An Efficient Method for Preparing the α-Deuterated-α,β-Unsaturated Carbonyl Compounds by Reaction of Stable Phosphonium Ylides with Carbonyl Compounds in Deuterium Oxide

Carbonyl compounds reacted with stable phosphonium ylides in D₂O to give α-deuterated-α,β-unsaturated carbonyl compounds in the same flask. The chemical yield and deuterium incorporation are excellent under our procedure. The fragile group like ozonide was compatible with our reaction condition.     

Crowning Proteins: Modulating the Protein Surface Properties using Crown Ethers

Crown ethers are small, cyclic polyethers that have found wide‐spread use in phase‐transfer catalysis and, to a certain degree, in protein chemistry. Crown ethers readily bind metallic and organic cations, including positively charged amino acid side chains. We elucidated the crystal structures of several protein‐crown ether co‐crystals grown in the presence of 18‐crown‐6. We then employed biophysical methods and molecular dynamics simulations to compare these complexes with the corresponding apoproteins and with similar complexes with ring‐shaped low‐molecular‐weight polyethylene glycols. Our studies show that crown ethers can modify protein surface behavior dramatically by stabilizing either intra‐ or intermolecular interactions. Consequently, we propose that crown ethers can be used to modulate a wide variety of protein surface behaviors, such as oligomerization, domain–domain interactions, stabilization in organic solvents, and crystallization.     

Electrostatic Charge Measurement and Charge Neutralization of Fine Aerosol Particles during the Generation Process

An aerosol charge analyzer has been constructed to measure the charge distribution of NaCl particles generated in the laboratory. A radioactive electrostatic charge neutralizer utilizing Po‐210 was used to neutralize the electrostatic charge of the particles. The atomization technique was used to generate NaCl particles with diameters of 0.2 to 0.8 μm, while the evaporation and condensation method was adopted to generate particles of 0.01 to 0.2 μm in diameter. The experimental data demonstrates that the absolute average particle charge depends on the particle diameter, and is higher than that calculated by the Boltzmann charge equilibrium for particles within the range of 0.2 to 0.8 μm. The charge increases with decreasing NaCl concentration. When these particles are neutralized using the Po‐210 neutralizer, it is found that the electrostatic charge reaches the Boltzmann charge equilibrium. For 0.01 to 0.2 μm NaCl particles generated using the evaporation and condensation method, test results show that the absolute average particle charge is higher than that calculated by the Boltzmann charge equilibrium for particles larger than 0.03 to 0.05 μm in diameter, while it is lower than that predicted by the Fuchs theory [1], for particles smaller than 0.03 to 0.05 μm. However, after charge neutralization, particles with diameter above 0.05 μm reach the Boltzmann charge equilibrium condition, and the charges for particles with diameters of 0.010 to 0.05 μm, agree well with Fuchs' theory.     

Dibromomethane as one-carbon source in organic synthesis: microwave-accelerated α-methylenation of ketones with dibromomethane and diethylamine

The reactivity of aryl alkyl ketone with a preheated mixture of dibromomethane and diethylamine is poor and gives an α-methylenation product in very low yield even under refluxing condition. It can be accelerated dramatically by microwave irradiation. Under microwave condition, the cyclic 1,3-dicarbonyls, aryl alkyl ketones, heteroaryl alkyl ketones and acyclic benzyl ketone give α-methylenation products in modest to good yields.     

Characteristics method with cubic‐spline interpolation for open channel flow computation

In the framework of the specified‐time‐interval scheme, the accuracy of the characteristic method is greatly related to the form of the interpolation. The linear interpolation was commonly used to couple the characteristics method (LI method) in open channel flow computation. The LI method is easy to implement, but it leads to an inevitable smoothing of the solution. The characteristics method with the Hermite cubic interpolation (HP method, originally developed by Holly and Preissmann, 1977) was then proposed to largely reduce the error induced by the LI method. In this paper, the cubic‐spline interpolation on the space line or on the time line is employed to integrate with characteristics method (CS method) for unsteady flow computation in open channel. Two hypothetical examples, including gradually and rapidly varied flows, are used to examine the applicability of the CS method as compared with the LI method, the HP method, and the analytical solutions. The simulated results show that the CS method is comparable to the HP method and more accurate than the LI method. Without tackling the additional equations for spatial or temporal derivatives, the CS method is easier to implement and more efficient than the HP method. Copyright © 2004 John Wiley & Sons, Ltd.     

Depth‐averaged two‐dimensional curvilinear explicit finite analytic model for open‐channel flows

A depth‐averaged two‐dimensional model has been developed in the curvilinear co‐ordinate system for free‐surface flow problems. The non‐linear convective terms of the momentum equations are discretized based on the explicit–finite–analytic method with second‐order accuracy in space and first‐order accuracy in time. The other terms of the momentum equations, as well as the mass conservation equation, are discretized by the finite difference method. The discretized governing equations are solved in turn, and iteration in each time step is adopted to guarantee the numerical convergence. The new model has been applied to various flow situations, even for the cases with the presence of sub‐critical and supercritical flows simultaneously or sequentially. Comparisons between the numerical results and the experimental data show that the proposed model is robust with satisfactory accuracy. Copyright © 2000 John Wiley & Sons, Ltd.     

Flexible ligand docking using a robust evolutionary algorithm

A flexible ligand docking protocol based on evolutionary algorithms is investigated. The proposed approach incorporates family competition and adaptive rules to integrate decreasing‐based mutations and self‐adaptive mutations to act as global and local search strategies, respectively. The method is applied to a dihydrofolate reductase enzyme with the anticancer drug methotrexate and two analogues of antibacterial drug trimethoprim. Conformations and orientations closed to the crystallographically determined structures are obtained, as well as alternative structures with low energy. Numerical results indicate that the new approach is very robust. The docked lowest‐energy structures have root‐mean‐square derivations ranging from 0.67 to 1.96 Å with respect to the corresponding crystal structures. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 988–998, 2000     

电感耦合等离子体原子发射光谱分析信息系统的开发 Ⅰ.系统分析

根据电感耦合等离子体原子发射光谱（ＩＣＰ－ＡＥＳ）分析的实际需要，开发了一种 ＩＣＰ－ＡＥＳ分析信息系统。该系统包括谱线管理系统、识别干扰程度系统、校准及干扰校正系 统、帮助系统等子系统。本文将讨论系统分析。系统设计和系统评价将在另文中讨论。     

Pentiptycene‐Derived Light‐Driven Molecular Brakes: Substituent Effects of the Brake Component

Five pentiptycene‐derived stilbene systems ( 1 R ; R =H, OM, NO, Pr, and Bu) have been prepared and investigated as light‐driven molecular brakes that have different‐sized brake components ( 1 H < 1 OM < 1 NO < 1 Pr < 1 Bu ). At room temperature (298 K), rotation of the pentiptycene rotor is fast (k_rot=10⁸–10⁹ s^?1) with little interaction with the brake component in the trans form ((E)‐ 1 R ), which corresponds to the brake‐off state. When the brake is turned on by photoisomerization to the cis form ((Z)‐ 1 R ), the pentiptycene rotation can be arrested on the NMR spectroscopic timescale at temperatures that depend on the brake component. In the cases of (Z)‐ 1 NO , (Z)‐ 1 Pr , and (Z)‐ 1 Bu , the rotation is nearly blocked (k_rot=2–6 s^?1) at 298 K. It is also demonstrated that the rotation is slower in [D₆]DMSO than in CD₂Cl₂. A linear relationship between the free energies of the rotational barrier and the steric parameter A values is present only for (Z)‐ 1 H , (Z)‐ 1 OM , and (Z)‐ 1 NO , and it levels off on going from (Z)‐ 1 NO to (Z)‐ 1 Pr and (Z)‐ 1 Bu . DFT calculations provide insights into the substituent effects in the rotational ground and transition states. The molar reversibility of the E–Z photoswitching is up to 46 %, and both the E and Z isomers are stable under the irradiation conditions.