Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

Diffusion Structural Analysis Study of Titania Films Deposited by Sol-Gel Technique on Silica Glass

The diffusion structural analysis (DSA) was used to characterize microstructure changes of hydrous titania gel films under in situ conditions of heating. TG and DTA were used in order to elucidate the processes controlling the formation of anatase film during heating of hydrous titania gel film. The annealing of porosity and near surface structure defects of the dehydrated titania films was indicated by DSA in the temperature range 255–700°C as the decrease of radon release rate. It was demonstrated that the annealing was enhanced on heating in oxygen in comparison with heating in argon. The DSA experimental results were compared with model curves describing the radon diffusion mobility and the annealing of radon diffusion paths.     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Über die Magnetischen Eigenschaften der Cobaltate Na6CoS4, Na6CoSe4 und K6CoS4

Magnetic Properties of the Cobaltates Na₆CoS₄, Na₆CoSe₄, and K₆CoS₄ The alkali metal cobalt chalcogenides Na₆CoS₄, Na₆CoSe₄, and K₆CoS₄ crystallize in the space group P6₃mc with Z = 4. The structure is characterized by isolated [CoX₄]-tetrahedra. The magnetic susceptibilities show Curie-Weiss behaviour. The deviations at low temperatures are caused by antiferromagnetic interactions. The magnetic moments are discussed with regard to ligand-field parameters.     

Proteinases from Carica papaya Latex

Data on the proteinase complex from Carica papaya latex were reviewed. The properties and applications of the domestic preparation cucumazyme and known medicinal preparations based on papaya proteinases (caripazyme, lecozyme, lecopain) were compared.     

Lanthanum nitrate decomposition by both temperature programmed heating and citrate gel combustion

Thermal decomposition of lanthanum nitrate to lanthanum oxide was carried out by both temperature programmed heating (TPH) and citrate-gel combustion. The temperature programmed heating was carried out under flow of oxidizing (air), neutral (nitrogen) and reducing (25 vol.% hydrogen+argone mixture) gases, and the processes were controlled by simultaneous thermogravimetry and differential thermal analysis. It was shown that hydrogen atmosphere helps to reduce temperatures of all decomposition steps. The results of TPH were utilized to check the nature of residues in the products of lanthanum nitrate-to-oxide conversion performed via citrate-gel combustion technique.     

A NOVEL METHOD FOR FABRICATING COMPOSITE MOSAIC MEMBRANE WITH UNIQUE NF SELECTIVITY

A novel method of fabricating composite mosaic membranes was studied on the basis of interracial polymerization （IP） by coating a thin selective layer onto the surface of a micro-porous hollow-fiber membrane, in which, 2,5-diaminobenzene sulfonic acid was used as one monomer of the IP reaction, and a mixture of trimesoyl chloride （TMCI） and 4-（chloromethyl） benzoyl chloride as the other monomer. Through the IP reaction a thin selective layer with negatively charged groups could be first formed on the polyethersulfone （PES） support membrane. Then trimethylamine solution was introduced to modify the IP layer through a quaternization reaction. Thus the selective layer of this composite membrane contained both negatively charged and positively charged groups to perform the mosaic functionality. Characterization of the composite mosaic membranes was carried out through permeation experiments using different inorganic salts and dyes. The experimental results showed that the membranes could permeate both mono- and bi-valent inorganic salts, but reject larger organic molecules. Such a mosaic membrane is potentially useful for the separation of salts from water-soluble organics, especially in dye and textile industries.     

Inorganic Sol-Gel Preparation of Medium Sized Microparticles of Li2TiO3 from TiCl4 as Tritium Breeding Material for Fusion Reactors

Microspheres of Li₂TiO₃ were fabricated by a classical, inorganic sol-gel process from commercially available TiCl₄. Elaborated process consists of the following main steps: (1) dissolving of TiCl₄ in concentrated aqueous HCl and addition of LiOH; (2) formation of sol emulsion in 2-ethylhexanol-1 containing the surfactant SPAN-80 (EH); (3) gelation of emulsion drops by extraction of water with partially dehydrated EH; (4) impregnation of gel to Li:Ti molar ratio MR = 2; (5) thermal treatment at 1200°C in order to receive chloride free product. This temperature can be significantly lowered (to 750°C) by dechlorination starting solution TiCl₄ by chemical treatment of the with nitric acid to form of nitrate-stabilized titania sols. Tritium release from sol-gel made Li₂TiO₃ microspheres were found very close to that observed for other traditional materials, however for the first sample process starts slightly earlier.     

Formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber blends: Effects of preparation method,composition, and thermal condition

The effects of preparation method, composition, and thermal condition on formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber (iPP/EPR) blends were studied using modulated differential scanning calorimeter (MDSC), wide angle X‐ray diffraction (WAXD), and phase contrast microscopy (PCM). It was found that the α‐iPP and β‐iPP can simultaneity form in the melt‐blended samples, whereas only α‐iPP exists in the solution‐blended samples. The results show that the formation of β‐iPP in the melt‐blended samples is related to the crystallization temperature and the β‐iPP generally diminishes and finally vanishes when the crystallization temperature moves far from 125 °C. The phenomena that the lower critical temperature of β‐iPP in iPP/EPR obviously increases to 114 °C and the upper critical temperature decreases to 134 °C indicate the narrowing of temperature interval, facilitating the formation of β‐iPP in iPP/EPR. Furthermore, it was found that the amount of β‐iPP in melt‐blended iPP/EPR samples is dependent on the composition and the maximum amount of β‐iPP formed when the composition of iPP/EPR blends is 85:15 in weight. The results through examining the effect of annealing for iPP/EPR samples at melt state indicate that this annealing may eliminate the susceptibility to β‐crystallization of iPP. However, only α‐iPP can be observed in solution‐blended samples subjected to annealing for different time. The PCM images demonstrate that an obvious phase‐separation happens in both melt‐blended and solution‐blended iPP/EPR samples, implying that compared with the disperse degree of EPR in iPP, the preparation method plays a dominant role in formation of β‐iPP. It is suggested that the origin of formation of β‐iPP results from the thermomechanical history of the EPR component in iPP/EPR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1704–1712, 2007