The hydroazocine route to highly functionalized pyrrolizidines

Studies of the preparation of 1,8-dihydroazocines and transannular cyclization of hydroazocines to produce functionalized pyrrolizidines are described. Results are presented which demonstrate that unsymmetrically substituted acetylenes bearing at least one electron withdrawing groups undergo efficient cycloaddition to 1 - β - styryl - 1,2 - dihydropyridine producing in a regio-selective fashion 3,4 - disubstituted - 1,8 - dihydroazocines. The dihydroazocines generated in this manner can be converted to 1 - formyl - Δ^4,5 - epoxyazocines which undergo interesting rearrangement reactions to form pyrrolizidines when subjected to methoxide deformylation followed by acid treatment. In addition, 1,6,7,8 - tetrahydroazocines can be converted to pyrrolizidines under bromination conditions. The intriguing chemical process which occur under the conditions outlined above are described.     

硫化物纳米级粒子化膜的形成与气相性质的影响

采用偏振光反光度、紫外及可见光谱、电子显微镜形貌观察、粒子大小测定及电子衍射等方法加以系统研究硫化锌纳米级粒子化膜的制备与气相性质的影响．     

A generalized equation describing isotope exchange kinetics at solid-liquid interface

A generalization of the kinetic equation for the isotope exchange at solid—liquid interface is presented. The generalized equation may be used to describe kinetics of the isotope exchange process limited by surface reactions and diffusion without assumption of spherical symmetry of solid particles.

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Eine generalisierte Gleichung für die Kinetik des Isotopenaustausches an Fest-Flüssig-Phasengrenzen

Zusammenfassung Es wird eine generalisierte kinetische Gleichung angegeben, die die Kinetik des Isotopenaustausches an Fest-Flüssig-Phasengrenzen beschreibt, wobei der Austauschprozeß durch Oberflächenreaktionen und Diffusion ohne der Annahme sphärischer Symmetrie für die festen Partikel begrenzt ist.

     

Formal Mathematical Analysis of the Existence of the Common Intersection Point in Relation to Determining the Parameters Describing Ion Adsorption at the Oxide/Electrolyte Interface: Comparison of the Triple and Four-Layer Models

For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods.     

The Binary System BaF2/AlF3

The system BaF₂/AlF₃ is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF₅, Ba₃Al₂F₁₂, Ba₅AlF₁₉, polymorphic Ba₃AlF₉ and Ba₅AlF₁₃. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works.     

Monolayer films of PS-b-PEO diblock copolymers at the air/water- and an oil/water-interface

 Amphiphilic diblock copolymers consisting of a hydrophobic polystyrene block (PS) and a hydrophilic poly(ethylene oxide) block (PEO) with block sizes of 1000 or 3000 g/mol for both blocks were studied at the air/water and toluene/water interface. Measurements of the film pressure π of spread monolayers at the water surface reveal two limiting regimes of the π−a _m isotherms, in which the mean molecular area a _m is determined either by the size of the hydrophilic or the hydrophobic blocks of the PS-PEO molecules. The interfacial activity of the block copolymers at the toluene/water interface was studied by measuring the interfacial tension σ over a wide range of concentrations. Pronounced differences in the temperature dependence of the interfacial tension were observed, depending mostly on the block length of the hydrophilic PEO block. From the temperature dependence of σ it is inferred that for the block copolymers with the PEO block size of 3000 g/mol the phase inversion temperature (PIT) is well above 60 °C while for those with a PEO block size of 1000 g/mol the PIT is below or near 25 °C in the toluene/water system. Received: 5 February 1998 Accepted: 16 February 1998     

Ce0.8Y0.2O1.9-Ca3(PO4)2-K3PO4复合电解质在中温区的质子导电性及在常压合成氨中的应用

A precursor of Ce_0.8Y_0.2O_1.9(YDC) solid electrolyte was synthesized by the gol-gel method. YDC and phosphates powders were prepared by mixing the YDC and phosphates according to different weight ratios. The mixtures of the YDC and binary phosphates were ground and sintered at 1 400 ℃. The proton conductivity in solid electrolyte of the sintered samples was examined using electrochemical methods at 400～800 ℃. Ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid state proton conducting cell reactor. The optimal condition for the ammonia production was determined. The result indicated that composite electrolyte of 80wt% YDC: 20wt% binary phosphates as proton conductor could obtain the highest ionic conductivity and ammonia production rate among the four samples, the rate of evolution of ammonia was up to 9.5 × 10^-9 mol·s^-1·cm^-2.     

Improvement of the spinning electrophorometer for zeta potential measurements

In this study, bubbles are held by centripetal force at the center of a rotating cylinder filled with an aqueous solution. Their velocities along the axe of rotation, after application of an electrophoretic force, are used for the calculation of the so-called electrokinetic potential. But this process necessitates the elimination of the electro-osmosis which occurs on the interior sides of the glass cylinder by superposing a concurrent force on the bubble. Efficiency of DEAE-Dextran reticulated with 1,4 Butanediol Diglycidyl Ether can be tested by the observation of a cloud of latex microspheres injected in the interior of the tube and allowed to move in respect with the application of an electric field. The experimental control of these velocity profiles proves the adequacy of the polymer for many cases such as surfactant solutions, presence of electrolytes, utilization with moderate pH.The dynamic interpretation of the electrophoretic motion of bubbles is possible by considering that small ones behave like rigid spheres moving in a rotating fluid. In the second part of this paper and in a previous publication, we have experimentally proved that the use of the theoretical expressions of the forces involved for rigid spheres is justified for small bubbles. So, the electrokinetic potential can be expressed versus the velocity, leading to possible interpretations of the adsorption on gas-water interfaces.     

室温固相反应一步合成N-亚水杨基-4-氨基安替比林

4-氨基安替比林与水杨酬醛通过室温固相反应合成N-亚水杨基-4-氨基安替比 林，反应无溶剂，15 min即可完成，产率达95%，用元素分析，IR，~1H NMR，X射 线粉末衍射和X射线单晶衍射对产物进行了表征。     

Surface mixed adsorption films of 2,4,6- trimethylphenol–2,4,6-trichlorophenol at aqueous solution/air interface

 The results of experimental studies of the adsorption at the solution/air interface from an aqueous mixture: 2,4,6-trimethylphenol–2,4,6-trichlorophenol are presented. The surface properties of the above-mentioned mixture were studied by surface potential and surface tension measurements. These measurements were carried out as a function of the concentration of 2,4,6-trimethylphenol aqueous solution at a constant concentration of 2,4,6-trichlorophenol. Using the results obtained and based on the Gibbs equation, Helmholtz formula and Motomura’s method the relative surface excesses of adsorbed substances, effective dipole moments, surface molar fractions of solutes and miscibility of adsorbed films were determined. Received: 7 November 1997 Accepted: 26 February 1998