Photoisomerizable bipyridine ligands and macroligands: absorption, photoisomerization properties and theoretical study.

Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R2N-C6H4-N=N-C6H4-CH=CH-[6 a, R2N=nBu2N; 6 b, R2N=(nBu)(C4H8OTHP)N; 6 c, R2N=(nBu)(C4H8OH)N], were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6 a has been determined. Esterification of 6 c with 2-bromoisobutyroylbromide afforded 6 d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6 e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6 a in solution and on 6 e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R2N=Me2N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol(-1) less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of pi-pi*, n-pi* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6 a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm.     

Elaboration of ZnO Thin Films with Preferential Orientation by a Soft Chemistry Route

Microcrystalline ZnO films presenting well-defined and tunable orientation were obtained by spin coating of alcoholic sols by two different approaches, based on controlled hydrolysis-condensation of Zn-ethanolamine complexes. As-deposited films are formed by amorphous zinc oxide-acetate submicronic particles, which are transformed into oriented ZnO after thermal treatment. The orientation of ZnO depends on the synthesis method, and the solvent. While in ethanol and [Zn] = 0.05 mol·L^–1, films consist of rectangular platelets oriented with the (100) planes parallel to the substrate (a//n), the orientation of the particles changes to (c//n) for systems in 2-methoxyethanol (2-ME) and [Zn] = 0.75 mol·L^–1. A study of chemical factors that influence the orientation (precursor, solvent, MEA/Zn ratio, concentration, coating parameters, heat treatment) is presented.     

Ultra-fast nonlinear response around 1.5 μm in 2D AlGaAs/AlOx photonic crystal

We report the fast switching capabilities of a two-dimensional Al_0.3Ga_0.7As photonic crystal slab around 1.5 μm. The slab is supported by an AlOx low-index thick layer that plays the role of an efficient heat sink. By pumping at 0.8 μm in the absorption of the Al_0.3Ga_0.7As quantum wells, the optical response is modified in the transparency region: a 200% change in the reflectivity is obtained with a total response time of 8ps.     

Polynomial operators and local approximation of solutions of pseudo-differential equations on the sphere

We study the solutions of an equation of the form Lu=f, where L is a pseudo-differential operator defined for functions on the unit sphere embedded in a Euclidean space, f is a given function, and u is the desired solution. We give conditions under which the solution exists, and deduce local smoothness properties of u given corresponding local smoothness properties of f, measured by local Besov spaces. We study the global and local approximation properties of the spectral solutions, describe a method to obtain approximate solutions using values of f at points on the sphere and polynomial operators, and describe the global and local rates of approximation provided by our polynomial operators. The research of this author was supported, in part, by grant DMS-0204704 from the National Science Foundation and grant W911NF-04-1-0339 from the U.S. Army Research Office     

Growth of Ni-Al alloys on Ni(1 1 1): (I) Formation of epitaxial Ni3Al from ultra-thin Al deposits

In this paper we describe the alloying process of ultra-thin Al layers (below 8 × 10¹⁵ Al/cm²) deposited on Ni(1 1 1). For this purpose Auger electron spectroscopy, low energy electron diffraction, and ion beam analysis-channelling measurements have been performed in situ in an ultra-high vacuum chamber. Al deposits formed at low temperature (about 130 K) are strained defective crystalline layers retaining the substrate orientation. Alloying takes place, with very progressive Ni enrichment, in a very broad temperature range between 250 K and 570 K. This feature shows that diffusion of the alloy species is more and more difficult when the Ni concentration increases. At 570 K a crystallographically and chemically ordered Ni₃Al phase is formed, and its order continuously improves upon annealing, up to 750 K. We have shown by ion beam methods that this alloy is three-dimensional, extending up to 16 (1 1 1) planes for the thickest deposits. The Ni₃Al phase can also be obtained directly by Al deposition at 750 K, but its crystalline quality is lower and the layer is probably formed of grains elongated along 〈1 1 −2〉 directions. The Al content of the thin Ni₃Al layers formed mostly dissolves in the bulk above 800 K. However a small amount of Al remains segregated at the Ni crystal surface.     

Heat exchanger design based on chaotic advection

Experiments on hydrodynamic and heat transfer behavior of the flow in a twisted curved channel were conducted in a water tunnel and also in two heat exchanger coils tested in a heat exchanger test facility. The flow regime, designated “chaotic advection,” is a subclass of laminar flow with high mixing properties. Preliminary results show that heat transfer is enhanced due to the chaotic trajectories generated in the flow.     

Plasmonic structure and electromagnetic field enhancements in the metallic nanoparticle-film system

We investigate the plasmonic structure of a metallic nanoparticle near a metallic thin film. We show that in the thin film limit, a virtual plasmon resonance composed of delocalized thin film plasmons is induced. We investigate how the physical properties of the virtual state depend on polarization, film thickness and nanoparticle-film separation. We show that the electromagnetic field enhancements associated with the virtual plasmon resonance are large, suggesting applications of metallic nanoparticle/thin film systems as substrates for surface enhanced spectroscopies and surface enhanced scanning probe microscopies. PACS 78.67.Bf; 73.20.Mf; 78.30.-j     

Oxygen—evloving Activity in PhotosystemⅡ Core Complex of Photosynthetic Membrane in the Presence of Native Lipid

The techniques of oxygen electrode polarography and Fourier transform infrared (FT‐IR) spectroscopy were employed to explore the involvement of digalactosyl diacylglycerol (DGDG) in functional and structural roles in the photosystem II core complex (PSIICC). It was shown that DGDG exhibited the ability to stimulate the oxygen evolution in PSIICC, which was accompanied by the changes in the structures of PSIICC proteins. The results revealed that there existed hydrogen‐bonding interactions between DGDG molecules and PSIICC proteins. It is most likely that the sites of PSIICC interaction with DGDG are in the extrinsic protein of 33 kDa.