Living Copolymerization of Ethylene with Norbornene Mediated by Heteroligated (Salicylaldiminato) (beta-enaminoketonato)Titanium Catalysts

Three heteroligated (salicylaldiminato)(beta-enaminoketonato)titanium complexes [3-Bu-t-2-OC6H3CH=N(C6F5)][(p-XC6H4)N=C(Bu-t)CHC(CF3)O]TiCl2 (3a: X = F, 3b: X = Cl, 3c: X = Br) were synthesized and investigated as the catalysts for ethylene polymerization and ethylene/norbornene copolymerization. In the presence of modified methylaluminoxane as a cocatalyst, these unsymmetric catalysts exhibited high activities toward ethylene polymerization, similar to their parallel parent catalysts. Furthermore, they also displayed favorable ability to efficiently incorporate norbornene into the polymer chains and produce high molecular weight copolymers under the mild conditions, though the copolymerization of ethylene with norbornene leads to relatively lower activities. The sterically open structure of the beta-enaminoketonato ligand is responsible for the high norbornene incorporation. The norbornene concentration in the polymerization medium had a profound influence on the molecular weight distribution of the resulting copolymer.

Surface enhanced Raman scattering of brilliant green on ag nanoparticles and applications in living cells as optical probes

In this article, surface enhanced Raman scattering (SERS) of different concentrations of brilliant green (13G) on Ag nanoparticles (AgNPs) has been investigated. The results indicate that only 10(-12) M BG can be detected on AgNPs while as low as 10(-11) M BG can be detected upon the activation of AgNPs by chloride ions. The additional improvement of the detection of BG mainly derives from the increase of the electromagnetic field around AgNPs and partially from the reorientation of BG on AgNPs induced by chloride ions, which was proved by the different spectra feature in the two systems. Adsorption of BG on AgNPs has also been demonstrated in applications of living cells as optical probes based on SERS, indicating that dye-AgNPs can probe the local environment in the living cells. The related cytotoxicity measurements demonstrated that BG-AgNPs produced little cytotoxicity to the cells, which shows great potential in biornedical applications of BG labeled-AgNPs for SERS nanosensors in cells as optical probes. Meanwhile, SERS spectra of BG on AgNPs in the presence chloride ions are expected to be used in living cells as more sensitive optical probes.

Functional gold nanoparticles for studying the interaction of lectin with glycosyl complex on living cellular surfaces

In this study. lectin-conjugated gold nanoparticles (GNPs) were prepared by standard biotin-streptavidin chemistry. The lectin-conjugated GNPs call be used as ail indicator for studying the interaction of lectin with glycosyl complex on living cellular Surfaces due to the high affinity of the lectin with saccharides. The interactions of two well-known lectins (Ricinus communis agglutinin and concanavalin A) and three different cell lines (HeLa, 293, and 293T) were selected here to establish this assay. Highly binding affinity of R. communis agglutinin with cells was demonstrated by conventional microscopic and UV-visible spectroscopic Studies. In addition, the binding process can be inhibited by galactose, giving further proof of the binding mechanism. (c) 2009 Elsevier Inc. All rights reserved.

Electrospinning of multicomponent ultrathin fibrous nonwovens for semi-occlusive wound dressings

This work describes the design and assembly of multifunctional and cost-efficient composite fiber nonwovens as semi-occlusive wound dressings using a simple electrospinning process to incorporate a variety Of functional components into an Ultrathin fiber. These components include non-hydrophilic poly(L-lactide) (PLLA) as fibrous backbone, hydrophilic poly(vinyl pyrrolidone)iodine (PVP-I), TiO2 nanoparticles, zinc chloride as antimicrobial, odor-controlling, and antiphlogistic agents, respectively. The process of synthesis starts with a multicomponent solution Of PLLA, PVP, TiO2 nanoparticles plus zinc chloride, in which TiO2 nanoparticles are synthesized by in situ hydrolysis of TiO2 precursors in a PVP Solution for the sake of obtaining the particle-uniformly dispersive solution. Subsequent electrospinning generates the corresponding composite fibers. A further iodine vapor treatment to the composite fibers combines iodine with PVP to produce the PVP-I complexes. Experiments indicate that the assembled composite fibers (300-400 nm) possess the ointment-releasing characteristic and the phase-separate, core-sheath structures in which PVP-I residing in fiber Surface layer becomes the sheath, and PLLA distributing inside the fiber acts as the core.

Control led/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under Co-60 gamma-ray irradiation

A new vinyl acyl azide monomer, 4-(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 degrees C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under Co-60 gamma-ray irradiation in the presence of benzyl 1-H-imidazole-1-carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free-radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (< 1.20), and a linear relationship existing between In([M](0)/[M]) and the polymerization time. The data from H-1 NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR.

Synthesis of symmetric H-shaped block copolymer by the combination of ATRP and living anionic polymerization

A novel fluorescent dye labeled H-shaped block copolymer, (PMMA-Fluor-PS)(2)-PEO-(PS-Fluor-PMMA)(2), is synthesized by the combination of atom transfer radical polymerization (ATRP) and anionic polymerization (AP). To obtain the designated structure of the copolymer, a macroinitiator, 2,2-dichloro acetyl-PEO-2,2-dichloro acetyl (DCA-PEO-DCA), was prepared from DCAC and poly(ethylene oxide). The copolymer was characterized by H-1 NMR, GPC and fluorescence spectroscopy.

Synthesis of a (sic)-shaped amphiphilic block copolymer by the combination of atom transfer radical polymerization and living anionic polymerization

The functionalization of monomer units in the form of macroinitiators in an orthogonal fashion yields more predictable macromolecular architectures and complex polymers. Therefore, a new there exists E-shaped amphiphilic block copolymer, (PMMA)(2)-PEO-(PS)(2)-PEO-(PMMA)(2) [where PMMA is poly(methyl methacrylate), PEO is poly (ethylene oxide), and PS is polystyrene], has been designed and successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and living anionic polymerization. The synthesis of meso-2,3-dibromosuccinic acid acetate/diethylene glycol was used to initiate the polymerization of styrene via ATRP to yield linear (HO)(2)-PS2 with two active hydroxyl groups by living anionic polymerization via diphenylmethylpotassium to initiate the polymerization of ethylene oxide. Afterwards, the synthesized miktoarm-4 amphiphilic block copolymer, (HO-PEO)(2)-PS2, was esterified with 2,2-dichloroacetyl chloride to form a macroinitiator that initiated the polymerization of methyl methacrylate via ATRP to prepare the there exists E-shaped amphiphilic block copolymer.

Nanoelectrode ensembles based on semi-interpenetrating network of carbon nanotubes

A method for preparing nanoelectrode ensembles based on semi-interpenetrating network (SIN) of multi-walled carbon nanotubes (MWNTs) on gold electrode through phase-separation method is initially proposed. Individual nanoelectrode owns irregular three-dimensional MWNTs networks, which is denoted as SIN-MWNTs. On the as-prepared SIN-MWNTs nanoelectrode ensembles, the assembled MWNTs clusters in nanoscale serve as individual nanoelectrode and the electroinactive lipid networks located on the top of alkanethiol monolayer are used as a shielding layer. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), tapping-mode atomic force microscopy (TM-AFM) and scanning electron microscopy (SEM) were used to characterize the as-prepared SIN-MWNT nanoelectrode ensembles. Experimental results indicate that the well-defined nanoelectrode ensembles were prepared through self-assembly technology. Meantime, sigmoid curves in a wide scanning range can be obtained in CV experiments. This study may pave the way for the construction of truly nanoscopic nanoelectrode arrays by bottom-up strategy.

Surface enhanced Raman scattering of brilliant green on ag nanoparticles and applications in living cells as optical probes

In this article, surface enhanced Raman scattering (SERS) of different concentrations of brilliant green (13G) on Ag nanoparticles (AgNPs) has been investigated. The results indicate that only 10(-12) M BG can be detected on AgNPs while as low as 10(-11) M BG can be detected upon the activation of AgNPs by chloride ions. The additional improvement of the detection of BG mainly derives from the increase of the electromagnetic field around AgNPs and partially from the reorientation of BG on AgNPs induced by chloride ions, which was proved by the different spectra feature in the two systems. Adsorption of BG on AgNPs has also been demonstrated in applications of living cells as optical probes based on SERS, indicating that dye-AgNPs can probe the local environment in the living cells. The related cytotoxicity measurements demonstrated that BG-AgNPs produced little cytotoxicity to the cells, which shows great potential in biornedical applications of BG labeled-AgNPs for SERS nanosensors in cells as optical probes. Meanwhile, SERS spectra of BG on AgNPs in the presence chloride ions are expected to be used in living cells as more sensitive optical probes.

Synthesis of asymmetric H-shaped block copolymer by the combination of atom transfer radical polymerization and living anionic polymerization

A new asymmetric H-shaped block copolymer (PS)(2)-PEO-(PMMA)(2) has been designed and successfully synthesized by the combination of atom transfer radical polymerization and living anionic polymerization. The synthesized 2,2-dichloro acetate-ethylene glycol (DCAG) was used to initiate the polymerization of styrene by ATRP to yield a symmetric homopolymer (Cl-PS)(2)-CHCCCCH2CH2OH with an active hydroxyl group. The chlorine was removed to yield the (PS)(2)-CHCOOCH2CH2OH ((PS)(2)-OH). The hydroxyl group of the (PS)(2)-OH, which is an active species of the living anionic polymerization, was used to initiate ethylene oxide by living anionic polymerization via DPMK to yield (PS)(2)-PEO-OH. The (PS)(2)-PEO-OH was reacted with the 2,2-dichloro acetyl chloride to yield (PS)(2)-PEO-OCCHCl2 ((PS)(2)-PEO-DCA). The asymmetric H-shaped block polymer (PS)(2)-PEO-(PMMA)(2) was prepared via ATRP of MMA at 130 degrees C using (PS)(2)-PEO-DCA as initiator and CuCl/bPy as the catalyst system. The architectures of the asymmetric H-shaped block copolymers, (PS)(2)-PEO-(PMMA)(2), were confirmed by H-1 NMR, GPC and Fr-IR.

Conducting polyaniline confined in semi-interpenetrating networks

Communication: Conducting semi-interpenetrating network composites with low conductivity percolation threshold were synthesized from waterborne conducting polyaniline (cPAn) and melamine-urea resin, A perfect network of cPAn in the composite was observed by means of TEM (see Figure). The conductivity stability of cPAn in water was improved by confining the chain mobility of cPAn via in-situ crosslinking of melamine-urea resin. Cyclic voltammetry of the composites reveals electrochemical activities and reversibilities similarly to those of pure cPAn.

Particle-attached and free-living bacterial communities in a contrasting marine environment: Victoria Harbor, Hong Kong

Diversity of particle-attached and free-living marine bacteria in Victoria Harbor, Hong Kong, and its adjacent coastal and estuarial environments was investigated using DNA fingerprinting and clone library analysis. Denaturing gradient gel electrophoresis (DGGE) analysis of 16S rRNA genes showed that bacterial communities in three stations of Victoria Harbor were similar, but differed from those in adjacent coastal and estuarine stations. Particle-attached and free-living bacterial community composition differed in the Victoria Harbor area. DNA sequencing of 28 bands from DGGE gel showed Alphaproteobacteria was the most abundant group, followed by the Bacteroidetes, and other Proteobacteria. Bacterial species richness (number of DGGE bands) differed among stations and populations (particle-attached and free-living; bottom and surface). BIOENV analysis indicated that the concentrations of suspended solids were the major contributing parameter for the spatial variation of total bacterial community structure. Samples from representative stations were selected for clone library (548 clones) construction and their phylogenetic distributions were similar to those of sequences from DGGE. Approximately 80% of clones were affiliated to Proteobacteria, Bacteroidetes and Cyanobacteria. The possible influences of dynamic pollution and hydrological conditions in the Victoria Harbor area on the particle-attached and free-living bacterial community structures were discussed.

Particle-attached and free-living bacterial communities in a contrasting marine environment: Victoria Harbor, Hong Kong

Diversity of particle-attached and free-living marine bacteria in Victoria Harbor, Hong Kong, and its adjacent coastal and estuarial environments was investigated using DNA fingerprinting and clone library analysis. Denaturing gradient gel electrophoresis (DGGE) analysis of 16S rRNA genes showed that bacterial communities in three stations of Victoria Harbor were similar, but differed from those in adjacent coastal and estuarine stations. Particle-attached and free-living bacterial community composition differed in the Victoria Harbor area. DNA sequencing of 28 bands from DGGE gel showed Alphaproteobacteria was the most abundant group, followed by the Bacteroidetes, and other Proteobacteria. Bacterial species richness (number of DGGE bands) differed among stations and populations (particle-attached and free-living; bottom and surface). BIOENV analysis indicated that the concentrations of suspended solids were the major contributing parameter for the spatial variation of total bacterial community structure. Samples from representative stations were selected for clone library (548 clones) construction and their phylogenetic distributions were similar to those of sequences from DGGE. Approximately 80% of clones were affiliated to Proteobacteria, Bacteroidetes and Cyanobacteria. The possible influences of dynamic pollution and hydrological conditions in the Victoria Harbor area on the particle-attached and free-living bacterial community structures were discussed.