阳离子树脂催化合成古龙酸甲酯的动力学研究

古龙酸甲酯化反应是生产维生素C的一个重要中间过程,目前工业上主要采用古龙酸和甲醇为原料,以浓硫酸作催化剂催化酯化.这一反应存在副反应较多,甲酯的色泽深,质量差,后续反应中需用碱进行中和等缺点,给后续处理带来困难.     

Structure effects of palladium complexes with phosphinated polystyrene on their catalytic properties in phenylacetylene hydrogenation

The structure of palladium acetate complexes with phosphinated polystyrene has been studied by IR and UV spectroscopy. The results indicate that on polystyrene both mono- and dinuclear palladium complexes are formed. The comparison of the catalytic properties of palladium complexes on phosphinated polystyrene with those of mono- and dinuclear complexes supported on silica confirmed the formation of dinuclear palladium complexes on polystyrene surface.

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Adsorption of monoclonal antibody variants on analytical cation-exchange resin

Monoclonal antibody (MAb) variants differing by one or two C-terminal lysine residues can be separated by cation-exchange chromatography due to the difference in their charge distribution. The adsorption of the three MAb variants on a weak cation-exchange resin was characterized using directly the raw mixture in spite of the presence of some impurities. The effects of both, pH and eluent salt concentration, on the adsorption isotherm were investigated. Under certain experimental conditions distorted peak shapes and even peak doubling for single variant injections were obtained, in addition to unexpectedly long retention times. These observations were explained based on equilibrium theory. The separation of the MAb variants was designed for an isocratic and a linear salt gradient operation. The corresponding optimal values of pH and salt concentration were determined. The use of salt gradients not only allows reducing the process time and increasing enrichment of the variants, but also leads to some loss in purity. A baseline separation could be obtained under isocratic and strongly adsorbing conditions at pH 6.3. A lumped kinetic model and a procedure for estimating the corresponding parameters were developed and validated by comparison with experimental elution chromatograms in a wide range of operating conditions.     

Structure and catalytic activity of metal complexes on carriers 3. Rhodium complexes on modified polymers and their catalytic properties in the reduction of nitrobenzene by chemically bound hydrogen

Heterogenized catalysts based on rhodium complexes attached to polymers modified by the groups 3(5)-methylpyrazole, imidazole and benzimidazole have been synthesized. The process of their formation has been investigated by IR, UV, and EPR spectroscopy. Results have been obtained for the catalytic activity of the complexes in the hydrogenation of nitrobenzene by hydrogen transfer from propan-2-ol and NaBH₄.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pp. 268–273, February, 1990.     

High-speed simultaneous ion-exclusion/cation-exchange chromatography of anions and cations on a weakly acidic cation-exchange resin column

The simultaneous ion-exclusion/cation-exchange separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin of 3 microm particle size was used to achieve the simultaneous high-speed separation of anions and cations (Cl(-), NO3(-), SO4(2-), Na(+), K(+), NH4(+), Ca(2+) and Mg(2+)) commonly found in environmental samples. The high-speed simultaneous separation is based on a combination of the ion-exclusion mechanism for the anions and the cation-exchange mechanism for cations. The complete separation of the anions and cations was achieved in 5 min by elution with 15 mM tartaric acid-2.5 mM 18-crown-6 at a flow-rate of 1.5 ml/min. Detection limits at S/N=3 ranged from 0.36 to 0.68 microM for anions and 0.63-0.99 microM for cations. This method has been applied to the simultaneous determination of anions and cations in several environmental waters with satisfactory results.     

Imidazolidinium ferrate complexes: Synthesis and catalytic properties

The new well-defined and air stable anionic iron complexes bearing an imidazolidinium ligand (2a–d) have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction studies. Starting from FeBr₂, [imidazolidinium][FeBr₄] complexes 2a and 2b were prepared. The reaction of imidazolidinium chlorides with Fe(OAc)₂, followed by a recrystallization in the air led to bis(imidazolidinium) μ-oxido-bis[trichloroferrate(III)] complexes 2c and 2d. The catalytic activity of these novel complexes has been evaluated in the cross-coupling reactions of alkyl halides with Grignard reagents.     

Synthesis and catalytic properties of barium hexaaluminates incorporated with chromium and lanthanum

Summary Barium hexaaluminates incorporated with chromium and lanthanum (Ba_1-xLa_xCrAl₁₁O_19-a) were synthesized from aqueous metal nitrates and sulfates through the precipitation, and then followed by crystallization at 1300^oC for 2 h. They had the ability to maintain heat resistance and high conversion of CH₄in methane combustion at elevated temperature.     

Synthesis and catalytic properties of niobium indenyl peroxo complexes

Synthesis of four niobium sandwich peroxo complexes containing fragments of substituted indenes was performed and their structure was proved by NMR spectroscopy and ESI-MS mass spectrometry. Catalytic activity of the complexes in the oxidation of sulfides with hydrogen peroxide was studied, and a high selectivity in the oxidation of sulfides to sulfoxides and sulfones of the sandwich peroxo complexes was found.     

Immobilization of rhodium complexes at thiolate monolayers on gold surfaces: catalytic and structural studies

Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMs) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic properties of the metal center by the neighboring thiolate molecules. Colloids with a diameter of ca. 3 nm, coated with a mixed monolayer of n-octanethiolates and thiolates with chiral rhodium-PYRPHOS end groups, were studied as hydrogenation catalysts. With methyl alpha-acetamido-cinnamate as substrate, virtually the same enantioselectivities (up to 93% ee) and full conversion were obtained as with the corresponding homogeneous [Rh(COD)(PYRPHOS)]BAr(F) catalyst. The colloids were easily recovered by filtration and reused as catalysts three times without loss of enantioselectivity. STM studies of analogous SAMs on Au(111) gave a detailed picture of the structure and dynamics of mixed monolayers of this type. The STM images showed that the catalyst-bearing thiolates are distributed statistically on the surface and that the ordered structure of the n-octanethiolate SAM can be retained during incorporation of the catalyst-bearing thiols using the place-exchange methodology.     

Structure and properties of hydroxylated surfaces of oxides

A review of works dealing with the IR spectra and structure of hydroxylated surfaces of oxides is presented. Influence of crystal structure and other factors on OH stretching modes, as well as data about bending vibrations of hydroxy groups are discussed. Experimental results are compared with data of computer simulations.     

Carrier influence on the paramagnetic and catalytic properties of supported titanium complexes

Alumina-silica possessing various Al₂O₃/SiO₂ ratios was used as a carrier of surface titanium complexes. The systems obtained were examined as models for the investigation of the macroligand (inorganic gel) influence on the physicochemical properties of supported transition metal complexes. The titanium complexes were prepared first by the reaction of CpTiCl₃, with the hydroxyl groups of the gel and then reduced by an excess of BuLi. The influence was established of the basic gel properties on: (a) the amount of titanium(IV) and titanium(III) complexes on the alumina-silica gel surfaces; (b) the symmetry of the surface Ti^III surface complexes; (c) the electron density around the surface-Ti^III ions, ionic or covalent bonds character in a complex; and (d) the catalytic activity in olefin hydrogenation.     

Structure and catalytic properties of sulfated zirconia foams

Porous sulfated zirconia foams were manufactured by a simple methodology based on the sol–gel process combined with a liquid foam template that used a surfactant mixture. A block copolymer (Pluronic F-127) and an anionic surfactant [sodium dodecylsulfate (SDS)] were mixed in different proportions in order to optimize the porous and surface properties of the ceramic material. By adjusting the SDS/Pluronic ratio, it was possible to obtain sulfated zirconia with a combination of macropores and mesopores that provided high porosity (≈90 %) and surface area (≈80 m² g^?1). The sulfate groups linked to the zirconia surface stabilized the tetragonal phase, to the detriment of the thermodynamically stable monoclinic phase. The sulfate groups and the tetragonal phase decreased as a function of the amount of SDS in the liquid foam template. The combined porous and structural characteristics, together with surface acidity, provided enhanced catalytic activity when the sulfated zirconia foams were employed in the isopropanol dehydration reaction. A further benefit was the selectivity towards propene and negligible formation of acetone.     

Separation of selenite,sulkate and iron by cation-exchange resin

Selenite, sulfate and iron(III) are separated by cation-exchange resin. Microgram amounts of selenite in iron(III) sulfate solution at pH 2 are completely adsorbed on the resin together with the large excess of iron(III). while sulfate passes through. Selenite is eluted with 0.5 N hydrochloric acid, leaving iron(III) in the resin. The procedure is applied to the determination of these elements in natural iron sulfides.