Morphology and oxygen sensor response of luminescent Ir-labeled poly(dimethylsiloxane)/polystyrene polymer blend films

Polymer films consisting of a linear poly(dimethylsiloxane) end-functionalized with a luminescent Ir(III) complex (Ir-PDMS), blended with polystyrene (PS), function as optical oxygen sensors. The sensor response arises by quenching of the luminescence from the Ir(III) chromophore by oxygen that permeates into the polymer film. The morphology and luminescence oxygen sensor properties of blend films consisting of Ir-PDMS and PS have been characterized by fluorescence microscopy, atomic force microscopy, and scanning electron microscopy. The investigations demonstrate that microscale phase segregation occurs in the films. In blends that contain a relatively small amount of Ir-PDMS in PS (ca. 10 wt %), the Ir-PDMS exists as circular domains, with diameters ranging from 2 to 5 mum, surrounded by the majority PS phase. For larger weight fractions of Ir-PDMS in the blends, the film morphology becomes bicontinuous. A novel epifluorescence microscopy method is applied that allows the construction of Stern-Volmer quenching images that quantify the oxygen sensor response of the blend films with micrometer spatial resolution. These images provide a map of the oxygen permeability of the polymer blend films with a spatial resolution of ca. 1 mum. The results of this investigation show that the micrometer-sized Ir-PMDS domains display a 2-3-fold higher oxygen sensor response compared to the surrounding PS matrix. This result is consistent with the fact that PDMS is considerably more gas permeable compared to PS. The relationship of the microscale morphology of the blends to their performance as macroscale optical oxygen sensors is discussed.     

掺杂稀土配合物的无机/高分子纳米杂化薄膜的 制备与发光性能

通过在溶胶-凝胶过程中引入高分子组分,并将稀土配合物掺杂其中的方法得到了具有良好发光性能的无机/高分子杂化薄膜,它们有很好的韧性和透明性,测定了薄膜的荧光光谱和荧光寿命,发现它们均发射出稀土离子的特征荧光且寿命比本体配合物增长。透射电镜的观察表明配合物在SiO~2/高分子互穿网络中分布较均匀,分散尺度在20～30nm之间。     

Principal component analysis calibration method for dual-luminophore oxygen and temperature sensor films: application to luminescence imaging

Oxygen sensor films are frequently used to image air-pressure distributions on surfaces in aerodynamic wind tunnels. In this application, the sensor film is referred to as a pressure-sensitive paint (PSP). A Stern-Volmer calibration is used to relate the emission intensity ratio of a long-lifetime luminescent dye (the pressure-sensitive luminophore, PSL) to surface air pressure. A major problem in PSP measurements arises because the Stern-Volmer calibration of the PSL's emission varies with temperature. To correct for the temperature dependence, a second luminescent dye that has an emission that varies with temperature (the temperature-sensitive luminophore, TSL) is incorporated into the sensor film. With such a dual-luminophore PSP (DL-PSP), it is possible to measure the surface-temperature distribution with the TSL emission, and this information is then used to correct the temperature dependence of the PSL's pressure response. In the present article, we report the application of a DL-PSP to obtain high-resolution air-pressure distributions on a surface that is subjected to a 20 degrees C temperature gradient. Two different calibration methods are used to generate surface-temperature and air-pressure distributions from the luminescence imaging data, and a quantitative comparison of the results obtained from the two methods is provided. The first method is based on an intensity-ratio calibration that uses luminescence images collected at two wavelengths, one corresponding to the TSL emission and the second corresponding to the PSL emission. The second method is based on principal component analysis (PCA) of luminescence images obtained at four wavelengths throughout the spectral region of the TSL and PSL emission (hyperspectral imaging, 550-750 nm). The results demonstrate that the PCA method allows the measurement of surface air pressure with higher accuracy and precision compared to those of the intensity-ratio method. The improvement is especially significant at pressures near 1 atm, where the temperature interference is most pronounced. Surface-pressure distributions are measured with comparable accuracy and precision with the two methods.     

Preparation and spectroscopic properties of cyclodeca-1,6-diyne

The preparation of cyclodeca-1,6-diyne (=1) is reported. The PE results reveal a strong interaction between the in plane π molecular orbitals of {=1}.     

Preparation, luminescent, structural and electrical properties of Langmuir-Blodgett films of new organomercurial acetylide complex/heteropolyoxometalate hybrid composites

A new family of organometallic/inorganic nanohybrid Langmuir-Blodgett (LB) films consisting of rigid-rod organomercury acetylide complex (OMA) as the π-conjugated organometallic composite and heteropolyacid salts MPA (MPA = K₃PMo₁₂O₄₀, K₅BW₁₂O₄₀, Na₅IMo₆O₆₂) of the Keggin and Anderson structures as the inorganic composite, were prepared and characterized by π−A isotherms, UV−Vis absorption spectra, fluorescence spectra, scanning tunneling microscopy, atomic force microscopy imaging and low-angle X-ray diffraction. Our experimental results indicate that steady Langmuir and LB films are formed in pure water and heteropolyacid salt subphases. Luminescence spectra of hybrid LB films show that MPA can quench the emission of OMA to some extent. These alkynylmercury(II) based LB films display interesting electrical conductivity behavior. They all show decent electrical conductivity, and the tunneling current amounts to ±100 nA when the voltage is set at ±3 ∼ ±5 V.     

Preparation and spectroscopic properties of 2-benzothiazolyl araldehyde hydrazones

Notwithstanding its tendency toward air oxidation in solution, 2-hydrazinobenzothiazole I reacted with aromatic aldehydes in ethanol to give the corresponding hydrazones III-XV in high yields and analytical purity. In related examples, acylation took place under similar conditions to produce hydrazides XVI-XX . The near-infrared bands of the absorption spectra of the araldehyde hydrazones have been associated with charge transfer and appeared to correlate with structural elements of the compounds in a way suggesting that the charge transfer was intermolecular.     

Preparation and spectroscopic properties of 3-acyl-1,3,4-oxadiazolines

1,3,4-Oxadiazolines I , in which substituent groups R₁ through R₄ may be varied through appropriate choice of precursor reactants, can be prepared in good yields and purity by convenient cyclizations of acyl-hydrazones with anhydrides. The reactions can be effectively monitored by salient changes in the infrared spectra. The oxadiazolines are stable materials and thus serve as suitable derivatives for the chemical characterization of such tuberculostatic Schiff bases as IIa-c.     

Preparation and spectral properties of high-efficiency luminescent polyethylenimine-stabilized CdS quantum dots

Feasibility was demonstrated for obtaining ultrasmall colloidal CdS nanoparticles (with diameter about 2 nm) stabilized in aqueous solution by polyethylenimine with a narrow size distribution (~10%) and luminescing at 400-600 nm (quantum yield about 10%). Complexation between Cd^II and polyethylenimine is a necessary condition for formation of such nanoparticles.     

Preparation and properties of sol-gel coating films

The present state of our knowledge on sol-gel coating films has been reviewed. A qualitative discussion is made on the limit of the film thickness which can be achieved in the sol-gel method and the factors affecting the film thickness. Considering that properties of the film are intimately related to the microstructure, types of microstructures accomplished by the sol-gel coating are introduced with examples.     

The synthesis, crystal structure and spectroscopic properties of luminescent Zn(II) complex

A luminescent Zn(II) complex 1, ZnL2Cl2.2H2O has been synthesized where L=2,2',2'-(1,3,5-benzenetriyltrimethylidyne) as a yellow crystal. Single crystal X-ray analysis of the compound 1 shows a distorted tetrahedral structure. The compound 1 crystallizes in monoclinic, space group C2/c with a = 20.3151(19), b = 8.7299(9), c = 24.626(2) angstroms, beta = 107.474(2) degrees , V = 4165.9(7) A3. At room temperature, the complex 1 exhibits an intense blue emission at 474 nm upon 380 nm excitation.     

X-ray structure and temperature dependent luminescent properties of two bimetallic europium complexes

The structural, luminescent and temperature dependent luminescent properties of two homodinuclear europium complexes bridged by 2,2′-bipyrimidine (bpm) are reported. β-Diketonate ligands 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione (tfa) and 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (tta) are used as capping ligands resulting in complexes of the form [Eu(tfa)₃]₂bpm (1) and [Eu(tta)₃]₂bpm (2). All Eu^III ions are eight coordinate with six O atoms from the β-diketones and two N atoms from the polyazine bridging ligand. Excitation of the β-diketonate ligands tfa or tta at ca. 340 nm in toluene solutions results in the characteristic Eu^III emission in the visible region of the spectrum. The emission intensity and lifetime associated with the Eu^III centers decrease as the temperature of the solution is increased. Lifetime measurements are fit to a monoexponential while the temperature dependent lifetime data is fit to an Arrhenius-type equation. Evaluation of the data in comparison to data obtained from the monometallic Eu^III analogs reveal very similar photoluminescent properties. This suggests little electronic communication between Eu^III ions via the polyazine bpm bridging ligand.     

Preparation, morphology, and luminescent properties of europium-doped nanodispersed scandium sesquioxide

Scandium sesquioxide-based solid solutions of composition Sc_{2 ? 2x} Eu_2x O₃ (0.005 ?? x ?? 0.05) were prepared by thermolysis of Sc_{1 ? x} Eu _x (CH₃COO)₃ and by reacting mixtures of scandium and europium nitrates with ethylene glycol. Thermal decomposition of Sc_{1 ? x} Eu _x (CH₃COO)₃ was found to yield Sc_{2 ? 2x} Eu_2x O₃ with the shapes of aggregates atypical of the cubic structure of this oxide, and the reaction products of scandium and europium nitrates were found to have a loose spongelike structure. A spectroscopic study showed that Sc_{2 ? 2x} Eu_2x O₃ and Sc_{1 ? x} Eu _x (CH₃COO)₃ are potential luminescent materials active in the visible spectral region. The tervalent europium in the Sc_{2 ? 2x} Eu_2x O₃ structure is the source of strong red emission (⁵ D ₀ ?? ⁷ F ₂) and can be used in fluorescent lamps, colored lightning, and optoelectronic devices.     

Preparation and spectroscopic properties of 2'''',5''''-dideoxynucleosidylcobalamins

Two new coenzyme B12 analogues, 2',5'-dideoxycytidylcobalamin (2a) and 2',5'-dide-oxyuridinylcobalamin (2b), and two others, 2',5'-dideoxyadenosylcobalamin (2c), and 5'-deoxy-thymidylcobalamin (2d) were prepared by an improved method. All the four analogues were investigated by UV-vis and 2D 1H NMR spectroscopy. The comparisons and discussion about their spectroscopic properties were done.     

Preparation and photoelectric properties of mesoporous ZnO films

Mesoporous ZnO films doped with Ti⁴⁺ (M-ZnO) have been prepared by doping process and sol–gel method. The films have mesoporous structures and consist of nano-crystalline phase, as evidenced from small angle X-ray diffraction and high resolution transmission electron microscopy. The wide angle X-ray diffraction of M-ZnO films confirms that M-ZnO has hexagonal wurtzite structure and ternary ZnTiO₃ phases. Ultraviolet–visible transmittance spectra, absorbance spectra and energy gaps of the films were measured. The Eg of M-ZnO is 3.25 eV. Photoluminescence intensity of M-ZnO centered at 380 nm increases obviously with the excitation power, which is due to the doping process and enhanced emission efficiency. M-ZnO thin films display a positive photovoltaic effect compared to mesoporous TiO₂ (M-TiO₂) films.     

Novel luminescent Ir(III) dyes for developing highly sensitive oxygen sensing films

New sensing films have been developed for the detection of molecular oxygen. These films are based on luminescent Ir(III) dyes incorporated either into polystyrene (with and without plasticizer) or metal oxide, nanostructured material. The preparation and characterization of each film have been investigated in detail. Due to their high sensitivity for low oxygen concentration, the parameters pO₂(S=1/2) and ΔI_1% have been also evaluated in order to establish the most sensitive membrane for controlling concentrations between 0 and 10% and low oxygen concentrations (lower than 1%), respectively. The results show that the use of nanostructured material increased the sensitivity of the film; the most sensitive membrane for controlling O₂ between 0 and 10% is based on N1001 immobilized in AP200/19 (k_sv = 2848 ± 101 bar⁻¹ and pO₂(S=1/2)=0.0006), and the complex N969 incorporated into AP200/19 seems to be the most suitable for applications in oxygen trace sensing (ΔI_1% = 93.13 ± 0.13%).     

Electrochemically deposited organic luminescent films: the effects of deposition parameters on morphologies and luminescent efficiency of films

The electropolymerization behaviors of an electroactive and luminescent compound TCPC as precursor are studied. The resultant electrochemical deposition (ED) films are characterized by cyclic voltammetry (CV), UV-vis, fluorescence spectra, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Under the CV mode with potential range of -0.5 to 0.85 V vs Ag/Ag(+), the coupling reactions between the carbazole units of TCPC are very efficient, while the fluorescent trifluorene segment in TCPC is chemically inert in this potential range, which results in a highly fluorescent film formation on indium tin oxide (ITO) electrode. The deposition parameters for preparing the TCPC-based ED films are optimized, and the best ED film gives the fluorescence efficiency of 45.5% with surface roughness of 2.8 nm and morphologic stability as heating to 180 degrees C. The light-emitting devices (LEDs) using this ED film as light emitting layer with structure ITO/ED film (approximately 100 nm)/Ba/Al achieve maximum luminescence and external quantum efficiency of 4224 cd/m(2) at 17 V and 0.72% at 11.5 V, respectively, which are better than the device using TCPC spin-coating films as emitting layer. The technique provides a facile route toward a patternable luminescent film and device because such luminescent ED films can be manipulatively deposited on the electrified electrode.     

Mechanical properties and temperature dependence of grafted casein films

Casein was grafted with acrylonitrile and n-butyl methacrylate. The stress-strain characteristics at various temperatures were studied. The tensile strength and percent elongation increase, attain a maximum and then decrease with increase of temperature. Stress relaxation was also studied at various temperatures. The stress decays rapidly with a steep negative slope at 20° and 70°C suggesting that there are transitions at these temperatures.     

C~6~0-甲苯衍生物的制备及光谱特性研究

以C~6~0和甲苯为原料,选择适当的催化反应条件,制备了C~6~0-甲苯衍生物。产物经紫外可见光谱和H质子核磁共振谱测定,推测了产物结构和反应机理。对不同反应时间产物光致发光光谱的特性进行研究,并与C~6~0发光光谱比较,室温下观测到峰值位于460nm附近递增的光致发光现象。     

Infrared spectroscopic properties of water molecules dissolved in some oxygen bases

The infrared spectra in the OH-stretching and HOH-bending regions of H₂O, and in the OH-stretching region of HDO dissolved in a number of ketones and ethers have been recorded. The number of component bands and their wavenumbers, halfwidths and intensities, as well as the total OH-stretching intensity in each solvent, have been interpreted in terms of a model for the types of hydrogen bonded solvent:water complexes formed in these systems.The effect of temperature on the spectra of H₂O in some of the ketones has been rationalized on the basis of the equilibrium existing between the different hydrogen bonded species present in solution.