Study on highly ordered luminescent Langmuir-Blodgett films of heteropolytung state complexes containing lanthanide

Luminescent thin films of heteropolytungstate complexes containing lanthanide (europium or samarium) were successfully fabricated by the Langmuir-Blodgett (LB) technique. The pressure-area isotherm of the monolayer of dimethyldioctadecylammonium. bromide (DODA) is modified rather markedly when the subphase contains the complex of Na9EuW10O36 or Na9SmW10O36. The above results indicate that the monolayer of DODA has a strong interaction with the polyanions of EuW10O369-. (or SmW10O369-). X-ray photoelectron spectra and fluorescent spectra verify that europium and tungsten atoms are 36 36 incorporated into the LB films. Ultraviolet (UV), fluorescent spectra and low-angle X-ray diffraction experiments demonstrate that these LB films have a well-defined lamellar structure. The LB film containing EuW10O369- can give off strong fluorescence 16 on UV irradiation. The characteristic emission behaviors of europium ions in LB films and in the powder of Na9EuW10O369- are discussed. It is found that the intensity ratio of the D-5(0)-F-7(2) transition to the D-5(0)-->F-7(1) transition in LB film is quite different from that in the powder of Na9EuW10O36. The difference of the ratio indicates that the site symmetry of europiurn is distorted in LB film, which is probably due to the strong electrostatic interactions between DODA and polyanions.

Preparation of Y3Al5O12 : Eu phosphors by citric-gel method and their luminescent properties

By using metal nitrates as starting materials and citric acid as complexing agent, Y3Al5O12 (YAG) and Y3Al5O12:Eu (1 mol%) (YAG:Eu) powder phosphors were prepared by a citrate-gel method. The formation process of YAG and YAG:Eu were investigated by means of XRD, TG-DTA and FT-IR spectra. The purified crystalline phases of YAG and YAG:Eu were obtained at 800 degreesC. The crystalline YAG:Eu phosphors showed an orange-red emission with D-5(0)-F-7(1) (591 nm) as the most prominent group, whose intensity was dependent on the pH value of the starting solution, citric acid content and firing temperature. It has been found that the suitable pH and citric acid/metal ratio are 3 and 2 for obtaining the highest emission intensity, respectively. The emission intensity increases steadily with increasing the annealing temperature from 800 to 1200 degreesC, and nearly remains constant after 1200 degreesC. Furthermore, great differences were observed for the lifetimes and the charge transfer band of Eu3+ in crystalline and amorphous states of YAG.

Electrochemical study of ion channel behavior in incorporated poly L-glutamate bilayer lipid membranes

The lipid layer membranes were fabricated on the glassy carbon electrode (GC) and demonstrated to be bilayer lipid membranes by impedance spectroscopy. The formation of incorporated poly L-glutamate bilayer lipid membrane was achieved. The ion channel behavior of the incorporated poly L-glutamate membrane was determined. When the stimulus calcium cations were added into the electrolyte, the ion channel was opened immediately and exhibited distinct channel current. Otherwise, the ion channel was closed. The cyclic voltammogram at the GC electrode coated with incorporated poly L-glutamate DMPC film response to calcium ion is very fast compared with that at the GC electrode coated only with DMPC film. Ion channel current is not dependent on the time but on the concentration of calcium. The mechanism of the ion channel formation was investigated.

Preparation and characterization of novel luminescent sol-gel films containing a RE3+ carboxylic acid complex

RE3+ (Eu3+, Tb3+) complexes with carboxylic acid (salicylic acid and benzoic acid) were introduced into the sol, which was prepared by the hydrolysis of tetraethoxysilane (TEOS). A sol-gel luminescent thin film (SG-LTF) was then prepared by dispersing the sol onto a silica substrate by a spin coating method. Multi-layer luminescent thin films were prepared by repeating the same process. The luminescent spectra, fluorescence lifetime and thermal stability of the SG-LTFs were investigated. For the reason of comparison polyvinylbutyral (PVB) was added into a N,N-dimethylformamide (DMF) solution in which the comparative RE3+ carboxylic acid complexes were previously dissolved to form the DMF/PVB solution and the PVB luminescent thin film (PVB-LTF) was prepared. The results show that a broad excitation band indicates the formation of RE complexes in the solid SG-LTFs. RE ions, which are restrained in the silica matrix, present longer lifetimes and higher thermal stability than that in the PVB-LTF containing the corresponding pure complexes. The different doping concentration of RE (III) complexes in the SG-LTFs and the different change of the emission intensities with the heat treatment temperature in the sol-gel thin film and the sol-gel bulk gel were also discussed in this paper.

Sol-gel deposition and luminescent properties of oxyapatite Ca-2(Y,Gd)(8)(SiO4)(6)O-2 phosphor films doped with rare earth and lead ions

Rare-earth and lead ions (Eu3+, Tb3+, Dy3+, Pb2+) doped Ca2Y8 (SiO4)(6)O-2 and Ca2Gd8(SiO4)(6)O-2 thin films have been dip- coated on silicon and quartz glass substrates through the sol- gel route. X- Ray diffraction (XRD), TG- DTA, scanning electron microscopy (SEM), atomic force microscopy (AFM), FT- IR and luminescence excitation and emission spectra as well as luminescence decays were used to characterize the resulting films. The results of XRD reveal that these films remain amorphous below 700 degreesC, begin to crystallize at 800 degreesC and crystallize completely around 1000 degreesC with an oxyapatite structure. The grain structure of the film can be seen clearly from SEM and AFM micrographs, where particles with various shapes and average size of 250 nm can be resolved. Eu3+ and Tb3+ show their characteristic red (D-5(0)-F-7(2)) and green (D-5(4) - F-7(5)) emission in the films with a quenching concentration of 10 and 6 mol% (of Y3+), respectively. The lifetime and emission intensity of Eu3+ increase with the temperature treatment from 700 to 1100 degreesC, while those of Tb3+ show a maximum at 800 degreesC. Energy transfer phenomena have been observed by activating the oxyapatite film host- lattice Ca2Gd8(SiO4)(6)O-2 with Tb3+ (Dy3+). In addition, Pb2+ can sensitize the Gd3+ sublattice in Ca2Gd8(SiO4)(6)O-2.

Covalent grafting of luminescent rare earth complex onto MCM-41 by postsynthesis

New luminescent hybrid mesoporous material was prepared by covalent anchoring rare earth complex onto MCM-41 by a postsynthesis approach. The monomer (referred to here as PABI) which plays double roles, i.e., as a ligand for lanthanide ion and as an organic functional molecule to modify MCM-41 is synthesized and characterized by H-1 NMR and MS. The fluorescence spectra show clearly that the hybrid mesoporous material possesses excellent luminescence characteristics. The hybrid mesoporous material retains the structure of MCM-41 after modification.

Ion channel behavior of supported bilayer lipid membranes on a glassy carbon electrode

A new kind of solid substrate, a glassy carbon (GC) electrode, was selected to support lipid layer membranes. On the surface of the GC electrode, we made layers of didodecyldimethylammonium bromide (a synthetic lipid). From electrochemical impedance experiments, we demonstrated that the lipid layers on the GC electrode were bilayer lipid membranes. We studied the ion channel behavior of the supported bilayer lipid membrane. In the presence of perchlorate anions as the stimulus and ruthenium(II) complex cations as the marker ions, the lipid membrane channel was open and exhibited distinct channel current. The channel was in a closed state in the absence of perchlorate anions.

Bilayer lipid membranes and their application in electrochemical biosensors

The preparation and characteristics of bilayer lipid membranes including conventional bilayer membrane, solid supported self-assembling bilayer lipid membrane, solid supported hybrid bilayer membrane are described in this paper, The applications of bilayer lipid membranes in electrochemical biosensors are reviewed and the future development of electrochemical biosensor based on bilayer lipid membranes is discussed.

Effect of polyvinylidene fluoride hollow fiber membranes on mass transfer of samarium

The influence of swelling and stripping acidity on the mass transfer coefficient based on water phase and the inner diameters of membranes were studied with P507-HCl-Sm as working system in the two different kinds of hollow fiber membranes. Effects of extractant concentration, H+ concentration in aqueous phase and Sm3+ concentration on extraction rate were discussed and the corresponding reaction series were obtained. According to the investigations on the interfacial kinetics, the reaction kinetics equation and reaction rate constant were obtained.

Luminescent properties of organic-inorganic hybrid monoliths containing rare-earth complexes

Transparent organic-inorganic hybrid monoliths containing rare-earth complexes (Eu(TTA)(3)Phen, Tb(Sal)(3)) were prepared via the sol-gel technique. It could be observed by transmission electron microscopy that the fluorescent particles are distributed in the matrix at the microscopic level. The matrix is composed of organic-inorganic semiinterpenetrating networks, i.e., PHEMA-SiO2 system. The fluorescence emission spectra of samples are similar to those from corresponding powdered Eu(III) and Tb(III) complexes, and the half-widths of the strongest bands are less than 10 nm, which indicates that the monolith exhibits high fluorescence intensity and color purity. Furthermore, the fluorescence spectra exhibit no obvious change with decreasing nanoparticle size of the rare-earth complex. The fluorescence lifetimes of samples are longer than pure Eu(III), Tb(III) complexes, respectively. Samples irradiated with an UV lamp (365 nm) are still transparent but become bright red and green in color due to fluorescence of Eu(III) and Tb(III) complexes. (C) 2000 Elsevier Science B.V. All rights reserved.

Luminescent properties of Langmuir-Blodgett films of europium bisphthalocyanine

Eu(III)-octa-4-(tetrahydrofurfuroxy) phthalocyanine (EuPc2') was synthesied and characterized by elementary analysis, IR, MS, UV-vis spectra. EuPc2' has good film-forming ability from determination of isotherm of pi-A. The complex LB film was formed by depositing of EuPc2' on a quartz slide with the LB techniques of the Z-type, The luminescent properties of pure and doped LS films were determined. The results showed that pure films have good luminescent properties, the thicker the LB films, the stronger the fluorescent intensity. The films doped with o-phenanthroline (abbreviated as phen) made the relative intensity of fluorescent emission behavior enhance in comparison to that of pure LB film, But the amount of phen may be not too much. Our results showed that EuPc2':phen = 1: 10 (molar ratio) has the best fluorescent behavior. The electronic spectroscopic characterization of the LB films is also given.

Preparation and characterization of luminescent thin films doped with rare earth (Tb3+, Eu3+) complexes derived from a sol-gel process

Sol-gel derived luminescent thin films doped with rare earth (RE) complexes were prepared using an in-situ synthesis method with a two-step hydrolysis process and the luminescence spectra were measured. Fluorescence Lifetime and thermal stability were investigated. The results show that a broad excitation band indicates the formation of RE complexes in the solid thin films. RE ions, which are restrained in a silica matrix, present longer lifetime and higher thermal stability than that in DMF/PVB films containing the corresponding pure complexes. (C) 2000 Elsevier Science B.V. All rights reserved.

Influence of a kind of polyanion to hybrid bilayer membranes

Hybrid bilayer membrane consisting of self-assembled alkanethiol and lipid monolayer on gold electrode was fabricated by the paint - freeze method. The interaction of a kind of polyanion, K7Fe3+P2W17O62H2 with such bilayer membrane was investigated by cyclic voltammetry and ac impedance. The hybrid bilayer membrane on the gold electrode showed remarkable insulating property, however, the property was lessened to some extent after interaction with the polyanion. It was found the process was in-eversible. It is presumed that the interaction between the polyanion and lipid is an interaction of K7Fe3+P2W17O62H2 with the polar head group of PC, which lessens the interaction among PC polar head groups. The resulting molecular arrangement becomes looser, even some pores are produced.

Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes

The permeation behavior of water vapor, H-2, CO2, O-2, N-2, and CH4 gases in a series of novel poly(aryl ether sulfone)s has been examined over a temperature range of 30-100 degreesC. These polymers include four alkyl-substituted cardo poly(aryl ether sulfone)s and four intermolecular interaction enhanced poly(aryl ether sulfone)s. Their water vapor and gas transport properties were compared to the unmodified cardo poly(aryl ether sulfone) (PES-C). It was found that the bulky alkyl substituents on the phenylene rings were advantageous for gas permeability, while the intermolecular hydrogen bonds and ionic bonds resulted in a considerable increase in gas permselectivity. The causes of the trend were interpreted according to free volume, interchain distance, and glass transition temperature, together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest was the observation that IMPES-L, which simultaneously bears bulky isopropyl substituent and pendant carboxylic groups, displayed 377% higher O-2 permeability and 5.3% higher O-2/N-2 permselectivity than PES-C. Furthermore, sodium salt form PES-Na+ and potassium salt form PES-K+ exhibited water vapor permeability twice as high as PES-C and H2O/N-2 selectivity in 10(5) order of magnitude.

Sol-gel deposition of calcium silicate red-emitting luminescent films doped with Eu3+

Eu3+-activated calcium silicate (CaO-SiO2:Eu3+) luminescent films were prepared by the sol-gel method. The structural evolution of the film was studied by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the luminescence properties of the phosphor films were investigated as a function of heat treatment temperature. The XRD study indicates that a kilchoanite phase forms in the film sintered at 800 degreesC, which is different from that in gel powder treated under the same conditions. The SEM results show that the film thickness decreases and the particles in the film become smaller with increasing heat treatment temperature. The CaO-SiO2:Eu film shows the characteristic emission of Eu3+ under UV excitation, with the Eu3+ D-5(0)-->F-7(2) band (616 nm) being the most prominent. A large difference in the Eu3+ lifetime is observed between the film samples treated at 500 and 700 degreesC (or above). Concentration quenching occurs when the Eu3+ doping concentration is above 6 mol% of Ca2+ in the film.