Synthesis and chiroptical properties of two new planar-chiral macrocycles

Could simple intraannular-arm macrocyclic systems exist in enantiopure stable forms? The effective synthesis of two representative compounds of such a class, their resolution into enantiomers, and experiments justifying their stability toward racemization are presented.     

Effect of short glass fiber on structure and viscoelastic behavior of olefinic polymers synthesized with metallocene catalyst

Several composites were prepared on the basis of an ethylene homopolymer and different copolymers of ethylene and 1‐hexene, synthesized with a metallocene catalyst, as matrices and a content of a 5 wt % of short glass fiber. The effect of the fiber incorporation on the structure and mechanical and viscoelastic behaviors was analyzed for the different samples. The glass fibers induced a slightly higher crystallinity, and the crystallite morphology significantly changed (long spacings and crystal orientation). The incorporation of fibers did not reinforce the different matrices under study at this low content; consequently, the mechanical parameters, such as Young's modulus, yielding stress, and microhardness, were lower in the composites as compared with those values found in the neat polyolefins. The location and apparent activation energies of distinct relaxation processes are also discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1244–1255, 2003     

Influence of transition metal ions on the textural properties of alumina and aluminasilicates

Accelerated phase transformations and chemical reactions of metastable aluminas and kaolinite, doped with Cu^{2 +}, Mn^{3 +}/Mn^{2 +} and Fe^{3 +}/Fe^{2 +} ions, are accompanied with accelerated decrease of surface area and pore volume values. The phenomena in metal ion doped samples are explained by a catalytic mechanism, in terms of the Jahn-Teller effect. This revised version was published online in June 2006 with corrections to the Cover Date.     

Absorption and propagation of light in quaterthiophene crystals

We examine absorption of light in quaterthiophene crystals for different directions of the ray and wave-normal vector after refraction on the vacuum/crystal interface. Experimental non-normal incidence spectra are reported where different absorption bands show different behaviour as a function of the angle of incidence. This allows to identify those originating from the b_u Frenkel exciton state.     

Effects of diamines and their fluorinated groups on the color lightness and preparation of organosoluble aromatic polyimides from 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐hexafluoropropane

To investigate the position and amount of the CF₃ group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF₃ groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF₃ group close to the imide group was more effective in lowering the color; this means that CF₃ of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF₃ groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003     

一类含有P-Laplacian算子的奇异边值问题解的确切个数

讨论了一类p-L ap lac ian算子型的奇异边值问题正解的确切个数以及解的性质.     

Theoretical study of exchange coupling constants in an Fe19 complex

The application of theoretical methods based on density functional theory using generalized-gradient approximation functionals provides reasonable estimates of the exchange coupling constants for polynuclear transition metal complexes. Calculations for the complete, non-modeled Fe₁₉ complex have been performed and a comparison with the experimental magnetic susceptibility values using Monte Carlo simulations is presented.     

New poly(butylene succinate)/layered silicate nanocomposites. II. Effect of organically modified layered silicates on structure,properties, melt rheology,and biodegradability

A series of new poly(butylene succinate) (PBS)/layered silicate nanocomposites were prepared successfully by simple melt extrusion of PBS and organically modified layered silicates (OMLS). Three different types of OMLS were used for the preparation of nanocomposites: two functionalized ammonium salts modified montmorillonite and a phosphonium salt modified saponite. The structure of the nanocomposites in the nanometer scale was characterized with wide-angle X-ray diffraction and transmission electron microscopic observations. With three different types of layered silicates modified with three different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, materials properties, melt rheological behavior, and biodegradability. Interestingly, all these nanocomposites exhibited concurrent improvements of material properties when compared with pure PBS. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3160–3172, 2003     

New insights on amorphous silicon-nitride microcavities

All amorphous silicon-nitride planar optical microcavities operating in the visible range have been grown by plasma enhanced chemical vapor deposition. The luminescence intensity of the N-rich silicon-nitride layer from a microcavity with 6 period distributed Bragg reflectors (DBRs) is two order of magnitude higher than that of the luminescent layer without the cavity. Moreover, a strong directionality of the microcavities emission can be observed. Such results can be ascribed to the anisotropic optical density of states induced in the Fabry–Perot structure. The quality factors of the resonators are strictly correlated to the number of periods of the DBRs.     

In-Situ Intrinsic Interface Strength Measurement at Elevated Temperatures and its Relationship to Interfacial Structure

A previously developed laser spallation technique has been modified to measure the tensile strength of thin film interfaces in-situ at temperatures up to 1100°C. Tensile strengths of Nb/A-plane sapphire, FeCrAl/A-plane sapphire and FeCrAlY/A-plane sapphire were measured up to 950°C. The measured strengths at high temperatures were substantially lower compared with their corresponding strengths at ambient temperature. For example, at 850°C, the interface tensile strength for the Nb/sapphire (151 ± 17 MPa), FeCrAl/sapphire (62 ± 8 MPa) and FeCrAlY/sapphire (82 ± 11 MPa) interface systems were lower by factors of approximately, 3, 5, and 8, respectively, over their corresponding ambient values. These results underscore the importance of using such in-situ measured values under operating conditions as the failure criterion in any life prediction or reliability models of such coated systems where local interface temperature excursions are expected. The results on alloy film interfaces also demonstrate that the presence of Y increases the strength of FeCrAl/Al₂O₃ interfaces.