Gas Phase Catalysis by Metal Nanoparticles in Nanoporous Alumina Membranes

Nanoporous alumina membranes, loaded with palladium and ruthenium nanoparticles of various size, were used for gas phase hydrogenation of 1, 3‐butadiene and for oxidation of carbon monoxide, respectively. Those membranes contain 10⁹ ‐ 10¹¹ pores per cm², all running perpendicular to the surface. Membrane discs of 20 mm in diameter and only 60 μm thick, incorporated in a reactor in which the reactants can be pumped in a closed circuit through the pores, turned out to very actively catalyze hydrogenation of butadiene (Pd) and oxidation of CO (Ru). The activity of the Pd catalysts depends characteristically on the particles size, the gas flow, and of the educts ratio. As could be expected, larger particles are less active than smaller ones, whereas increasing gas flows in case of hydrogenation accelerates the reactions. Excessive hydrogen reduces selectivity with respect to the various butenes, but favours formation of butane.     

功能化程序对笼形聚偕氨肟树脂吸附和吸留性质的影响

聚丙烯颗粒在水溶液中与丙烯腈和二乙烯基苯反应,得接枝交联产物（Ⅰ）。Ⅰ被氨肟化再经成笼反应．得笼形聚偕氨肟树脂（Ⅱ）。笼内仅吸留易于除去的溶剂丙酮。若Ⅰ成笼后再氨肟化,所得吸收剂（Ⅲ）将吸留大量的羟胺,它缓慢地释放出来,干扰吸收剂对酸、碱离子或分子吸附容量的测定。Ⅱ对一些离子例如Hg2+和MnO4-的吸附能力与Ⅲ不同,被认为是两者的网络结构不同所致。     

烯烃氢甲酰化催化剂活性物种的原位1H NMR研究

The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pressurized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃. The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Ph-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process.     

New method for the determination of adsorption space volume for sorbents with an arbitrary porous structure from excess gas adsorption isotherm measurements

A new method for the determination of adsorption space volume has been proposed, which is applicable to adsorbents with an arbitrary porous structure, including nonporous adsorbents with open surfaces. The method is based on the use of an experimental excess adsorption isotherm measured over a wide range of pressures in the equilibrium gaseous phase (as a rule up to 100–150 MPa) and the absolute adsorption isotherm equation with unspecified parameters in the most general form, given by statistical physics. The method has been tested for a number of adsorption systems, and it has been found that the result was always unambiguous, correct, and stable in the sense of input data.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2381–2385, December, 1995.     

聚电解质──壳聚糖浓溶液流变学性质研究：浓度、温度、溶剂pH值和外加盐对粘度及流动性的影响

本工作用日本岩本ＲＰＸ－７０５多功能流变仪测定了在不同浓度、温度、溶剂ｐＨ值和外加盐浓度对壳聚糖在甲酸水溶液中其浓溶液粘度η随剪切速率γ的变化关系．讨论了浓度、温度等对溶液粘度、流动活化能Ｅ_γ和流动指数ｎ的影响．发现溶剂ｐＨ值减小或溶液中外加盐浓度增加，溶液粘度变小，ｎ增大，表明非牛顿流动性减弱，并且进一步讨论了零剪切粘度η_０和外加盐浓度Ｃ_ｓ的依赖关系．     

Surface recombination in breakdown time delay experiments: Effect of different cathode materials

The late afterglow in nitrogen with iron electrode is studied by the breakdown time delay method, i.e., by measuring the breakdown time delay t_d as a function of the afterglow time . It is proposed that the cause of the secondary electrons initiating the breakdown is the energy of the surface recombination of nitrogen atoms on the iron electrode. The gas-phase and macrokinetic diffusive models are used to describe the experimental breakdown time delay data. By fitting the theoretical curve to the experimental data: (1) it has been confirmed that the recombination on the molybdenum glass is of the second order and the value of the surface recombination coefficient is determined at 4 mbar; (2) it has been shown that the surface recombination on the iron electrode is of the second order, and the effective recombination coefficients are determined; (3) the analytical form of the recombination coefficient as a function of the adsorption characteristics of surfaces and the pressure of the parent gas has been derived. In addition, the orders of surface recombination on the molybdenum-, aluminum-, and gold-plated electrode were determined by the same method.     

DPPH (= 2,2‐Diphenyl‐1‐picrylhydrazyl = 2,2‐Diphenyl‐1‐(2,4,6‐trinitrophenyl)hydrazyl) Radical‐Scavenging Reaction of Protocatechuic Acid Esters (= 3,4‐Dihydroxybenzoates) in Alcohols: Formation of Bis‐alcohol Adduct

Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD₃OD/(D₆)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents.     

An Absence of Non-specific Immune Response towards para-Sulphonato-calix[n]arenes

The effects of para-Sulphonato-calix[4]arene, para-Sulphonato-calix[6]arene and para-Sulphonato-calix[8]arene on the activation of NADPH oxidase in neutrophils has been studied. All three molecules do not induce NADPH oxidase activation, and hence do not stimulate neutrophils. Measurement of cell viability demonstrates that these three water-soluble calix[n]arene derivatives are not cytotoxic.     

Chiral separation of N-(trans-4-isopropylcyclohexylcarbonyl)-D,L-phenylalanine isomers by high performance liquid chromatography

Summary A high-performance liquid chromatographic method was developed for the chiral separation of a new anti-diabetic agent, N-(trans-4-isopropylcyclohexylcarbonyl)-D-phenylalanine, and its L-enantiomer. The separation was performed on a Sumichiral OA-3300 column. Optimized mobile phase was 0.025 mol.L⁻¹ ammonium acetate in methanol solution. UV detection was at 210 nm. Baseline chiral separation was obtained within 12 minutes. The detection limits are 80 pg for the D-enantiomer and 120 pg for the L-enantiomer. RSD of the method was below 1% (n=5).