Memory devices based on lanthanide (SM3+, EU3+, Gd3+) complexes

Memory effects in single-layer organic light-emitting devices based on Sm3+, Gd3+, and Eu3+ rare earth complexes were realized. The device structure was indium-tin-oxide (ITO)/3,4-poly(ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT)/Poly(N-vinyl carbazole) (PVK): rare earth complex/LiF/Ca/Ag. It was found experimentally that all the devices exhibited two distinctive bistable conductivity states in current-voltage characteristics by applying negative starting voltage, and more than 10(6) write-read-erase-reread cycles were achieved without degradation. Our results indicate that the rare earth organic complexes are promising materials for high-density, low-cost memory application besides the potential application as organic light-emitting materials in display devices.

Didodecyldimethylammonium bromide lipid bilayer-protected gold nanoparticles: Synthesis, characterization, and self-assembly

Didodecyldimethylammonium bromide (DDAB) lipid bilayer-protected gold nanoparticles (AuNPs), which were stable and hydrophilic, were synthesized by in situ reduction of HAuCl4 with NaBH4 in an aqueous medium in the presence of DDAB. As-prepared nanoparticles were characterized by UV-vis spectra, transmission electron microscopy, dynamic light scattering analysis, and X-ray photoelectron spectroscopy. All these data supported the formation of AuNPs. Fourier transform infrared spectroscopy (FTIR) and differential thermal analysis/thermogravimetric analysis data revealed that DDAB existed in a bilayer structure formed on the particle surface, resulting in a positively charged particle surface. The FTIR spectra also indicated that the DDAB bilayer coated on the surface of AuNPs was probably in the ordered gel phase with some end-gauche defects. On the basis of electrostatic interactions between such AuNPs and anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS), we successfully fabricated (PSS/AuNP)(n) multilayers on a cationic polyelectrolyte poly(ethylenimine) coated indium tin oxide substrate via the layer-by-layer self-assembly technique and characterized as-formed multilayers with UV-vis spectra and atomic force microscopy.

Highly efficient green light emitting polyfluorene incorporated with 4-diphenylamino-1,8-naphthalimide as green dopant

The dopant/host methodology, which enables efficient tuning of emission color and enhancement of the electroluminescence (EL) efficiency of organic light emitting diodes (OLEDs) based on small molecules, is applied to the design and synthesis of highly efficient green light emitting polymers. Highly efficient green light emitting polymers were obtained by covalently attaching just 0.3-1.0 mol% of a green dopant, 4-(N,N-diphenyl) amino-1,8-naphthaliniide (DPAN), to the pendant chain of polyfluorene (the host). The polymers emit green light and exhibit a high photoluminescence (PL) quantum yield of Lip to 0.96 in solid films, which is attributed to the energy transfer from the polyfluorene host to the DPAN dopant unit. Single layer devices (device configuration: ITO/PEDOT/Polymer/Ca/Al) of the polymers exhibit a turn on voltage of 4.8 V, luminance efficiency of 7.43 cd A(-1), power efficiency of 2.96 lm W-1 and CIE coordinates at (0.26, 0.58). The good device performance can be attributed to the energy transfer and charge trapping from the polyfluorene host to the DPAN dopant unit as well as the molecular dispersion of the dopant in the host.

Phenylene vinylene-based electroluminescent polymers with electron transport block in the main chain

We report a new route for the design of soluble phenylene vinylene (PV) based electroluminescent polymers bearing electron-deficient oxadizole (OXD) and triazole (TZ) moieties in the main chains with the aryloxy linkage. Both series of the PV-based polymers were prepared by Wittig reaction. By properly adjusting the OXD and/or TZ content through copolymerization, we can achieve an enhanced balance of hole- and electron injections, such that the device efficiency is significantly improved. Light-emitting diodes fabricated from P1, P2, P3, P4, P5, P6, and P7 with the configuration of Indium-Tin Oxide (ITO)/Poly (styrene sulfonic acid) doped poly (ethylenedioxythiophene) (PEDOT)/polymer/Ca/Al, emit bright green light with the maximum peak around 500 nm. For the device using the optimal polymer (P4) as emitting layer, a maximum brightness of 1300 cd/m(2) at 20 V and a maximum luminance efficiency of 0.325 cd/A can be obtained.

Electrogenerated chemiluminescence biosensor based on Ru(bpy)(3)(2+) and dehydrogenase immobilized in sol-gel/chitosan/poly(sodium 4-styrene sulfonate) composite material

A new electrogenerated chemiluminescence biosensor was fabricated by immobilizing ECL reagent Ru(bPY)(3)(2+) and alcohol dehydrogenase in sol-gel/chitosan/poly(sodium 4-styrene sulfonate) (PSS) organically modified composite material. The component PSS was used to immobilize ECL reagent Ru(bpy)(3)(2+) by ion-exchange, while the addition of chitosan was to prevent the cracking of conventional sol-gel-derived glasses and provide biocompatible microenvironment for alcohol dehydrogenase. Such biosensor combined enzymatic selectivity with the sensitivity of ECL detection for quantification of enzyme substrate and it was much simpler than previous double-layer design. The detection limit was 9.3 x 10(-6) M for alcohol (S/N = 3) with a linear range from 2.79 x 10(-5) to 5.78 x 10(-2) M. With ECL detection, the biosensor exhibited wide linear range, high sensitivity and good stability.

Surface modification of poly(L-lactic acid) to improve its cytocompatibility via assembly of polyelectrolytes and gelatin

Poly(L-lactide) (PLLA) surface was modified via aminolysis by poly(allylamine hydrochloride) (PAH) at high pH and subsequent electrostatic self-assembly of poly(sodium styrenesulfonate) (PSS) and PAH, and the process was monitored by X-ray photoelectron spectroscopy (XPS) and contact angle measurement. These modified PLLAs were then used as charged substrates for further incorporation of gelatin to improve their cytocompatibility. The amphoteric nature of the gelatin was exploited and the gelatin was adsorbed to the negatively charged PLLA/PSS and positively charged PLLA/PAH at pH = 3.4 and 7.4, respectively. XPS and water contact angle data indicated that the gelatin adsorption at pH = 3.4 resulted in much higher surface coverage by gelatin than at pH = 7.4. All the modified PLLA surfaces became more hydrophilic than the virgin PLLA. Chondrocyte culture was used to test the cell attachment, cell morphology and cell viability on the modified PLLA substrates.

Polymer light-emitting diodes based on a bipolar transporting luminescent polymer

A soluble electroluminescent polymer containing hole-deficient triphenylamine and electron-deficient oxadiazole units in the main chains has been designed and studied. The design is based on the consideration that the triphenylamine group possesses good hole-transporting property and the oxadiazole unit is known to be of electron-transporting character. Because of the good bipolar transporting performance, the brightness and electroluminescent efficiency are significantly improved and the turn-on voltage is reduced compared with a similar polymer without the electron-deficient oxadiazole units in the main chains. For a device with configuration ITO/PEDOT/polymer/CsF/Al, a maximum brightness of 3600 cd m(-2) and a maximum luminescent efficiency of 0.65 cd A(-1) (quantum efficiency of 0.3%) were obtained in the polymer with oxadiazole units, about 15 times brighter and 15 times more efficient than the corresponding polymer without oxadiazole units.

Electrochemiluminescence of tris(2,2 '-bipyridyl)ruthenium (II) ion-exchanged in polyelectrolyte-silica composite thin-films

The organic-inorganic hybrid, PSS-silica composite material was developed for the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) on glassy carbon electrode via ion-exchange (PSS stands for poly(sodium 4-styrene-sulfonate)). The electrochemiluminescence (ECL) and electrochemistry of Ru(bpy)(3)(2-) immobilized in the composite thin films have been investigated with tripropylamine (TPA) as the coreactant. The immobilized Ru(bpy)(3)(2-) underwent a surface process. The modified electrode was used for the ECL detection of TPA and showed high sensitivity. Detection limit was 0,1 mumol L-1 for TPA (S/N = 3) with a linear range from 0.5 mumol L-1 to 5 mmol L-1 (R = 0.998), Moreover, the resulting modified electrode was stable over six months and the good stability may be due to the strong interaction between Ru(bpy)(3)(2-) and the high ion-exchange able PSS-silica composite films on GCE. Compared with other materials. the PSS-silica composite films containing incorporated Ru(bpy)(3)(2-) showed improved sensitivity and long-term stability, Thus, such composite thin film can be a promising material for the construction of ECL sensor.

Preparation and nonlinear optical properties of ultrathin composite films containing both a polyoxometalate anion and a binuclear phthalocyanine

An ultrathin composite film containing both polyoxometalate anion [PMo12O40](3-) ( PMo12) and a planar binuclear phthalocyanine, bi-CoPc, has been prepared by the electrostatic layer-by-layer self-assembly method. UV-vis measurements revealed regular film growth with each four-layer {PMo12/bi-CoPc/PSS/PAH} adsorption. The lm structure was characterized by small-angle X-ray reflectivity measurements, X-ray photoelectron spectra, and AFM images. The nanothick film shows a third-order nonlinear optical response of chi((3)) = 4.21 x 10(-12) esu. Experimental investigations also indicate that the combination of polyoxometalate anions [PMo12O40](3-) with the phthalocyanine bi-CoPc in multilayer films can enhance the third-order NLO susceptibility and modify the third-order NLO absorption of bi-CoPc.

Photoluminescent multilayer films based on polyoxometalates

Ultrathin multilayer films consisting of the polyoxotungstoeuropate cluster K-12[EuP5W30O110] (EuP5W30) and poly( allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer self-assembly method. The (EuP5W30 /PAH) multilayer films have been characterized by small-angle X-ray reflectivity measurements, X-ray photoelectron spectra, and atomic force microscopy (AFM). From the AFM images, the thickness of the {PEI/PSS/PAH(EuW30/PAH)} multilayer film was estimated to be 6.5 nm, corresponding to an average thickness of ca. 1.1 nm for a EuW30/PAH layer pair. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(0)-->F-7(J). The fluorescence behavior of the multilayer film is essentially identical to that of H-n[EuP5W30O110]((12-n)-) in a concentrated aqueous solution, except for the relative intensities and peak bandwidths. The occurence of photoluminescent activity confirms the potential for creating luminescent multilayers with polyoxometalates (see ref. 23).

Ultrathin multilayer films incorporating Keggin-type heteropolyanion clusters

Two new ultrathin multiplayer films have been successfully prepared fi-om Keggin-type heteropoly acids H-4[SiW12O40] and H-3[PMo12O40] with polyelectrolytes PEI, PSS, and PAH, using the electrostatic layer-by-layer self-assembly, technique. The XR results reveal their film thickness at nanoscale (similar to 20 nm). According to the AFM images, it is believed that the surface roughness (rough degree of film surface) of the polyelectrolyte-polyoxometalate film greatly depends on the kind of polyoxometalates.

Electrochemiluminescence of tris(2,2 '-bipyridine)ruthenium(II) immobilized in poly(p-styrenesulfonate)-silica-Triton X-100 composite thin-films

The electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) [Ru(bpy)(3)(2+)] immobilized in poly(p-styrenesulfonate) (PSS)-silica-Triton X-100 composite films was investigated. The cooperative action of PSS, sol-gel and Triton X-100 attached Ru(bpy)(3)(2+) to the electrode strongly, and the presence of Triton X-100 prevented drying fractures of the sol-gel films during gelation and even on repeated wet-dry cycles. The modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and NADH in a flow injection analysis (FIA) system with a newly designed flow cell. The detection scheme exhibited good stability, short response time and high sensitivity. Detection limits were 0.1, 0.1 and 0.5 mu mol L-1 for oxalate, TPA and NADH, respectively, and the linear concentration range extended from 0.001 to 1 mmol L-1 for the three analytes. Applications of the flow cell in ECL and electrochemical detection, as well as the immobilization of reagents based on the cooperative action, are suggested.

Mixed ion transfer analysis in redox processes of electroactive thin films

Electrochemical quartz crystal microbalance (EQCM) technique was used to measure the ion transfer in redox processes in electroactive organic thin films, such as self-assembled monolayer (SAM) (4-pyridyl hydroquinone, abbr. 4PHQ), multilayer based on SAM and conducting polymer film (here poly-(3,4-ethylenedioxythiophene), abbr. PEDOT). A mechanism of mixed ion transfer is developed and presented. Analysis of mixed ion transfer during redox processes successfully elucidates the deviation of oscillation frequency of the quartz crystal from theoretical expectation.

SYNTHESIS AND PHOTOCHROMISM IN SOLUTION OF PHENOXYNAPHTHACENEQUINONE DERIVATIVES

Two new phenoxynaphthacenequinone derivatives, 6-[4-(2-(4-hydroxyphenyl)isopropyl)phenoxy] -5,12-naphthacenequinone (7) and 6-[4-(potassium sulfophenylazo)phenoxy]-5,12-naphthacenequinone (8), were synthesized, and their photochromism in solution was investigated and compared with that of 6-phenoxy-5,12-naphthacenequinone (1). On the basis of the spectral data and the selective irreversible reaction of ammonia with the colored phenoxy-ana-naphthacenequinone, the concentrations of the ana forms at the photostationary state (PSS), achieved by 365 nm UV irradiation, and the molar extinction coefficients of the pure ana forms at 481-482 nm of compounds 1, 7 and 8 in dimethylsulfoxide (DMSO) were found to be 83 mol.% and 1.70x10(4) mol(-1) dm(3) cm(-1), 82 mol.% and 1.62x10(4) mol(-1) dm(3) cm(-1) and 16 mol.% and approximately 1.34x10(4) mol(-1) dm(3) cm(-1) respectively; the absorption spectra of the colored ana forms of 7 and 1 in DMSO were estimated; the rate;constants of photoconversion induced by 365 nm light were obtained. The results show the strong effect of the structure of the phenoxynaphthacenequinones on their photochromism in solution. In addition to DMSO solution, compound 7 exhibited normal photochromism in toluene, benzene, chloroform and a DMSO-ethanol mixed solvent, but not in dimethylformamide (DMF) in which a photoinduced reaction occurred between 7 and DMF or impurities.

Algal biotechnology industries and research activities in China

In old China there were very few people engaged in the study of the algae, but in new China, freshwater and marine algae are studied by over one hundred old and new phycologists. There is now an algal biotechnology industry consisting of an aquaculture industry, producing large amounts of the seaweeds Laminaria, Porphyra, Undaria, Gracilaria, eucheumoids, and the microalgae Dunaliella and Spirulina. There is also a phycocolloid industry, producing algin, agar and carrageenan; an industry producing chemicals and drugs, such as iodine, mannitol, phycocyanin, beta -carotene, PSS (propylene glycol alginate sulfate) and FPS (fucose-containing sulfated polysaccharides) and an industry producing food, feed and fertilizer. The Laminaria cultivation industry produces about 900,000 t dry Laminaria, probably the largest producer in the world and 13,000 t algin, undoubtedly one of the largest algin producer in the world.