering. For POEGMA (co)polymers the cloud point temperature (T_CP) increased linearly with increasing content of more hydrophilic comonomer. The mesoglobules formed by POEGMAs in dilute aqueous solutions above T_CP were studied by light scattering. The size of mesoglobules depended on the concentration and the heating procedures. The aggregates became smaller with decreasing initial concentration of polymer and increasing rates of temperature change. By selecting the proper heating and dilution procedures, the influence of the (co)polymer structure on the size of the mesoglobules could be determined. The size of the mesoglobules decreased with the length of the OEG side chains and increased with increasing content of more hydrophilic comonomer. The light scattering parameters of the mesoglobules—A₂ values and shape factors ${R_{\rm g}\over R_{\rm h}}$ —suggested that the hydrophilic OEG side chains placed at the periphery of the mesoglobules in direct contact with the surrounding water controlled the size of mesoglobules and their stability. Shape factors for all POEGMA mesoglobules indicated that the mesoglobules remained highly hydrated after formation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013