Remarkable changes in the optical properties of CeO2 nanocrystals induced by lanthanide ions doping

Highly uniform and well-dispersed CeO2 and CeO2:Eu3+ (Sm3+, Tb3+) nanocrystals were prepared by a nonhydrolytic solution route and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), UV/vis absorption, and photoluminescence (PL) spectra, respectively. The result of XRD indicates that the CeO2 nanocrystals are well crystallized with a cubic structure. The TEM images illustrate that the average size of CeO2 nanocrystals is about 3.5 nm in diameter. The absorption spectrum of CeO2:Eu3+ nanocrystals exhibits red-shifting with respect to that of the undoped CeO2 nanocrystals. Under the excitation of 440 nm (or 426 nm) light, the colloidal solution of the undoped CeO2 nanocrystals shows a very weak emission band with a maximum at 501 nm, which is remarkably enhanced by doping additional lanthanide ions (Eu3+, Tb3+, Sm3+) in the CeO2 nanocrystals. The emission band is not due to the characteristic emission of the lanthanide ions but might arise from the oxygen vacancy which is introduced in the fluorite lattice of the CeO2 nanocrystals to compensate the effective negative charge associated with the trivalent ions.

Luminescence functionalization of SBA-15 by YVO4 : Eu3+ as a novel drug delivery system

Luminescence functionalization of the ordered mesoporous SBA-15 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process, resulting in the formation of the YVO4:Eu3+@SBA-15 composite material. This material, which combines the mesoporous structure of SBA-15 and the strong red luminescence property of YVO4:Eu3+, can be used as a novel functional drug delivery system. The structure, morphology, porosity, and optical properties of the materials were well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, N-2 adsorption, and photoluminescence spectra. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the YVO4:Eu3+ layer and the adsorption of ibuprofen (IBU, drug). The IBU-loaded YVO4:Eu3+@SBA-15 system still shows the red emission of Eu3+ (617 nm, D-5(0)-F-7(2)) under UV irradiation and the controlled drug release property. Additionally, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU in the system, making the extent of drug release easily identifiable, trackable, and monitorable by the change of luminescence. The system has great potential in the drug delivery and disease therapy fields.

Monodisperse and core-shell-structured SiO2@YBO3 : Eu3+ spherical particles: Synthesis and characterization

Y0.9Eu0.1BO3 phosphor layers were deposited on monodisperse SiO2 particles of different sizes (300, 570, 900, and 1200 nm) via a sol-gel process, resulting in the formation of core-shell-structured SiO2@Y0.9Eu0.1BO3 particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and cathodoluminescence (CL) spectra as well as lifetimes were employed to characterize the resulting composite particles. The results of XRD, FE-SEM, and TEM indicate that the 800 degrees C annealed sample consists of crystalline YBO3 shells and amorphous SiO2 cores, in spherical shape with a narrow size distribution. Under UV (240 nm) and VUV (172 nm) light or electron beam (1-6 kV) excitation, these particles show the characteristic D-5(0)-F-7(1-4) orange-red emission lines of Eu3+ with a quantum yield ranging from 36% (one-layer Y0.9Eu0.1BO3 on SiO2) to 54% (four-layer Y0.9Eu0.1BO3 on SiO2).

MCM-41 functionalized with YVO4 : Eu3+: a novel drug delivery system

Luminescence functionalization of ordered mesoporous MCM-41 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process. This material, which combines the mesoporous structure of MCM-41 and the strong red luminescence property of YVO4: Eu3+, has been studied as a host carrier for drug delivery/release systems. The structure, morphology, texture and optical properties of the materials were well characterized by x-ray diffraction ( XRD), Fourier infrared spectroscopy ( FT-IR), transmission electron microscopy ( TEM), N-2 adsorption and photoluminescence ( PL) spectra. The results indicated that the specific surface area and pore volume of MCM-41, which were directly correlated to the drug-loading amount and ibuprofen ( IBU) release rate, decreased in sequence after deposition of YVO4:Eu3+ and loading of IBU as expected. The IBU-loaded YVO4:Eu3+@ MCM-41 system still showed red luminescence under UV irradiation ( 365 nm) and a controlled release property for IBU. In addition, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU, making the extent of drug release easily identified, tracked and monitored by the change of luminescence, which demonstrates its potential application in drug delivery/release systems.

Tunable luminescence properties of Tb3+-doped LaGaO3 nanocrystalline phosphors

Nanocyrstalline Tb3+-doped LaGaO3 phosphors were prepared through a Pechini-type sol-gel process. X-ray diffraction, field-emission scanning electron microscopy (FESEM), photoluminescence, cathodoluminescence spectra, and lifetimes were utilized to characterize the synthesized phosphors. XRD results reveal that the sample begins to crystallize at 900 degrees C and pure LaGaO3 phase can be obtained at 1000 degrees C. FESEM images indicate that the Tb3+-doped LaGaO3 phosphors are composed of aggregated spherical particles with sizes ranging from 40 to 80 nm. Under the excitation of ultraviolet light and low-voltage electron beams (0.5-3 kV), the Tb3+-doped LaGaO3 phosphors show the characteristic emissions from the LaGaO3 host lattice and the Tb3+ (D-5(3,4)-F-7(6,5,4,3) transitions). The emission colors of Tb3+-doped LaGaO3 phosphors can be tuned from blue to green by changing the excitation wavelength of ultraviolet light and the doping concentration of Tb3+ to some extent. Relevant luminescence mechanisms are discussed.

Host-sensitized luminescence of Dy3+, Pr3+, Tb3+ in polycrystalline SrIn2O4 for field emission displays

SrIn2O4:Dy3+/Pr3+/Tb3+ white/red/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence, cathodoluminescence spectra, and lifetimes were utilized to characterize the samples. XRD reveal that the samples begin to crystallize at 800 degrees C and pure SrIn2O4 phase can be obtained at 900 degrees C. FE-SEM images indicate that the SrIn2O4:Dy3+, SrIn2O4:Pr3+, and SrIn2O4:Tb3+ samples consist of fine and spherical grains with size around 200-400 nm. Under the excitation of ultraviolet light and low-voltage electron beams (1 - 5 kV), the SrIn2O4:Dy3+, SrIn2O4: Pr3+, and SrIn2O4: Tb3+ phosphors show the characteristic emissions of Dy3+ (F-4(9/2) - H-6(15/2) at 492 nm and 4F(9/2) - 6H(13/2) at 581 nm, near white), Pr3+ (P-3(0) - H-3(4) at 493 nm, D-1(2) - H-3(4) at 606 nm, and P-3(0) - H-3(6) at 617 nm, red) and Tb3+ (D-5(4) - F-7(6,5,4,3) transitions dominated by D-5(4) - F-7(5) at 544 nm, green), respectively. All of the luminescence resulted from an efficient energy transfer from the SrIn2O4 host lattice to the doped Dy3+, Pr3+, and Tb3+ ions, and the luminescence mechanisms have been proposed.

Tris(2,2 '-bipyridyl) ruthenium(II) doped silica film modified indium tin oxide electrode and its electrochemiluminescent properties

An approach was reported to synthesize silica hybridized ruthenium bipyridyl complex through amidation reaction by covalent attachment of bis(bipyridyl)-4,4'-dicarboxy-2,2'-bipyridyl-ruthenium to (3-aminopropyl)-triethoxysilane. The hybrid complex then was gelatinized through acid catalytic hydrolysis method and a sol-gel modified indium, tin oxide electrode was prepared via spin coating technique. As prepared indium tin oxide electrode possesses good stability therein with excellent electrochemiluminescence behavior.

Synthesis and characterization of monodisperse spherical core-shell structured SiO2@Y3Al5O12 : Ce3+/Tb3+ phosphors for field emission displays

Nanocrystalline Y3Al5O12: Ce3+/Tb3+ ( average crystalline size 30 nm) phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by the sol-gel method, resulting in the formation of core-shell structured SiO2@Y3Al5O12:Ce3+/Tb3+ particles. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO2@Y3Al5O12: Ce3+/Tb3+ phosphor particles. The obtained core-shell structured phosphors consist of well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the Y3Al5O12:Ce3+/Tb3+ shells on the SiO2 cores ( average size about 500 nm, crystalline size about 30 nm) could be easily tailored by varying the number of deposition cycles (100 nm for four deposition cycles). Under the excitation of ultraviolet and low-voltage electron beams (1-3 kV), the core-shell SiO2@Y3Al5O12:Ce3+/ Tb3+ particles show strong yellow-green and green emission corresponding to the 5d-4f emission of Ce3+ and D-5(4)-F-7(J) ( J = 6, 5, 4, 3) emission of Tb3+, respectively.

Host-sensitized luminescence of Dy3+, Pr3+ , Tb3+ in polycrystalline CaIn2O4 for field emission displays

Caln(2)O(4):Dy3+/Pr3+/Tb3+ blue-white/green/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence (PL) and cathodoluminescencc (CL) spectra as well as lifetimes were utilized to characterize the samples. The XRD results reveal that the samples begin to crystallize at 800 degrees C 3-1 and pure CaIn2O4 phase can be obtained after annealing at 900 degrees C. The FE-SEM images indicate that the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ samples consist of spherical grains with size around 200-400nm. Under the excitation of ultraviolet light and low electron beams (1-5kV), the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ phosphors show the characteristic emissions of Dy3+ ((F9/2-H15/2)-F-4-H-6 and (F9/2-H13/2)-F-4-H-6 transitions, blue-white), Pr3+ ((P0-H4)-P-3-H-3, (D2-H4)-D-1-H-3 and (P1-H5)-P-3-H-3 transitions, green) and Tb3+ ((D4-F6,5,4,3)-D-5-F-7 transitions, green), respectively. All the luminescence is resulted from an efficient energy transfer from the CaIn2O4 host lattice to the doped Dy3+ ,Pr3+ and Tb3+ ions, and the corresponding luminescence mechanisms have been proposed.

Enhanced photoluminescence of Ba2GdNbO6: Eu3+/Dy3+ phosphors by Li+ doping

The Ba2GdNbO6: Eu3+/Dy3+ and Li+-doped Ba2GdNbO6: Eu3+/Dy3+ phosphors were prepared by solid-state reaction process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and photoluminescence (PL) as well as lifetimes, was utilized to characterize the resulting phosphors. Under the excitation of ultraviolet light, the Ba2GdNbO6: Eu3+/Dy3+ and Li+-doped Ba2GdNbO6: Eu3+/Dy3+ show the characteristic emissions of Eu3+ (D-5(0)-F-7(1,2,3) transitions dominated by D-5(0)-F-7(1) at 593 nm) and Dy3+ (F-4(9/2)-H-6(15/2),(13/2) transitions dominated by F-4(9/2)-H-6(15/2) at 494 nm), respectively. The incorporation of Li+ ions into the Ba2GdNbO6: Eu3+/Dy3+ phosphors has enhanced the PL intensities depending on the doping concentration of Li+, and the highest emission was obtained in Ba2Gd0.9NbO6: 0.10Eu(3+), 0.01Li(+) and Ba2Gd0.95NbO6: 0.05Dy(3+), 0.07Li(+), respectively. An energy level diagram was proposed to explain the luminescence process in the phosphors.

Effects of polar group saturation on physical gelation of Amphiphilic polymer solutions

Monte Carlo simulation on the basis of the comblike coarse grained nonpolar/polar (NP) model has been carried out to study the polar group saturation effect on physical gelation of amphiphilic polymer solutions. The effects of polar group saturation due to hydrogen bonding or ion bridging on the sol-gel phase diagram, microstructure of aggregates, and chain conformation of amphiphilic polymer solutions under four different solvent conditions to either the nonpolar backbone or the polar side chain in amphiphilic polymer chains have been investigated. It is found that an increase of polar group saturation results in a monotonically decreased critical concentration of gelation point, which can be qualitatively supported by the dynamic theological measurements on pectin aqueous solutions. Furthermore, various solvent conditions to either the backbone or the side chain have significant impact on both chain conformation and microstructure of aggregates. When the solvent is repulsive to the nonpolar backbone but attractive to the polar side chain, the polymer chains are collapsed, and the gelation follows the mechanism of colloidal packing; at the other solvent conditions, the gelation follows the mechanism of random aggregation.

Synthesis and luminescent properties of europium (III) schiff base complexes covalently bonded to silica xerogels

A new kind of luminescent organic-inorganic hydrid material consisting of Eu(III)-schiff base complex covalently bonded to silica xerogel was synthesized via the sol-gel method using a Eu (N-propylene salicylimine ligand) complex modified with pendant triethoxysilane groups (Eu(III)(salenHSi)). The Eu(III)(salenHSi) complex is characterized by Fourier transform infrared (FT-IR) spectroscopy. Luminescent properties of the complex and the resulted hybrid silica xerogels have been investigated at room temperature.

Sensitive biomimetic sensor based on molecular imprinting at functionalized indium tin oxide electrodes

We initially report an electrochemical sensing platform based on molecularly imprinted polymers (MIPs) at functionalized Indium Tin Oxide Electrodes (ITO). In this research, aminopropyl-derivatized organosilane aminopropyltriethoxysilane (APTES), which plays the role of functional monomers for template recognition, was firstly self-assembled on an ITO electrode and then dopamine-imprinted sol was spin-coated on the modified surface. APTES which can interact with template dopamine (DA) through hydrogen bonds brought more binding sites located closely to the surface of the ITO electrode, thus made the prepared sensor more sensitive for DA detection. Potential scanning is presented to extract DA from the modified film, thus DA can rapidly and completely leach out. The affinity and selectivity of the resulting biomimetic sensor were characterized using cyclic voltammetry (CV). It exhibited an increased affinity for DA over that of structurally related molecules, the anodic current for DA oxidation depended on the concentration of DA in the linear range from 2 x 10(-6) M to 0.8 x 10(-3) M with a correlation coefficient of 0.9927.In contrast, DA-templated film prepared under identical conditions on a bare ITO showed obviously lower response toward dopamine in solution.

Effect of silver nanoparticles on luminescent properties of europium complex in di-ureasil hybrid materials

Organic-inorganic hybrids containing luminescent lanthanide complex Eu(tta)(3)Phen (tta = thenoyltrifluoroaceton, phen = 1,10-phenanthroline) and silver nanoparticles have been prepared via mixing rare earth complex and nanoparticles with the precursors of di-ureasil using a sol-gel process. The obtained hybrid materials with transparent and elastomeric features were characterized by transmission electron microscope, solid-state Si-29 magic-angle spinning NMR spectra, diffuse reflectance, UV-visible absorption and photoluminescence spectroscopies. The effect of the silver nanoparticles on the luminescence properties was investigated. The experimental results showed that the luminescence intensity of the Eu(tta)(3)phen complex could be enhanced by less than ca. 9.5 nM of silver nanoparticles with the average diameter of 4 nm, and reached its maximum at the concentration of ca. 3.6 nM. Further increasing the concentration of the silver nanoparticles (> 9.5 nM) made the luminescence quenched. The enchancement and quench mechnism was discussed.