Synthetic Applications of 3‐(Phenylsulfinyl)‐3‐sulfolene

The title compound 2 was readily prepared by MCPBA oxidation of the sulfide 1. Thermal desulfonylation of 2 gave the sulfoxide‐substituted diene 3. The Diels‐Alder reactions of 3 with various dienophiles gave the cyclized products 4‐9 in good yields. The regiochemistry was found to be dominated by the phenylsulfinyl group, but could be reversed by the presence of a Lewis acid. Deprotonation of 2 by BuLi, followed by the reaction with alkyl halides, gave the substituted 2‐sulfolenes 10. A synthetic application of 10 was demonstrated by converting 10e to the bicyclic product 11.     

A NEW DIFFERENCE SCHEME WITH MULTI-TIME LEVELS

In view of making the best use of information coming from past observational data, a new difference scheme with multi-time levels (p>3) is suggested. Some mathematical characteristics of the scheme, which is called the retrospective scheme, are discussed. The numerical results of some examples show that the calculation accuracy of linear and nonlinear advection equations computed with the retrospective scheme is higher than that obtained via the leapfrog scheme. The scheme can be applied to many fields, such as meteorology, engineering physics, astronautics, environment and economy etc, where systematic observations are made normally.     

Self-similar solutions for the anisotropic affine curve shortening problem

Similarity between the roles of the group on the equation for self-similar solutions of the anisotropic affine curve shortening problem and of the conformal group of on the Nirenberg problem for prescribed scalar curvature is explored. Sufficient conditions for the existence of affine self-similar curves are established. Received June 26, 1999 / Accepted January 28, 2000 / Published online December 8, 2000     

Studies on the Chemical Synthesis of Nanosized Nickel Powder and its Stability

The synthesis of nanosized nickel colloids is investigated by using nickel chloride as the precursor, hydrazine as the reducing agent and palladium as the nucleation agent. High purity nickel can be obtained when the reaction temperature is above 80^°C. At a lower reaction temperature, nickel hydroxide is also present in the precipitate form. Starting concentration of nickel ion is a dominant factor in affecting colloidal sizes, while other parameters such as reaction temperature and quantity of poly(vinyl pyrrolidone) (PVP) exhibit only minor effects. Although PVP has some dispersion power, it is not capable of preventing nickel colloids from gradual agglomeration. Our study shows that the subsequent addition of poly(acrylic acid) (PAA) after synthesis can help to stabilize the nickel suspension. This stabilized suspension can then be de-stabilized by changing pH to lower than 4 and vice versa. This reversible stabilization–de-stabilization process is likely due to the behaviour of PVP–PAA complex in the aqueous solutions.     

Collisional source of the second moment and pressure tensor for inhomogeneous rapid granular flows of highly inelastic spheres

By extending the constitutive theories for homogeneous granular flows of highly inelastic spheres by Richman (J. Rheol 33 (1989) 1293), Chou (J. CSME 16-6 (1995) 577), and Chou and Richman (Physica A 259 (1998) 430), the collisional source of the second moment of fluctuation velocity and pressure tensor were developed in this study for inhomogeneous rapid granular flows of identical smooth highly inelastic spheres. The important mean fields in this flow are the solid fraction, mean velocity, and full second moment of fluctuation velocity. The collisional source of second moment and the collisional flux of momentum are based upon an anisotropic Maxwellian velocity distribution function. The constitutive theory was combined with the experimental results measured by Hsiau and Jang (Exp. Thermal Fluid Sci. 17 (1998) 202) so as to determine the profiles of pressure tensor and collision source of second moment in the inhomogeneous rapid granular shear flows of inelastic spheres. The normal pressure discrepancies were also observed.     

C2, Symmetric Dibenzosuberanes as Templates for the Chirality Determination of Helicenes and Their Applications as Optically Switchable Memory Device

We have recently developed a new type of chiral templates, dibenzosuberanes. Thess C₂, symmetric diaryl modifiers have been successfully applied to the synthesis of chiral triarylcarbenium ions. They can serve as catalysts in the asymmetric Mukaiyama aldol reactions with moderate enantioselectivities of up to 50% [1]. We have subsequently found that one major side reaction between the catalyst and the substrate-silyl ketene acetal which releases extra silyl-X species is responsible for the erosion of asymmetric induction. The dibenzosuberane scaffold was found essential to prevent this type of side reaction. For the selection of carbenium counter ions, we have resorted to the chloride in order to completely suppress the undesired silyl catalysis [2].     

Critical Conformational Change of Poly(oxypropylene)diamines in Layered Aluminosilicate Confinement

The intercalation of aluminosilicate clays proceeds via a critical conformation change. Ion exchange of the poly(oxypropylene)diamine salts allows widening of the clay layers from 12 Å to 20 Å and then a sharp increase to 58 Å. The data indicate a critical conformation change of the intercalated amines, thus providing a new way for manipulating nanomaterials and control of polymer conformations in layered silicate confinement.

Schematic illustration of POP‐amine self‐assembly in silicate confinements.     

Recent advances in heterostructured cathodic electrocatalysts for non-aqueous Li–O2 batteries

Developing efficient energy storage and conversion applications is vital to address fossil energy depletion and global warming. Li–O₂ batteries are one of the most promising devices because of their ultra-high energy density. To overcome their practical difficulties including low specific capacities, high overpotentials, limited rate capability and poor cycle stability, an intensive search for highly efficient electrocatalysts has been performed. Recently, it has been reported that heterostructured catalysts exhibit significantly enhanced activities toward the oxygen reduction reaction and oxygen evolution reaction, and their excellent performance is not only related to the catalyst materials themselves but also the special hetero-interfaces. Herein, an overview focused on the electrocatalytic functions of heterostructured catalysts for non-aqueous Li–O₂ batteries is presented by summarizing recent research progress. Reduction mechanisms of Li–O₂ batteries are first introduced, followed by a detailed discussion on the typical performance enhancement mechanisms of the heterostructured catalysts with different phases and heterointerfaces, and the various heterostructured catalysts applied in Li–O₂ batteries are also intensively discussed. Finally, the existing problems and development perspectives on the heterostructure applications are presented.

The structure–function relationships between heterostructures and their catalytic properties were discussed in detail, and the challenges and improvement strategies for heterostructure based cathodes towards Li–O₂ catalysis were also summarized.