Characterization of host-lattice emission and energy transfer in BaMgAl10O17:Eu

Host-lattice emission, energy transfer and degradation processes are characterized in undoped and Eu-doped BaMgAl₁₀O₁₇. Undoped BaMgAl₁₀O₁₇ exhibits a broad emission centered at 265 nm when excited at wavelengths shorter than 190 nm. This emission is assigned to exciton recombination at Ba-O groups in the cation layer of the lattice. The emission exhibits excellent overlap with the excitation band of Eu²⁺ in this host, providing a means of host-to-activator energy transfer in the doped phosphor. The exciton emission is relatively stable to thermal damage, but undergoes a peak shift and significant decrease in intensity after exposure to VUV radiation. Heating of VUV-damaged materials in air leads to some repair of the spectral properties.     

Divinylsiloxane‐bisbenzocyclobutene‐based polymer modified with polystyrene–polybutadiene–polystyrene triblock copolymers

Divinylsiloxane‐bisbenzocyclobutene (DVS‐bisBCB) polymer has very low dielectric constant and dissipation factor, good thermal stability, and high chemical resistance. The fracture toughness of the thermoset polymer is moderate due to its high crosslink density. A thermoplastic elastomer, polystyrene–polybutadiene–polystyrene triblock copolymer, was incorporated into the matrix to enhance its toughness. The cured thermoset matrix showed different morphology when the elastomer was added to the B‐staged prepolymer or when the elastomer was B‐staged with the DVS‐bisBCB monomer. Small and uniformly distributed elastomer domains were detected by transmission electron micrographs (TEM) in the former case, but TEM did not detect a separate domain in the latter case. A high percentage of the polystyrene–polybutadiene–polystyrene triblock copolymer could be incorporated into the DVS‐bisBCB thermoset matrix by B‐staging the triblock copolymer with the BCB monomer. The elastomer increased the fracture toughness of DVS‐bisBCB polymer as indicated by enhanced elongation at break and increased K1c values obtained by the modified edge‐lift‐off test. Elastomer modified DVS‐bisBCB maintained excellent electrical properties, high T_g and good thermal stability, but showed higher coefficient of linear thermal expansion values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1591–1599, 2006     

Immobilization of thiabendazole-specific monoclonal antibodies to silicon substrates via aqueous silanization

Monoclonal antibodies specific for thiabendazole were immobilized to silicon, silicon dioxide, stoichiometric silicon nitride, and silicon-rich silicon nitride surfaces. This work provides the foundation for the development of a homogeneous sensor system for rapid detection and quantification of thiabendazole residues in produce and animal tissue. Immobilization was performed via aqueous silanization of the substrate followed sequentially by treatment with glutaraldehyde and contact with antibody solution in the presence of detergent. Surfaces were challenged with thiabendazole-horseradish peroxidase conjugate in an ELISA format to estimate immobilized antibody load. A stable and reproducible surface loading of 2 x 10¹¹ antibodies/cm² was obtained only after surfaces received postimmobilization treatments to remove nonspecifically adsorbed antibody. No difference in surface loading was noted when using 30% hydrogen peroxide rather than nitric acid for silanol activation. Little difference was noted among the antibody loadings achieved on the various silicon substrates. Bound antigen-enzyme conjugate was eluted with 0.1N acetic acid and reproducible surface activity was measured for up to four consecutive antigen challenges. Immobilized antibody surfaces were stabilized with 2% sucrose, dehydrated at 37‡C and stored in vacuum or stored at 4‡C in phosphate buffered saline containing 0.01% sodium azide without significant loss of activity.     

Applications of chalcogenide glass optical fibers

Chalcogenide-glass fibers based on sulfide, selenide, telluride and their rare-earth-doped compositions are being actively pursued worldwide. Great strides have been made in reducing optical losses using improved chemical purification techniques, but further improvements are needed in both purification and fiberization technology to attain the theoretical optical losses. Despite this, chalcogenide-glass fibers are enabling numerous applications that include laser power delivery, chemical sensing, and imaging, scanning near field microscopy/spectroscopy, IR sources/lasers, amplifiers and optical switches.     

Ammonium hexafluorosilicate salts

The preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]⁺ [SiF₆]²⁻ (where R=piperidinium (2), methylammonium (3), quinolinium (4), acridinium (5), 2,2,6,6-tetramethylpiperidinium (6), and propylammonium (7)) is described.The salts were prepared from the reaction of the corresponding alkylammonium fluoride with silica gel. The compounds were characterized by NMR, IR, mass spectrometry and in the case of 1 (piperidinium fluoride), 2-4 by X-ray crystallography. Compounds 1-3 crystallize in the orthorhombic crystal system (space groups Iba2, Fdd2, and Pnnm, respectively), with Z=8, 14, and 4, respectively. Compound 4 crystallizes in the triclinic space group P-1, with Z=2. Compounds 1-4 exhibit hydrogen bonding.     

Backbonding contributions to small molecule chemisorption in a metal–organic framework with open copper(i) centers

Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework Cu^I-MFU-4l, which contains coordinatively unsaturated copper(i) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(i) sites in Cu^I-MFU-4l via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within Cu^I-MFU-4l. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metal centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry.

In situ near edge X-ray absorption fine structure spectroscopy directly probes unoccupied states associated with backbonding interactions between the open metal site in a metal–organic framework and various small molecule guests.     

Adsorption, desorption, and clustering of H2O on Pt111

The adsorption, desorption, and clustering behavior of H2O on Pt111 has been investigated by specular He scattering. The data show that water adsorbed on a clean Pt111 surface undergoes a structural transition from a random distribution to clustered islands near 60 K. The initial helium scattering cross sections as a function of temperature are found to be insensitive to the incident H2O flux over a range of 0.005 monolayers (ML)/s-0.55 ML/s indicating that the clustering process is more complex than simple surface diffusion. The coarsening process of an initially random distribution of water deposited at 25 K is found to occur over a broad temperature range, 60相似文献   

Direct, stereoselective substitution in [Rh(CO)(2)Cl](2)-catalyzed allylic alkylations of unsymmetrical substrates

[Rh(CO)(2)Cl](2) has been found to possess the unusual property of catalyzing allylic alkylations of unsymmetrical allylic carbonates with high levels of regioselectivity to provide products arising from substitution at the carbon atom bearing the leaving group, irrespective of the structure of the starting carbonate. The substitution reaction occurs with retention of stereochemistry at the reacting center, and the carbon-carbon double-bond stereochemistry of primary (Z)-allylic carbonates is maintained. [reaction: see text]     

Form fluctuations of carbosilane dendrimers in dilute solution: a study using neutron spin echo spectroscopy

A series of carbosilane dendrimers with perfluorinated end groups has been prepared. The structure of these molecules in dilute solution is studied using small angle neutron scattering. For generations g<3 we find a non-spherical shape of the particles and a tendency for aggregation. This result is supported by the analysis of the diffusion coefficient obtained from photon correlation spectroscopy. The overall shape of the molecules is that of a core-shell particle. The generation 4 molecule is obtained as a compact sphere. Neutron spin echo spectroscopy reveals a relaxation time which is attributed to the form fluctuations of this particle.