Molecular characterization of beef liver catalase by scanning tunneling microscopy

Beef liver catalase molecules can stick tenaciously to the highly oriented pyrolytic graphite (HOPG) surface which has been activated by electrochemical anodization. The immobilized sample is stable enough for high resolution scanning tunneling microscope (STM) imaging. When the anodized conditions are controlled properly, the HOPG surface will be covered with a very thin oxide layer which can bind the protein molecules. Individual molecules of native beef liver catalase are directly observed in detail by STM, which shows an oval-shape structure with a waist. The dimensions of one catalase molecule in this study are estimated as 9.0 x 6.0x 2.0 nm(3), which are in good agreement with the known data obtained from X-ray analysis, except the height can not be exactly determined from STM. Electrochemical results confirm that the freshly adsorbed catalase molecules maintain their native structures with biological activities. However, the partly unfolding structure of catalase molecules is observed after the sample is stored for 15 days, this may be caused by the long-term interaction between catalase molecules and the anodized HOPG surface.

High resolution electron microscopy study of single chain single crystals of gutta percha

Single chain single crystals (SCSC) of gutta percha (GP) were prepared by a dilute-solution spraying method. Electron diffraction (ED) patterns revealed that the single chain single crystal was of a new crystalline modification, the delta form. The images of SCSC of GP obtained with a high resolution electron microscope (HREM) showed a two dimensional periodic structure. Most of the images consisted of lattice fringes derived from the (001) zone. This is the first time that the single chain single crystal images of GP have been observed at a molecular level. Micrographs were image processed using optical filtering methods to improve the signal-to-noise ratio, and were compared with computer-generated simulations of the images. From the viewpoint of the defects seen in high resolution images, the crystal formation and melting processes are discussed. (C) 1998 Elsevier Science Ltd. All rights reserved.

Electrochemical scanning tunneling microscopy and electrochemical quartz crystal microbalance study of the adsorption of phenanthraquinone accompanied by an electrochemical redox reaction on the Au electrode

In situ electrochemical scanning tunneling microscopy (ECSTM) and an electrochemical quartz crystal microbalance (EQCM) have been employed to follow the adsorption/desorption processes of phenanthraquinone (PQ sat. in 0.1 mol l(-1) HClO4, solution) accompanied with an electrochemical redox reaction on the Au electrode. The result shows that: (1) the reduced form PQH(2) adsorbed at the Au electrode and the desorption occurred when PQH(2) was oxidized to PQ; (2) the adsorption process initiates at steps or kinks which provide high active sites on the electrode surface for adsorption, and as the potential shifts to negative, a multilayer of PQH(2) may be formed at the Au electrode; (3) the reduced PQH(2) adsorbed preferentially in the area where the tip had been scanned continually; this result suggests that the tip induction may accelerate the adsorption of PQH(2) on the Au(111) electrode. Two kinds of possible reason have been discussed; (4) high resolution STM images show the strong substrate lattice information and the weak monolayer adsorbate lattice information simultaneously. The PQH(2) molecules pack into a not perfectly ordered condensed physisorbed layer at potentials of 0.1 and 0.2 V with an average lattice constant a = 11.5 +/- 0.4 Angstrom, b = 11.5 +/- 0.4 Angstrom, and gamma = 120 +/- 2 degrees; the molecular lattice is rotated with respect to the substrate lattice by about 23 +/- 2 degrees. (C) 1997 Elsevier Science S.A.

Scanning tunnelling microscopy observation of cytochrome-c denaturation induced by bromopyrogal red on highly oriented pyrolytic graphite

The denaturation of cytochrome-e (cyt-c) induced by bromopyrogal red (BPR) was studied by scanning tunnelling microscopy (STM) on the electrochemically pretreated highly oriented pyrolytic graphite (HOPG) surface. STM images reveal that denatured cyt-c molecules exist in variable states including aggregates, globular compact, partially unfolded and combined with BPR molecule. The apparently low image contrast of denatured cyt-c observed in this experiment comparing to that of native cyt-c molecules, and the relative low image contrast of the unfolded part comparing with the compact globular part, are ascribed to the unfavourable tunnelling paths for the conformational variations of denatured cyt-c molecules. (C) 1997 Elsevier Science B.V.

In situ scanning tunneling microscopy studies of nanometer size palladium particles on highly oriented pyrolytic graphite

A special electrodeposition process of palladium was studied by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS) and in situ scanning tunneling microscopy (STM). A kind of palladium(IV) complex was attached to the highly oriented pyrolytic graphite (HOPG) electrode surface by electro-oxidation of palladium(II) complex first, and was then reduced to palladium particles. The surface complexes and particles of palladium were both characterized by in situ STM and XPS. The Pd particles are in the nanometer range of size and exhibit electrocatalytic activity towards the oxidation of hydrazine and hydroxylamine.

Tip-induced dynamic characterization of multilayers and variable morphologies of cytochrome c molecules on highly oriented pyrolytic graphite revealed by in-situ scanning tunnelling microscopy

The dynamic states of cytochrome c multilayers on electrochemically pretreated highly oriented pyrolytic graphite (HOPG) have been studied by in-situ scanning tunnelling microscopy (STM) under potential control of both the tip and the substrate in cytochrome c and phosphate buffer solution. The dynamic characterization of cytochrome c multilayers and relatively stable adsorbed single cytochrome c molecules scattered on HOPG imply that physically adsorbed multilayers were more easily influenced by the STM tip than those of chemically adsorbed single molecules. In-situ STM images of chemically adsorbed cytochrome c molecules with discernible internal structures on HOPG revealed that morphologies of cytochrome c molecules also suffered tip influence; possible tip-sample-substrate interactions have been discussed.

Scanning tunneling microscopy characterization of electrode materials in electrochemistry

Ex situ and in situ STM characterization of the electrode materials, including HOPG, GC, Au, Pt and other electrodes, is briefly surveyed and critically evaluated. The relationship between the electrode activity and surface microtopography is discussed.

IN-SITU SCANNING-TUNNELING-MICROSCOPY IMAGE OF A HIGHLY ORIENTED PYROLYTIC-GRAPHITE ELECTRODE MODIFIED WITH POTASSIUM BIS(11-MOLYBDOSILICATO) DYSPROSATE(III) IN SODIUM-SULFATE SOLUTION

The variation in molecule adsorption mode on pretreated highly oriented pyrolytic graphite electrodes, modified with the title complex K10H3[Dy(SiMo11O39)(2)] by cyclic voltammetry in the title complex solution, was observed in situ by electrochemical scanning tunnelling microscopy (ECSTM) with molecular resolution in sodium sulphate solution. According to the ECSTM images and the known molecular structure we conclude that the adsorption mode of the title complex modified electrode changed during potential cycling from ''vertical'' to ''inclined'' and then ''horizontal'' or ''flat'' mode, i.e. the title complex adsorbed on the surface of electrode by one ligand of the complex at first, then began to incline and was finally adsorbed by two ligands of the complex. This result indicates that the adsorption mode on the modified electrode surface changed during potential cycling in the sulphate solution and a much more stable molecular layer was formed. The change in adlattice of adsorbates on the modified electrode surface from hexagonal to rectangular was also observed by ECSTM. A plausible model was given to explain this process.

ORDERED ARRAYS OF MYOGLOBIN ADSORBED ON THE SURFACTANT MODIFIED SURFACE BY SCANNING-TUNNELING-MICROSCOPY

Myoglobin molecules were deposited on a surfactant sodium dodecyl sulfate modified HOPG surface and imaged in air with a high resolution scanning tunneling microscope (STM) for the first time. STM images exhibit not only ordered arrays of the surfactant m

SCANNING-TUNNELING-MICROSCOPY (STM) AND LATERAL FORCE MICROSCOPY (LFM) INVESTIGATION OF THE STRUCTURE AND CHARACTER OF CONDUCTIVE POLYPYRROLE FILM

Polypyrrole doped with p-toluenesulfonate was electropolymerized onto highly oriented pyrolytic graphite (HOPG), glassy carbon (GC) and Pt electrode surfaces under the same experimental conditions. The resulting films were studied by scanning tunneling m

FABRICATION AND CHARACTERIZATION OF TIPS FOR ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY

We report a new technique for preparing tips for electrochemical scanning tunneling microscopy (ECSTM) with particular consideration of its simplicity and reproducibility. In preparing scanning tunneling microscopy (STM) tips by electrochemical etching, w

IN-SITU SCANNING TUNNELING MICROSCOPIC STUDY OF NICKEL ELECTRODEPOSITION ON HOPG

The early stages of the electrodeposition of nickel on highly oriented pyrolytic graphite (HOPG) were investigated by in situ scanning tunnelling microscopy, scanning electron microscopy and electrochemical measurements. Experimental results showed that t