Assembly of multilayer films containing iron(III)- substituted Dawson-type heteropolyanions and its electrocatalytic properties: cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis spectrometry

Ultrathin multilayer films have been prepared by means of alternate adsorption of iron(Ill)-substituted heteropolytungstate anions and a cationic redox polymer on the 4-aminobenzoic acid modified glassy carbon electrode surface based on electrostatic layer-by-layer assembly. Cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis absorption spectrometry have been used to easily monitor the uniformity of thus-formed multilayer films. Especially, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes and is a very useful technique in the characterization of multilayer films because it provides valuable information about the interfacial impedance features. All these results reveal regular film growth with each layer adsorption. The resulting multilayer films can effectively catalyze the reduction of H2O2,NO2- and BrO3-.

Probing UPD-induced surface atomic rearrangement of polycrystalline gold nanofilms with surface plasmon resonance spectroscopy and cyclic voltammetry

Silver underpotential deposition (UPD)-induced surface atomic rearrangement of polycrystalline gold nanofilms was probed with use of surface plasmon resonance spectroscopy (SPRs) as a novel probe tool in combination with cyclic voltammetry. Interestingly, upon repetitive electrochemical UPD and stripping of Ag, the surface structure of the resulting bare Au film is rearranged due to strong adatom-substrate interactions, which causes a large angle shift of SPR R-theta curves, in a good linear relationship with the number of UPDs, to a lower SPR angle. The n, K values of the surfacial Au monolayers before and after the repetitive Ag UPD and stripping for 27 times are found to be 0.133, 3.60 and 0.565, 9.39, respectively, corresponding to the huge shift of 1.61degrees to the left of the SPR minima. Cyclic voltammetry experiments in 0.10 M H2SO4 are carried out before and after the UPD treatment to examine the quality of the whole electrode surface and confirmed this change. To correlate the angle change in SPRs with the profile change in the cyclic voltammogram, the UPD treatment was also performed on a Au(111) textured thin film. It was therefore confirmed that the resonance position of the SPR spectrum is very sensitive to the surface crystallographic orientation of the bare Au substrates. Some surface atomic rearrangement can cause a pronounced SPR angle shift.

Mossbauer spectroscopy and chemical bonds in BaFe12O19 hexaferrite

Barium hexaferrite was synthesized by chemical co-precipitation. Its Mossbauer spectra were obtained. A semi-empirical model, based on the Phillips theory of bonding, has been developed for quantitative explanation of the Mossbauer isomer shifts of Fe ions in BaFe12O19 crystals. The results show that, using the relationship between isomer shifts and covalency, the site assignments in hexaferrites will be resolved easily. This paper provides a powerful tool for studying other members of the hexagonal ferrimagnetic oxides family.

Synthesis of the complex fluoride LiBaF3 and optical spectroscopy properties of LiBaF3 : M(M = Eu,Ce) through a solvothermal process

The complex fluoride LiBaF3 and LiBaF3:M(M = Eu, Ce) is solvothermally synthesized at 180 degreesC and characterized by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy. In the solvothermal process, the solvents, molar ratios of initial mixtures and reaction temperature play important roles in the formation of products. The excitation and emission spectra of the LiBaF3:M(M= Eu,Ce) have been measured by fluorescence spectrophotometer. In the LiBaF3: Eu emission spectra, there is one sharp line emission located at 360 nm arising from f --> f transition of Eu2+ in the host lattice, and typical doublet 5d-4f emission of Ce3+ in LiBaF3 powder is shown.

Amplified DNA detection sensitivity using streptavidin-biotinylated protein complex: Characterization by electrochemical impedance spectroscopy

Thiol-terminated oligonucleotide was immobilized to gold surface by self-assembly method. A novel amplification strategy was introduced for improving the sensitivity of DNA. hybridization using biotin labeled protein-streptavidin network complex. This complex can be formed in a cross-linking network of molecules so that the amplification of the response signal will be realized due to the big molecular size of the complex. It could be proved from the impedance technique that this amplification strategy caused dramatic improvement of the detection sensitivity. These results give significant advances in the generality and sensitivity as it is applied to biosensing.

Surface-enhanced Raman spectroscopy of microperoxidase-11 on roughed silver electrodes

The conformation of microperoxidase-11 (MP-11) adsorbed on roughened silver electrodes was studied using surface-enhanced Fourier transform Raman spectroscopy. The results demonstrate that MP-11 was initially adsorbed via its polypeptide chain with a alpha-helix conformation, as indicated by the enhancement of the characteristic bands related to the amides I and III. The weak resonance effect of the porphyrin macrocycle in the near IR region contributes to the spectrum of the heme group. The presence of imidazole as the sixth ligand to the heme iron influences the conformation of the polypeptide chain of MP-11 on the electrode surface. Evaporation of solvent water results in an opened conformation of the adsorbed MP-11. which allows the heme group to contact the electrode surface directly.

Ion channel behavior of amphotericin B in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes investigated by electrochemistry and spectroscopy

Amphotericin B (AmB) is a popular drug frequently applied in the treatment of systemic fungal infections. In the presence of ruthenium (II) as the maker ion, the behavior of AmB to form ion channels in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes were studied by cyclic votammetry, AC impedance spectroscopy, and UV/visible absorbance spectroscopy. Different concentrations of AmB ranging from a molecularly dispersed to a highly aggregated state of the drug were investigated. In a fixed cholesterol or ergosterol content (5 mol %) in glassy carbon electrode-supported model membranes, our results showed that no matter what form of AmB, monomeric or aggregated, AmB could form ion channels in supported ergosterol-containing phosphatidylcholine bilayer model membranes. However, AmB could not form ion channels in its monomeric form in sterol-free and cholesterol-containing supported model membranes. On the one hand, when AmB is present as an aggregated state, it can form ion channels in cholesterol-containing supported model membranes; on the other hand, only when AmB is present as a relatively highly aggregated state can it form ion channels in sterol-free supported phosphatidylcholine bilayer model membranes. The results showed that the state of AmB played an important role in forming ion channels in sterol-free and cholesterol-containing supported phosphatidylcholine bilayer model membranes.

Chemical bond properties and Mossbauer spectroscopy in (La1-xMx)(2)CuO4(M=Ba, Sr)

By using the average band-gap model, the chemical bond properties of (La1-x, M-x)(2)CuO4(M=Ba, Sr) were calculated. The calculated covalencies for Cu-O and La-O bond in the compounds are 0.3 and 0.03 respectively. Mossbauer isomer shifts of Fe-57 doped in La2CuO4 and Sn-119 doped in La2CuO4 were calculated by using the chemical surrounding factor defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified in Fe-57 and Sn-119 doped La2CuO4.

Study of the ionic conductivity of polymer electrolyte using imaginary impedance spectroscopy

Polymeric electrolytes of (PEO1)(10) LiClO4-Al2O3 (PEO: poly (ethyleneoxide)) and (PEO2)(16)LiClO4-EC (EC: ethylene carbonate) were prepared. We proposed an equivalent circuit and gave the meaning of the concerned circuit elements. When the impedance spectrum deformed severely, the ionic conductivity of polymer electrolyte was determined by using the maximum of imaginary impedance, which is a convenient method.

Application of 2D Raman correlation spectroscopy to studing the effect of rare-earth Eu3+ on hemoglobin

The effect of rare-earth ion Eu3+ on hemoglobin (Hb) was studied by using two-dimensional Raman correlation spectroscopy. The results show that with the variation of Eu3+ concentrations as perturbation, the oxidation state of Hb and its spin state are both sensitive to the perturbation. Eu3+ added to Hb affects the oxidation and spin state synchronously. The four structure-sensitive bands of Hb are more accessible to the Eu3+ than other bands.

Conformational transition of DNA induced by cationic lipid vesicle in acidic solution: spectroscopy investigation

The conformational transition of DNA induced by the interaction between DNA and a cationic lipid vesicle, didodecyidimethylammonium bromide (DDAB), had been investigated by circular dichroism (CD) and UV spectroscopy methods. We used singular value decomposition least squares method (SVDLS) to analyze the experimental CD spectra. Although pH value influenced the conformation of DNA in solution, the results showed that upon binding to double helical DNA, positively charged liposomes induced a conformational transition of DNA molecules from the native B-form to more compact conformations. At the same time, no obvious conformational changes occurred at single-strand DNA (ssDNA). While the cationic lipid vesicles and double-strand DNA (dsDNA) were mixed at a high molar ratio of DDAB vesicles to dsDNA, the conformation of dsDNA transformed from the B-form to the C-form resulting in an increase in duplex stability (DeltaT(m) = 8 +/- 0.4 degreesC). An increasing in T-m was also observed while the cationic lipid vesicles interacted with ssDNA.

Chemical bond properties and Mossbauer spectroscopy in REBa2Cu3O7 (RE = Eu, Y)

By using the chemical bond theory of complex crystals, the chemical bond properties of REBa2Cu3O7 (RE = Eu, Y) were calculated. The calculated covalencies for Cu(1)-O and Cu(2)-O bond in REBa2Cu3O7 compounds are 0.41 and 0.28 respectively. Mossbauer isomer shifts of Fe-57 doped, and Sn-119 doped in REBa2Cu3O7-x were calculated by using the chemical environmental factor, h(e), defined by covalency and electronic polarizability. Four valence state tin ion and iron ion sites were identified in Fe-57 and Sn-119 doped REBa2Cu3O7-x superconductors.

Characterization of organic-inorganic multilayer films by cyclic voltammetry, UV-Vis spectrometry, X-ray photoelectron spectroscopy, small-angle X-ray diffraction and electrochemical impedance spectroscopy

We have employed several techniques, including cyclic voltammetry, UV-Vis spectrometry, small-angle X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy, to characterize the formation processes and interfacial features of ultrathin multilayer films of silicotungstate and a cationic redox polymer on cysteamine-coated Au electrodes self-assembled monolayers. All of these techniques confirm that the multilayer films are built up stepwise as well as uniformly in a layer-by-layer fashion. In particular, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes. It has been proved that the electrochemical impedance spectroscopy is a very useful technique in characterization of multilayer films because it provides valuable information about the interfacial impedance features.

Real-time analysis of the interaction between calmodulin and melittin by SPR spectroscopy

The dynamic interaction process of calmodulin with an immobilized peptide melittin was investigated in real time by surface plasmon resonance spectroscopy, and dissociation constant of the complex was calculated to be 3.37 x 10(-6) mol/L.

Application of resonance raman spectroscopy to study the effect of rare-earth ion Er3+ on myoglobin

The effect of rare-earth ion Er3+ On myoglobin(Mb) was studied by using Resonance Raman spectroscopy. The results show that with the variation of Er3+ concentrations, both the oxidation state and spin state of Mb are sensitive to the perturbation of Er3+. Er3+ added to Mb affects the oxidation and spin state synchronously. The structure-sensitive groups of Mb are more accessible to the Er3+ than other groups. According to the fluorometry and CD spectra studied and our results as mentioned above, we considered that Er3+ does not interact with heme directly, and Er3+ probably leads to the conformational changes of Mb due to the change of oxidation and spin state of Heme.