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.

Formation of a supported hybrid bilayer membrane on gold: A sterically enhanced hydrophobic effect

Adsorption of a monolayer of didecanoyl-L-alpha-phosphatidylcholine (DDPC) from dispersions of small unilamellar vesicles onto hydrophobic surfaces was investigated by mean of cyclic voltammetry and impedance spectroscopy. The hydrophobic surfaces were self-assembled monolayers of 2-mereapto-3-n-octylthiophene (MOT) on gold. One characteristic of the MOT monolayer is its permeability to organic molecules in aqueous solution, thus providing a more energetically favorable hydrophobic surface for the addition of phospholipid vesicles. The kinetics of the lipid monolayer formation were followed by measuring the time-dependent interfacial capacitance. Unusual values of thickness and capacitance of the MOT/ DDPC bilayers were observed. An interdigitating conformation of the bilayer structure was proposed to interpret the experimental results, The horseradish peroxidase reconstituted into the bilayer demonstrated the expected protein activity, showing practical use in research and in biosensor application.

Interactions of thiamine monophosphate (TMP) with one- and two-dimensional polymeric halogenomercurate anions. Crystal structures of (TMP)(Hg2Br5)center dot 0.5H(2)O and (TMP)(2)(Hg3I8)

An investigation into the interactions between thiamine monophosphate (TMP) and anions has resulted in the preparation and X-ray characterization of the compounds (TMP)(Hg2Br5).0.5H(2)O (1) and (TMP)(2)(Hg3I8) (2). In each compound the TMP molecule exists as a monovalent cation in the usual F conformation. The halogenomercurate anions occur in two-dimensional (2-D) network in 1 or one-dimensional (1-D) chain in 2. In both 1 and 2, the structures consist of alternating cationic sheets of the hydrogen-bonded TMP molecules and anionic sheets of the polymeric halogenomercurate anions. The TMP molecule binds to the polymeric anions through the characteristic 'anion bridge I', C(2)-H..X...pyrimidinium (X = Br in 1 and 1 in 2), and electrostatic interactions between electropositive S(1) and halogen atoms. The 'anion bridge II' of the type N(4'1)-H...X...thiazolium (X = phosphate group) plays a role in stabilizing the molecular conformation. The biological implication of the host-guest-like complexation between TMP and polymeric anions is discussed.

Progress in deoxyribonucleic acid electroanalysis

The electroanalysis research of deoxyribonucleic acid (DNA) is an attractive project in life science. This paper reviews the recent progress of DNA electrochemical analysis, which includes DNA electroanalysis and DNA electrochemical biosensors. The prospects of the research are very bright. 77 papers are cited.

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.

Single-crystal X-ray structure and properties of K-10[Ni-4(H2O)(2)(AsW9O34)(2)]center dot 4H(2)O

The rational synthesis and the structural and magnetic characterization of a nickel cluster are presented. The compound comprises a rhomblike Ni4O16 group encapsulated between two-heptadentate tungstoarsenate ligands [AsW9O34](9-). The crystal structure of K-10[Ni-4(H2O)(2)(AsW9O34)(2)](.)4H(2)O was solved in monoclinic, P2(1)/n symmetry, with a = 12.258(3) Angstrom, b = 21.232(4) Angstrom, c = 15.837(3) Angstrom, beta = 92.05(3)degrees, V = 4119.1(14) Angstrom(3), Z = 2, and R = 0.0862. The crystal structure of the Ni(II) derivative was compared with that of the Cu(II), Zn(II), Co(II) and Mn(II) derivatives. The Ni4O14(H2O)(2) unit in the compound shows no Jahn-Teller distortion. On the other hand, the Ni(II) derivative shows ferromagnetic exchange interactions within the Ni4O16 group (J = 7.8 cm(-1), J' = 13.7 cm(-1)) and an S = 4 ground state, the highest spin state reported in a heteropoly complex. Its redox electrochemistry has been studied in acid buffer solutions using cyclic voltammetry. It exhibited two steps of one-electron redox waves attributed to redox processes of the tungsten-oxo framework. The new catalyst showed an electrocatalytic effect on the reduction of NO2-.

Surface renewable graphite organosilicate composite electrode containing indium(III) hexacyanoferrate(II/III)

Indium(III) hexacyanoferrate(II/III) (InHCF) supported on graphite powder was prepared using the in situ chemical deposition procedure and subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive graphite organosilicate composite. The composite was used as the electrode material to fabricate a three-dimensional InHCF-modified electrode. InHCF acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The chemically modified electrode can electrocatalyze the oxidation of thiosulfate, and exhibits a good repeatability of surface-renewal by simple mechanical polishing, as well as simple preparation, good chemical and mechanical stability.

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.

Amperometric quantification of polar organic solvents based on a tyrosinase biosensor

A novel amperometric biosensor for quantification of the electrochemically inert polar organic solvents based on tyrosinase electrode was preliminarily reported. The biosensor was fabricated by simply syringing an aqueous solution of tyrosinase/PVAVP (PVAVP: copolymer of poly(vinyl alcohol) grafting with 4-vinylpyridine) onto glassy carbon electrode surface followed by drying the modified electrode at +4 degrees C in a refrigerator. The current generated from electrochemical reduction of quinone is a probe signal. The biosensor can be used for quantification of polar organic solvents, and its mechanism was characterized with in situ steady-state amperometry-quartz crystal microbalance experiments. The detection limit, sensitivity, and dynamic range for certain organic solvents are dependent on the kind and concentration of the substrate probe and the hydrophobicity of the immobilization matrix. The response time for all the tested organic solvents is less than 2 min.

Self-assembled monolayer growth of phospholipids on hydrophobic surface toward mimetic biomembranes: Scanning probe microscopy study

Atomic force microscopy (AFM) and lateral force microscopy (LFM) were used simultaneously to analyze a model membrane bilayer structure consisting of a phospholipid outer monolayer deposited onto organosilane-derivatized mica surfaces, which were constructed by using painting and self-assembly methods. The phospholipid used as outer monolayer was dimyristoylphosphatidylcholine (DMPC). The hydrocarbon-covered substrate that formed the inner half bilayer was composed of a self-assembly monolayer (SAM) of octadecyltrichloroorganosilane (OTS) on mica. SAMs of DMPC were formed by exposing hydrophobic mica to a solution of DMPC in decane/isobutanol and subsequently immersing into pure water. AFM images of samples immersed in solution for varying exposure times showed that before forming a complete monolayer the molecules aggregated into dense islands (2.2-2.6 nm high) on the surface. The islands had a compact and rounded morphology. LFM, coupled with topographic data obtained with the atomic force mode, had made possible the distinction between DMPC and OTS. The rate constant of DMPC growth was calculated. This is the first systematic study of the SAM formation of DMPC by AFM and LFM imaging. It reveals more direct information about the film morphology than previous studies with conventional surface analytical techniques such as infrared spectroscopy, X-ray, or fluorescence microscopy.

Electrochemical behavior of redox species at carbon fibre microdisk array electrode modified with mixed-valent molybdenum(VI, V) oxide

In this study, electrode responses to a large number of electroactive species with different standard potentials at the molybdenum oxide-modified carbon fibre microdisk array (CFMA) electrode were investigated. The results demonstrated that the electrochemical behavior for those redox species with formal potentials more positive than similar to 0.0 V at the molybdenum oxide-modified CFMA electrode were affected by the range and direction of the potential scan, which were different from that at a bare CFMA electrode. If the lower limit of the potential scan was more positive than the reduction potential of the molybdenum oxide film, neither the oxidation nor the reduction peaks of the redox species tested could be observed. This indicates that electron transfer between the molybdenum oxide film on the electrode and the electroactive species in solution is blocked due to the existence of a high resistance between the film and electrolyte in these potential ranges. If the lower limit of the potential scan was more negative than the reduction potential of the molybdenum oxide film (similar to - 0.6 V), the oxidation peaks of these species occurred at the potentials near their formal potentials. In addition, the electrochemical behavior of these redox species at the molybdenum oxide-modified CFMA electrode showed a diffusionless electron transfer process. On the other hand, the redox species with formal potentials more negative than similar to - 0.2 V showed similar reversible voltammetric behaviors at both the molybdenum oxide-modified CFMA electrode and the bare electrode. This can be explained by the structure changes of the film before and after reduction of the film. In addition we also observed that the peak currents of some redox species at the modified electrode were much larger than those at a bare electrode under the same conditions, which has been explained by the interaction between these redox species and the reduction state of the molybdenum oxide film. (C) 2000 Elsevier Science Ltd. All rights reserved.

Fabrication of layer-by-layer deposited multilayer films containing DNA and its interaction with methyl green

Multilayer films were fabricated by layer-by-layer electrostatic deposition techniques between poly(diallyIdimethylammonium chloride) (PDDA) and calf thymus DNA (CT DNA) on glassy carbon and quartz substrates. Electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FTIR) spectroscopy and UV-vis spectroscopy demonstrated the uniform assembly of PDDA/DNA multilayer films, and X-ray photoelectron spectroscopy confirmed the elemental composition of the films. Moreover, the interaction of DNA in PDDA/DNA films with methyl green was investigated by UV-vis spectroscopy and circular dichroism (CD). (C) 2001 Elsevier Science B.V. All rights reserved.

A novel method for preparing ordered SnO2/TiO2 alternate nanoparticulate films

A novel method using LB films as precursors to prepare pure inorganic ordered film with periodic structure was developed. Surfactant-stabilized SnO2 nanoparticulate organosols and TiO2 nanoparticulate organosols were prepared and used as spreading solutions. Using LB technique, the good film-forming ability of the surfactant-stabilized SnO2 nanoparticles and TiO2 nanoparticles was confirmed by the determination of the pi -A isotherms. The surfactant-stabilized SnO2 and TiO2 nanoparticulate monolayers were fabricated on the water surface and then were transferred to solid substrates (CaF2, quartz, silicon, and so on) alternately, layer-by-layer. Then the as-deposited alternate LB film was treated at different temperatures. The as-deposited alternate LB film and the treated film were characterized by Fourier transform infrared spectroscopy, UV visible spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results indicate that our method was successful. The as-deposited alternate LB film formed a periodic structure with a long spacing of 6.5 nm that was composed of SnO2 nanoparticles, TiO2 nanoparticles, and arachidic acid. The treated film composed of SnO2 nanoparticles and TiO2 nanoparticles formed a pure inorganic periodic structure with an ordered distance of 5.4 nm. (C) 2001 Academic Press.

Amplification of antigen-antibody interactions based on biotin labeled protein-streptavidin network complex using impedance spectroscopy

Antibody was covalently immobilized by amine coupling method to gold surfaces modified with a self-assembled monolayer of thioctic acid. The electrochemical measurements of cyclic voltammetry and impedance spectroscopy showed that the hexacyanoferrate redox reactions on the gold surface were blocked due to the procedures of self-assembly of thioctic acid and antibody immobilization. The binding of a specific antigen to antibody recognition layer could be detected by measurements of the impedance change. A new amplification strategy was introduced for improving the sensitivity of impedance measurements using biotin labeled protein- streptavidin network complex. This amplification strategy is based on the construction of a molecular complex between streptavidin and biotin labeled protein. This complex can be formed in a cross-linking network of molecules so that the amplification of response signal will be realized due to the big molecular size of complex. The results show that this amplification strategy causes dramatic improvement of the detection sensitivity of hIgG and has good correlation for detection of hIgG in the range of 2-10 mug/ml. (C) 2001 Elsevier Science B.V. All rights reserved.

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.