Engineering of functional supramacromolecular complexes of proteins (enzymes) using reversed micelles as matrix microreactors

The size of the inner water cavity of reversed micelles formedin a triple system ‘water-surfactant-organic solvent’can be widely varied by changing the degree of surfactant hydration.This gives grounds to use reversed micelles as matrix microreactorsfor the design of supramolecular complexes of proteins. Usingultracentrifugation analysis, it has been demonstrated thatthe oligomeric composition of various enzymes (ketoglutaratedehydrogenase, alkaline phosphatase, lactic dehydrogenase, glyceraldehyde-3-phosphatedehydrogenase) solubilized in reversed micelles of Aerosol OT[sodium bis(2-ethylehexyl)sulfosuccinate] in octane changesupon variation of the degree of hydration. An oligomeric complexforms under conditions when the radius of the micelle innercavity is big enough to incorporate this complex as a whole.At lower degrees of hydration the micelles ‘uncouple’such complexes to their components. The catalytic propertiesof various oligomeric complexes have been studied. Possibilitiesof using reversed micelles for the separation of subunits ofoligomeric enzymes under non-denaturating conditions have beendemonstrated. In particular, the isolated subunits of alkalinephosphatase, lactic dehydrogenase and glyceralde-hyde-3-phosphatedehydrogenase have been found to be active in Aerosol OT reversedmicelles. The dependences of the catalytic activity of oligomericenzymes represent saw-like curves. The maxima of the catalyticactivity observed at these curves relate to the functioningof various oligomeric forms of an enzyme. The radii of the micelleinner cavity under conditions when these maxima are observedcorrelate with the linear dimensions of the enzyme oligomericforms. Correlation of the position of a maximum with the shapeof an oligomeric complex is discussed.     

Sex attractants for Geometrid and Noctuid moths

Male moths belonging to 17 species of Geometridae and nine species of Noctuidae were captured in traps baited with synthetic chemicals as part of a field screening program. The compounds tested were the C₁₈-C₂₂ homologs of: (1) (3Z,6Z,9Z)-triene hydrocarbons; (2) mixtures containing equal quantities of (3Z,6Z)-cis-9,10-expoxydienes, (3Z,92Z)-cis-6,7-epoxydienes, and (6Z,9Z)-cis-3,4-epoxydienes; (3) (3Z,6Z)-9S,10R-epoxydienes; (4) (3Z,6Z)-9R,10S-epoxydienes; and (5) (3Z,6Z,9Z,11E)-nonadecatetraene. Field captures and electroantennographic assays revealed a high degree of specificity in the responses of many species to the synthetic chemicals. In several species the ability of males to discriminate between the 9S,10R and 9R,10S enantiomers of the monoepoxydiene isomers was clearly shown. Synergists and inhibitors were discovered for several of the reported attractants, some of which were not previously known to have semiochemical activity. The geometrid moths captured includedEpirrhoe sperryi (Herbulot),Mesoleuca ruficillata (Guenée),Triphosa haesitata (Guenée),Metanema inatomaria (Guenée),Prochoerodes transversata (Drury),Cabera erythemaria (Guenée),Synaxis jubararia (Hulst),Dysstroma brunneata ethela (Hulst),Eulithes testata (Linnaeus),Sicya macularia (Harris),Xanthorhoe iduata (Guenée),X. abrasaria aquilonaria (Herrich-Schäffer),X. munitata (Hübner),Itame loricaria (Eversmann),Eupithecia annulata (Hulst),E. rovocastaliata (Packard) andE. satyrata dodata (Taylor). The noctuid moths captured includedBleptina caradrinalis (Guenée),Idia américalis (Guenée),I. aemula (Hübner),Rivula propinqualis (Guenée),Lomanaltes eductalis (Walker),Spargaloma sexpunctata (Grote),Caenurgina distincta (Neumuller),Euclidia cuspidea (Hübner), andZale duplicata (Bethune). Six of the nine noctuid species captured belong to three subfamilies for which sex attractants had not been reported previously. Details for the stereospecific synthesis of (3Z,6Z)-cis-9,10-epoxydienes are also reported.Issued as NRCC No. 24314.     

Catalysts for the selective dehydrogenation of high molecular weight paraffins

Selective dehydrogenation of high molecular weight linear paraffins is an important process step for the production of biodegradable detergents. Pt, PtSn, PtGe and PtPb supported on -A1₂O₃ doped with alkaline metals were characterized and tested in then-decane dehydrogenation reaction. When alkaline metals are added to Pt/Al₂O₃ a promoting effect on the selectivity to olefins in then-decane dehydrogenation is observed. Regarding PtSn/Al₂O₃ -doped catalysts their performance depends on the alkaline metal used as dopant, the Sn content and the preparation method. Moreover these bimetallic catalysts show a better olefin yield and a lower selectivity to gases and aromatics than the monometallic platinum catalysts. PtGe and PtPb based catalysts have an analogous behavior to the PtSn one but its selectivity to olefins is lower.     

三氯异氰尿酸生产技术研究

对三氯异氰尿酸合成反应过程中的主要工艺参数进行分析和实验研究,并成功地开发出了连续法生产三氯异氰尿酸的新工艺,该工艺和传统工艺相比,具有生产安全、高效、节能的特点。     

Sintering behaviour of La1−xSrxFeO3−δ mixed conductors

The sintering properties of La_1−xSr_xFeO_3−δ (x = 0.1, 0.25) mixed conductors have been investigated with particular emphasis on the effect of secondary phases due to cation non-stoichiometry (±5 mol% La excess and deficiency). Secondary phases, located at grain boundaries in cation non-stoichiometric materials, increased the sintering temperature compared to single-phase materials. Extensive swelling in final stage of sintering was observed in all materials, which resulted in micro-porous materials. The swelling was most pronounced in the phase pure and two-phase materials due to La-deficiency, while refractory secondary phases in La-excess materials inhibited both sintering, grain growth and swelling. In La-deficient materials, formation of molten secondary phases resulted in rapid swelling due to viscous flow. The present findings demonstrated the importance of controlling sintering temperature and time, as well as careful control of the cation stoichiometry of La_1−xSr_xFeO_3−δ in order to achieve fully dense and homogenous La_1−xSr_xFeO_3−δ ceramics.     

An EXAFS study of the Mo/TiO2 hydrodesulphurization catalysis

In-situ EXAFS studies of sulphided Mo/TiO₂ catalysts have shown that at low Mo loadings (2–4 wt%), an active species with a short Mo-S distance of 2.25 Å is formed, while on Mo/TiO₂ with high Mo loadings as well as on Mo/-Al₂O₃, bulk MoS₂ (Mo-S, 2.42 Å) is formed. The species with the short Mo-S distance has Mo in an oxidation state close to 6 + and is likely to result from the sulphidation of the tetrahedral molybdate species present in the oxidic precursor at low Mo loadings. The calcination temperature of the oxidic precursor appears crucial, a high calcination temperature of 973 K favouring the formation of MoS₃ on sulphidation, and a low calcination temperature of 623 K favouring MoS₂.Contribution No. 790 from the Solid State and Structural Chemistry Unit.     

一种基于并联机构的航天器姿态模拟装置的设计开发

航天器发射升空前进行地面测试和试验是航天器研制过程中的重要环节。文中针对一种基于并联机构的姿态模拟装置的设计开发,从位置分析、速度分析和虚拟样机的建造和仿真分析等方面对3UPS-PU并联机构进行研究,完成姿态模拟装置的设计,为航天器装配、试验和测试设备的设计提供一种新的思路。     

熟料烧结过程中氧化铁反应行为的热力学分析

通过对Fe2O3与碳酸钠、氧化钙以及硅酸钙反应的热力学分析,明确Fe2O3在铝土矿炉料烧结过程中的热力学反应规律。热力学计算、分析结果表明:Fe2O3在正常烧结温度范围内能与Na2CO3或CaO发生反应,但更易与CaO反应形成2CaO.Fe2O3或CaO.Fe2O3,Fe2O3和Na2O.Fe2O3能使2CaO.SiO2和3CaO.2SiO2转变为CaO.SiO2,CaO.SiO2进一步与Na2O.Al2O3或Na2O.Fe2O3反应生成不溶的三元化合物而造成烧结法生产氧化铝过程中Na2O和Al2O3的损失。4CaO.Al2O3.Fe2O3不能由铁酸钙和铝酸钠相互反应产生,而可能是CaO、Al2O3和Fe2O3三者直接反应的产物,且在烧结条件下Na2O.Fe2O3可分解4CaO.Al2O3.Fe2O3。     

Oxidation behavior of 2.25Cr-1Mo steel with prior tempering at different temperatures

The oxidation behavior of a normalized 2.25Cr-1Mo steel tempered previously for 10 hr at different temperatures between 873 and 1023 K has been studied up to a maximum duration of 1000 hr in air at 773–973 K. The oxidation resistance of the steel was found to decrease significantly with the temperature of tempering. Tempering of this steel is reported to cause microstructural changes involving precipitation of Cr as carbides and a decrease in the effective (free) Cr contents, that could influence the oxidation resistance of the Cr-containing alloys. Relative compositions across the thickness of the oxide scales, as analyzed by SEM/EDX and SIMS, suggest that a less Cr-rich (and less protective) and thicker scale on the steel formed because previous tempering caused extensive depletion of free Cr.     

Defect structure and chemical diffusion in nickel sulfide β-Ni3S2

The chemical composition, defect structure, and diffusion in nickel sulfide -Ni₃S₂ have been investigated in H₂S-H₂ mixtures containing between 1 and 65% H₂S between 560 and 700°C. Gravimetric, density, and X-ray studies were carried out. In the thermodynamically stable compound the ratio of Ni/S varied between 1.3 and 1.75. The X-ray examination showed a step change in the lattice parameter at the Ni/S ratio 1.4. A linear dependence of the density values (between 5.5 and 6.2 g/cm³) on the composition was observed. On the basis of the chemical composition and density measurements the number of nickel and sulfur atoms in 1 cm³ were determined. It has been shown that the Ni₃S₂ phase is defected in both anion and cation sublattices and that its chemical formula may be described as follows: Ni_3±yS_2x, where y 2x. It has been found that in the mixture containing 10% H₂S the process of defect formation is determined by their diffusion in the sulfide. The temperature dependence of the diffusion coefficient is described by the equation D = 13.15 exp(-30,000/RT) cm²/sec. No dependence of D on the sulfur partial pressure was observed, but this may be due to the relatively large uncertainties in the measurement of the diffusion coefficients.