Free radical-mediated vinyl amination: a mild, general pyrrolidinyl enamine synthesis

The complete scope of free radical-mediated vinyl amination is described, using 5-exo-trig cyclizations of vinyl radicals to the nitrogen of azomethines. The focus is primarily on N,N-dialkyl enamines since their nucleophilicity renders them the most challenging enamines to synthesize using redox conditions. These studies establish several encouraging precedents for the broader application of this strategy.     

A new VOF‐based numerical scheme for the simulation of fluid flow with free surface. Part II: application to the cavity filling and sloshing problems

Finite element analysis of fluid flow with moving free surface has been performed in 2‐D and 3‐D. The new VOF‐based numerical algorithm that has been proposed by the present authors (Int. J. Numer. Meth. Fluids, submitted) was applied to several 2‐D and 3‐D free surface flow problems. The proposed free surface tracking scheme is based on two numerical tools; the orientation vector to represent the free surface orientation in each cell and the baby‐cell to determine the fluid volume flux at each cell boundary. The proposed numerical algorithm has been applied to 2‐D and 3‐D cavity filling and sloshing problems in order to demonstrate the versatility and effectiveness of the scheme. The proposed numerical algorithm resolved successfully the free surfaces interacting with each other. The simulated results demonstrated applicability of the proposed numerical algorithm to the practical problems of large free surface motion. It has been also demonstrated that the proposed free surface tracking scheme can be easily implemented in any irregular non‐uniform grid systems and can be extended to 3‐D free surface flow problems without additional efforts. Copyright © 2003 John Wiley & Sons, Ltd.     

Spherically symmetric static inhomogeneous cosmological models

Spherically symmetric static cosmological models filled with black-body radiation are considered. The models are isotropic about a central observer but inhomogeneous. It is suggested that the energy density of the free gravitational field, which is coupled to the isotropic radiation energy density, might play an important role in generating sufficient field (vacuum) energy (when converted into thermal energy) and initiate processes like inflation. On the central world line the energy density of the free gravitational field vanishes whereas the proper pressure and density of the isotropic black-body radiation are constants. Further, it is shown that the cosmological constant is no more arbitrary but given in terms of the central pressure and density. Also, at its maximum value the energy density of the free gravitational field is proved to be equal to one third of the combined value of radiation pressure and density.     

亚细胞器诱导的2,4,6-三硝基甲苯阴离子自由基的ESR研究

本文在无氧条件下利用ESR分别观察了肝脏和晶状体的微粒体及线粒体酶在NADPH存在下还原三硝基甲苯(TNT)的过程,检测到参数为g=2.0048±0.0005,A_对位~N=1.215mT,A~N=0.800±0.010mT,A~H=0.122±0.0206mT的自由基信号,并通过电子计算机对ESR谱的模拟证明该自由基信号为TNT硝基阴离子自由基,根据其超精细分裂常数认为,其不配对电子的电子云密度主要分布在对位硝基上。     

变参数波振器中小信号增益公式

利用微扰展开技术推导出变参数波振器的小信号增益两个近似求积表达式并将其计算结果与数值模拟结果进行了比较,二者吻合很好。利用近似解析式对小信号增益进行了初步探讨,得到了电子入射能量可低于初始谐振能,能散度允许范围受波振器设计影响以及降低锥度改变率可提高小信号增益等新结论。     

Iodine‐Catalyzed Friedlander Quinoline Synthesis under Solvent‐Free Conditions

Polyfunctional quinolines were synthesized using Friedlander method catalyzed by molecular iodine in high yields at 60 °C under solvent‐free conditions.     

γ辐射引发淀粉目由基衰减的动力学研究

用ESR方法研究了红薯淀粉在γ射线预辐照下,产生的淀粉自由基特性及其室温下的自由基衰减动力学反应。结果表明在室温条件下,淀粉自由基的相对浓度随辐射剂量的增大而增加。自由基相对浓度的室温衰减用二级反应动力学处理,求得了衰减速率常数和淀粉自由基反应的半衰期。     

Vector Lattices on a Set of Two Generators

It is proved that the center of an automorphism group Aut(FVL2) of a free vector lattice FVL2 on a set of two free generators is isomorphic to a multiplicative group of positive reals. It is shown that the free vector lattice FVL2 has an isomorphic representation by continuous piecewise linear functions of the real line; as a consequence, the ideal lattice and the root system for rectifying ideals in FVL2 are amply described. Similar results are obtained for a free vector lattice FVL2 _Q 2 generated by two elements over a field of rational numbers.     

A hybrid finite-element–volume-of-fluid method for simulating free surface flows and interfaces

A numerical technique is developed for the simulation of free surface flows and interfaces. This technique combines the strength on the finite element method (FEM) in calculating the field variables for a deforming boundary and the versatility of the volume-of-fluid (VOF) technique in advection of the fluid interfaces. The advantage of the VOF technique is that it allows the simulation of interfaces with large deformations, including surface merging and breaking. However, its disadantage is that is solving the flow equations, it cannot resolve interfaces smaller than the cell size, since information on the subgrid scale is lost. Therefore the accuracy of the interface reconstruction and the treatment of the boundary conditions (i.e. viscous stresses and surface tension forces) become grid-size-dependent. On the other hand, the FEM with deforming interface mesh allows accurate implementation of the boundary conditions, but it cannot handle large surface deformations occurring in breaking and merging of liquid regions. Combining the two methods into a hybrid FEM-VOF method eliminates the major shortcomings of both. The outcome is a technique which can handle large surface deformations with accurate treatment of the boundary conditions. For illustration, two computational examples are presented, namely the instability and break-up of a capillary jet and the coalescence collision of two liquid drops.     

Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006