Preparation of In2O3 ceramic nanofibers by electrospinning and their optical properties

Electrospinning was employed to fabricate polymer-ceramic composite fibers from solutions containing polyvinyl pyrrolidone (PVP) and In(NO3)(3)center dot 4(1)/2H2O. Upon firing the composite fibers at 800 degrees C, In2O3 fibers with diameters ranging from 200 to 400 nm were synthesized. This indium oxide calcined at 800 degrees C is a body-centered cubic cell. The photoluminescence (PL) properties of the as-formed In2O3 nanofibers were investigated. The In2O3 nanofibers show a strong PL emission in the ultraviolet (UV) region under shorter UV light irradiation.

Synthesis and characterization of novel poly(ester carbonate)s based on pentaerythritol

Novel poly(ester carbonate)s were synthesized by the ring-opening polymerization Of L-lactide and functionalized carbonate monomer 9-phenyl-2,4,8,10-tetraoxaspiro[5,5]undecan-3-one derived from pentaerythritol with diethyl zinc as an initiator. H-1 NMR analysis revealed that the carbonate content in the copolymer was almost equal to that in the feed. DSC results indicated that T-g of the copolymer increased with increasing carbonate content in the copolymer. Moreover, the protecting benzylidene groups in the copolymer poly(L-lactide-co-9-phenyl-2,4,8,10-tetraoxaspiro[5,5]undecan-3-one) were removed by hydrogenation with palladium hydroxide on activated charcoal as a catalyst to give a functional copolymer, poly(L-lactide-co-2,2-dihydroxylmethyl-propylene carbonate), containing pendant primary hydroxyl groups. Complete deprotection was confirmed by H-1 NMR and FTIR spectroscopy. The in vitro degradation rate of the deprotected copolymers was faster than that of the protected copolymers in the presence of proteinase K. The cell morphology and viability on a copolymer film evaluated with ECV-304 cells showed that poly(ester carbonate)s derived from pentaerythritol are good biocompatible materials suitable for biomedical applications.

In-situ fabrication of hybrid polyoxometalate nanoparticles composite films

inorganic-organic hybrid nanoparticles multilayer films were fabricated by extending the method of nucleation and growth of particles in polymer assemblies. The polyelectrolyte matrix was constructed by layer-by-layer self-assembly method. Synthesis of polyoxometalate nanoparticles was achieved by alternately dipping the precursor polyelectrolyte matrix into AgNO3 and H4SiW12O40 aqueous solutions. Repeating the above synthesis process, Ag4SiW12O40 nanoparticles with controllable diameters of 20 to 77 nm were synthesized in the multilayer films in-situ. UV-vis absorption spectra indicate that the nanoparticles grew gradually in the synthesis process. Transmission electron microscopy was used to observe the size and morphology of the nanoparticles.

White electroluminescence from a single-polymer system with simultaneous two-color emission: Polyfluorene as blue host and 2,1,3-benzothiadiazole derivatives as orange dopants on the side chain

Four single polymers with two kinds of attachment of orange chromophore to blue polymer host for white electroluminescence (EL) were designed. The effect of the side-chain attachment and main-chain attachment on the EL efficiencies of the resulting polymers was compared. The side-chain-type single polymers are found to exhibit more efficient white EL than that of the main-chain-type single polymers. Based on the side-chain-type white single polymer with 4-(4-alkyloxy-phenyl)-7-(4-diphenylamino-phenyl)-2,1,3-benzothiadiazoles as the orange-dopant unit and polyfluorene as the blue polymer host, white EL with simultaneous orange (lambda(max) = 545 nm) and blue emission (lambda(max) = 432 nm/460 nm) is realised. A single-layer device (indium tin oxide/poly(3,4-ethylenedioxythiophene)/polymer/Ca/Al) made of these polymers emits white light with the Commission Internationale de l'Eclairage coordinates of (0.30,0.40), possesses a turn-on voltage of 3.5 V, luminous efficiency of 10.66 cd A(-1), power efficiency of 6.68 lm W-1, and a maximum brightness of 21240 cd m(-2).

Synthesis and characterization of white-light-emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9-hexyl-9-(iridium (III)bis(2-(4'-fluorophenyl)-4-phenylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-PIr) and 9-hexyl-9-(iridium(III)bis(2-(4'-fluorophenyl)-4-methylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-MIr), were successfully synthesized. The Suzuki polycondensation of 2,7-bis(trimethylene boronate)-9,9-dioctylfluorene with 2,7-dibromo-9,9-dioetylfluorene and Br-Plr or Br-MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5-3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue- and orange-emission peaks. A white-light-emitting diode with a configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br-PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br-MIr) was employed as the white-emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants.

Luminescent supramolecular polymers: Cd2+-directed polymerization and properties

A family of supramolecular polymers was prepared via Cd2+-directed self-assembly polymerization of his (2,2':6',2 ''-terpyridine)-based ligand monomers, using oligofluorenes and triphenylamine as bridges under mild conditions. The polymers were fully characterized using thermogravimetric analysis, inherent viscosity, electrochemical measurements, UV-visible spectroscopy, photoluminescence (PL) and electroluminescence (EL). Polymers with oligofluorenes as spacers exhibited blue emission (434-442 nm) in dimethyl acetamide (DMAc) solution, while polymers with triphenylamine as spacer presented an emission peak at 494 nn in DMAc solution. Complexation polymerization of bis(2,2':6',2 ''-terpyridine)-based ligand monomers with cadmium(II) improved fluorescence quantum yields dramatically, and the film PL quantum yields of these polymers were about 0.38-0.54. Single-layer light-emitting diodes were fabricated with the configuration indium tin oxide (ITO)/polymer/Ca/Al; the EL showed green emission and the onset voltages of the devices were 8-11 V.

Two- and three-dimensional Au nanoparticle/CoTMPyP self-assembled nanotructured materials: Film structure, tunable electrocatalytic activity, and plasmonic properties

Two- and three-dimensional Au nanoparticle/[tetrakis(N-methylpyridyl)porphyrinato]cobalt (CoTMPyP) nanostructured materials were prepared by "bottom-up" self-assembly. The electrocatalytic and plasmonic properties of the Au nanoparticle/CoTMPyP self-assembled nanostructured materials (abbreviated as Au/CoTMPyP SANMs) are tunable by controlled self-assembly of the An nanoparticles and CoTMPyP on indium tin oxide (ITO) electrode. The electrocatalytic activity of the Au/CoTMPyP SANMs can be tuned in two ways. One way is that citrate-stabilized An nanoparticles are positioned first on ITO surface with tunable number density, and then positively charged CoTMPyP ions are planted selectively on these gold sites. The other way is that An nanoparticles and CoTMPyP are deposited by virtue of layer-by-layer assembly, which can also tune the amount of the as-deposited electrocatalysts. FE-SEM studies showed that three-dimensional SANMs grow in the lateral expansion mode, and thermal annealing resulted in both surface diffusion of nanoparticles and atomic rearrangement to generate larger gold nanostructures with predominant (I 11) facets.

微芯片毛细管电泳电化学/电化学发光同时检测药物分子

提出了基于毛细管电泳芯片的电化学和电化学发光同时检测技术.在此芯片系统中,三联吡啶钌Ru(bpy)2+3[Tris(2,2'-bypiridyl) ruthenium(Ⅱ)]既作为电化学发光(ECL)检测所需的发光试剂与被分析物反应,生成激发态的Ru(bpy)2+3*,从而产生电化学发光信号;又具有催化作用参与电极表面的电化学反应,从而得到增强的电流响应.电化学信号与电化学发光信号同时产生并被分别纪录,从而实现了电化学和电化学发光的同时检测.这种芯片由两部分构成,分别是带有分离和进样通道的聚二甲基硅氧烷(PDMS)层和ITO(Indium tin oxide)工作电极底片.PDMS层与ITO电极底片采用可逆键合的方式组成芯片,该芯片大大简化了操作过程,提高了发光信号的采集效率.在整个实验过程中,ITO电极表现出良好的稳定性,可长时间多次使用.选用山莨菪碱和氧氟沙星两种药物分子作为被分析物,对芯片系统性能进行了表征.

UV-vis spectrophotometric titrations and vibrational spectroscopic characterization of meso-(p-hydroxyphenyl)porphyrins

Sequentially spectrophotometric titrations by sodium hydroxide of meso-tetraphenylporphyrin derivatives bearing one, two, three, or four p-hydroxyl groups result in new types of spectra. The strong new bands appear in the visible region with splitting or broadening of the Soret band and its significant loss of oscillator strength. To understand the molecular origin of these phenomena, the Resonance Raman (RR) and Fourier Transform Infrared (FTIR) experiments are carried out. The results demonstrate that the charges of the deprotonated para-hydroxy substituted meso-tetraphenylporphyrins are localized on the substituents, not delocalized into the pi system of the porphyrin macrocycles and that the ground states of the macrocycles remain essentially unperturbed. Both the related behavior of diprotonated tetrakis(p-(dimethylamino)phenyl) porphyrin and protonated Schiff base porphyrins show that the new bands considered as hyperporphyrin spectra are due to pi(phenoxide anion) --> pi*(porphyrin) transitions, where pi is an orbital on the phenoxide anion substitutent and pi* is a LUMO on the porphyrin.

Polymeric pH indicators immobilized PVA membranes for optical sensors of high basicity based on a kinetic process

Two kinds of polymeric pH indicators PPF (phenolphthalein-formaldehyde product) and CPF (o-cresolphthalein-formaldehyde product) immobilized cross-linked poly(vinyl alcohol) membranes (PPF-PVA and CPF-PVA) for optical intermittent determination of high basicity ([OH-] = 1-8 M) based on a kinetic process were developed. In our previous work, we had demonstrated that PPF-PVA and CPF-PVA could perform the determination of high pH values from pH 10.0 to 14.0. Here the discoloring kinetic behaviors of PPF-PVA and CPF-PVA were compared with those of free phenolphthalein, o-cresolphthalein and thymolphthalein. Experimental results and theoretical analysis indicated that the response behaviors of the optodes' membranes in concentrated NaOH solutions were diffusion-independent and still complied with the pseudo-first-order kinetics. In addition, two data analysis methods for determination were presented. One was directly based on the reduced absorbance: the other was based on the discoloring kinetic constant. It was found that the latter could perform a rapid (60 s) and reliable (relative standard deviation: 2.6%) determination for high basicity.

White electroluminescence from polyfluorene chemically doped with 1,8-napthalimide moieties

An efficient white light-emitting polymer was developed with blue polyfluorene (PFO) chemically doped with orange fluorescent 1, 8-naphthalimide moieties. The emission spectrum can be easily tuned by varying the content of 1, 8-naphthalimide moieties. A white polymeric light-emitting diode (WPLED) with a structure of indium tin oxide (ITO)/the complex of (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (PEDOT)/polymer/Ca/Al showed a current efficiency of 5.3 cd/A and a power efficiency of 2.8 Lm/W at 6 V with the Commission Internationale de L'Eclairage (CIE) coordinates at (0.25,0.35). Moreover, the WPLED from the copolymer showed a very stable white light emission at different driving voltage and brightness. The CIE coordinates of the WPLED were (0.25, 0.35), (0.26, O.36), and (0.26, 0.36) under driving voltages of 6, 8, and 10 V, corresponding to the brightness of 82, 3555, and 7530 cd/m(2), respectively. This approach for realization of white light emission is promising over the polymer blending system in terms of both efficiency and color stability.

Soluble, saturated-red-light-emitting poly(p-phenylenevinylene) containing triphenylamine units and cyano groups

A conjugated poly(p-CN-phenylenevinylene) (PCNPV) containing both electron-donating triphenylamine units and electron-withdrawing cyano groups was prepared via Knoevenagel condensation in a good yield. Gel permeation chromatography suggested that the soluble polymer had a very high weight-average molecular weight of 309,000. A bright and saturated red emission was observed under UV excitation in solution and film. Cyclic voltammetry showed that the polymer presented quasi-reversible oxidation with a relatively low potential because of the triphenylamine unit. A single-layer indium tin oxide/PCNPV/Mg-Ag device emitted a bright red light (633 nm).

Highly efficient green-emitting phosphorescent iridium dendrimers based on carbazole dendrons

Green-emitting iridium dendrimers with rigid hole-transporting carbazole dendrons are designed, synthesized, and investigated. With second-generation dendrons, the photoluminescence quantum yield of the dendrimers is up to 87% in solution and 45% in a film. High-quality films of the dendrimers are fabricated by spin-coating, producing highly efficient. non-doped electrophosphorescent organic light-ernitting diodes (OLEDs). With a device structure of indium tin oxide/poly(3,4-ethylenedioxythiopheiie):poly(styrene sulfonic acid)/neat dendrimer/1,3,5-tris(2-N-phenylbenzimidazolyl)benzene/LiF/Al, a maximum external quantum efficiency (EQE) of 10.3% and a maximum luminous efficiency of 34.7 cd A(-1) are realized. By doping the dendrimers into a carbazole-based host, the maximum EQE can be further increased to 16.6%. The integration of rigid hole-transporting dendrons and phosphorescent complexes provides a new route to design highly efficient solution-processable dendrimers for OLED applications.

White electrolumineseence from a single-polymer system with simultaneous two-color emission: Polyfluorene as the blue host and a 2,1,3-benzothiadiazole derivative as the orange dopant on the main chain

New single-polymer electroluminescent systems containing two individual emission species - polyfluorenes as a blue host and 2,1,3-benzothiadiazole derivative units as an orange dopant on the main chain - have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue(lambda(max) = 421 nm/445 nm) and orange emission (lambda(max) = 564 nm)from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light-emitting diodes (PLEDs) based on the single-polymer systems has been investigated. The introduction of the highly efficient 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single-layer device fabricated in air (indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure-white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m(-2), luminance efficiency of 7.30 cd A(-1), and power efficiency of 3.34 lm W-1 can be obtained.

Highly efficient pure-white-light-emitting diodes from a single polymer: Polyfluorene with naphthalimide moieties

Light-emitting diodes exhibiting efficient pure-white-light electroluminescence have been successfully developed by using a single polymer: polyfluorene derivatives with 1,8-naphthalimide chromophores chemically doped onto the polyfluorene backbones. By adjusting the emission wavelength of the 1,8-naphthalimide components and optimizing the relative content of 1,8-naphthalimide derivatives in the resulting polymers, white-light electroluminescence from a single polymer, as opposed to a polymer blend, has been obtained in a device with a configuration of indium tin oxide/poly(3,4-ethyleiledioxythiophene)(50 nm)/polymer(80 nm)/Ca(10 nm)/Al(100 nm). The device exhibits Commission Internationale de I'Eclairage coordinates of (0.32,0.36), a maximum brightness of 11900 cd m(-2), a current efficiency of 3.8 cd A(-1), a power efficiency of 2.0 lm W-1. an external quantum efficiency of 1.50 %, and quite stable color coordinates at different driving voltages, even at high luminances of over 5000 cd m(-2).