Synthesis and characterization of an active styrlthiophene monomer and its polyurethane with second-order optical nonlinearity

A novel monomer, (trans)-7-[4-N,N-(di-beta-hydroxyethyl) amino-benzene]-ethenyl-3,5-dinitrothiophene (HBDT), and the corresponding prepolymer, polyurethane were synthesized and characterized. The details of synthesis of the monomer and its further polymerization were presented. The prepolymer and polyurethane exhibited good thermal stability and good solubility in common organic solvents. The d(33) coefficient of the poled films was determined to be 40.3 pm/V. (C) 2000 Kluwer Academic Publishers.

Synthesis of covalently bonded cellulose derivative chiral stationary phases with a bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate

A bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate (TEPI) was initially adopted as a spacer reagent to prepare the bonded types of chiral stationary phases (CSPs) with cellulose derivatives. The silica-based CSPs were chemically prepared with non-regioselective and regioselective approaches and their chiral resolving capabilities were evaluated in terms of HPLC resolution of test enantiomers. It was observed that the chiral recognition capabilities of the non-regioselectively prepared CSPs were influenced by the amount of TEPI used. And also, the regioselectively prepared CSP generally showed a slightly higher resolution power than the non-regioselectively prepared CSP, while the non-regioselective procedures were highly advantageous to rapid preparation. In addition, chiral recognition of the prepared CSPs was affected by the properties of the used silica matrices. (C) 2003 Elsevier B.V. All rights reserved.

Branched polystyrene with abundant pendant vinyl functional groups from asymmetric divinyl monomer

Branched polystyrenes with abundant pendant vinyl functional groups were prepared via radical polymerization of an asymmetric divinyl monomer, which possesses a higher reactive styryl and a lower reactive butenyl. Employing a fast reversible addition fragmentation chain transfer (RAFT) equilibrium, the concentration of active propagation chains remained at a low value and thus crosslinking did not occur until a high level of monomer conversion. The combination of a higher reaction temperature (120 degrees C) and RAFT agent cumyl dithiobenzoate was demonstrated to be optimal for providing both a more highly branched architecture and a higher polymer yield.

A bifunctional structure for the direct electron transfer of Cytochrome c

It was found that silicon dioxide (SiO2) nanoparticles modified onto glassy carbon (GC) electrode exhibited a dramatic promotion on the direct electron transfer of Cytochrome c (Cyt c). The corresponding mechanism was discussed based on the electrochemical characteristics and a spatial geometrical model of the bifunctional structure. The model could offer insight to the study of biosensors and bioreactors without chemical mediator and serve as a basis for their fabrication. (c) 2008 Elsevier Ltd. All rights reserved.

Silica Materials Doped with Bifunctional Ionic Liquid Extractant for Yttrium Extraction

Two new silica-based organic-inorganic hybrid materials (B104SGs and O104SGs) doped with a binary mixture of imidazolium and phosphonium ionic liquids have been synthesized and used as sorbents in batch system for rare earths (RE) separation. Imidazolium ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate (C(4)mim(+)PF(6)(-)) or 1-octyl-3-methylimidazolium hexafluorophosphate (C(8)mim(+)PF(6)(-)) acted as porogens to prepare porous materials and additives to stabilize extractant within silica gel.

Thiacalix[4]arene-Supported Planar Ln(4) (Ln = Tb-III, Dy-III) Clusters: Toward Luminescent and Magnetic Bifunctional Materials

This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear Tb-III (1 and 3) and Dy-III (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H(4)PTC4A) and p-tert-butylthiacalix-[4]arene (H(4)TC4A). All four frameworks can be formulated as [Ln(4)(III)(PTC4A/TC4A)(2)(mu(4)-OH)Cl-3(CH3OH)(2)(H2O)(3)], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (mu(4)-OH)Ln(4) cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient "antenna" than H(4)TC4A.

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED VINYL POLYMERS FROM RAFT POLYMERIZATION OF AN ASYMMETRIC DIVINYL MONOMER

Hyperbranched vinyl polymers were prepared by reversible addition-fragmentation chain transfer ( RAFT) polymerization of a styrenic asymmetric divinyl monomer. This was achieved by using cumyl dithiobenzoate or S-dodecyl-S'-(alpha,alpha'-dimethyl-alpha ''-acetic acid) trithiocarbonate as the chain transfer agent, 1,1'-azobis(cyclohexanecarbonitrile) or thermal initiation as a source of radicals. Cross-linking was inhibited by a rapid RAFT-based equilibrium between active propagation chains and dormant species, and thus a hyperbranched polymer with a monomer conversion as high as 80% was obtained. The hyperbranched structure and properties of the resultant polymers were characterized by a combination of H-1-NMR spectroscopy and a triple detection size exclusion chromatography (TRI-SEC). The hyperbranched vinyl polymer has a broad molecular weight distributions and a low Mark-Houwink exponent alpha value compared with the linear counterpart.

Free-Radical Solution Copolymerization of the Ionic Liquid Monomer 1-Vinyl-3-Ethylimidazolium Bromide with Acrylonitrile

Ionic liquid monomer 1-vinyl-3-ethylimidazolium bromide (ViEtIM(+)Br(-)) was first used to copolymerize with acrylonitrile (AN) successfully under various conditions. This was achieved with azobisisobutyronitrile as the initiator and dimethyl sulfoxide as the solvent. The kinetics of this copolymerization were studied. The values of the monomer apparent reactivity ratios were calculated by the Kelen-Tudos method. The apparent reactivity ratios of ViEtIM(+)Br(-) (r(ViEtIM+Br-)) and AN (r(AN)) were similar at polymerization conversions of less than 10%, (r(AN) = 0.954, r(ViEtIM+Br-) = 0.976). The copolymers were obtained with high molecular weights and high hydrophilicides. The copolymers were characterized by H-1-NMR, differential scanning calorimetry, and thermogravimetric analysis. These copolymers may be potentially useful in the preparation of precursor fibers and carbon fibers.

A Novel Strategy to Branched Polyacrylonitrile Via One-Pot RAFT Copolymerization of Acrylonitrile and an Asymmetrical Divinyl Monomer

Branched polyacrylonitriles were prepared via the one-pot radical copolymerization of acrylonitirle and an asymmetric divinyl monomer (allyl methacrylate) that possesses both a higher reactive methacrylate and a lower reactive allyl. RAFT technique was used to keep a low-propagation chain concentration via a fast reversible chain transfer euilibration and thus the cross-linking was prevented until a high level of monomer conversions. This novel strategy was demonstrated to engenerate a branched architecture with abundant pendant functional vinyl and nitrile groups, and controlled molecular weight as a behavior of controlled/living radical polymerization characteristics. The effect of the various experimental parameters, including temperature, brancher to monomer molar ratio, and chain transfer agent to initiator molar ratio, on the control Of moleculer dimension (molecular weight and polydispersity indices) and the degree of branching were investigated in detail. Moreover, H-1 NMR and gel permeation chromatography confirm the branched architecture of the resultant polymer. The intrinsic viscosity of the copolymer is also lower than the linear counterpart.

Bifunctional Au@Pt hybrid nanorods

The controlled synthesis of bifunctional Au@Pt hybrid nanorods has been realized through a simple wet chemical approach. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-vis-near infrared spectroscopy (UV-vis-NIR) were employed to characterize the obtained hybrid nanorods. TEM results indicate that the thickness of Pt nanoislands on the surfaces of gold nanorods can be easily tunable via controlling the molar ratio of An nanorods to the H2PtCl6. These Au@Pt hybrid nanorods have dual functions, which can be used not only for surface enhanced Raman spectroscopy (SERS), but also to exhibit good catalytic activity for 02 reduction. It is expected that these hybrid nanorods can be used as new functional building blocks to assemble novel three-dimensional (31)) complex multicomponent nanostructures, which are believed to be useful for electrochemical nanodevices.