EFFECTS OF ANODIC-OXIDATION ON THE SURFACE-STRUCTURE OF HIGHLY ORIENTED PYROLYTIC-GRAPHITE REVEALED BY IN-SITU ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY IN H2SO4 SOLUTION

Effects of the potential of anodic oxidation and of potential cycling on the surface structure of a highly oriented pyrolytic graphite (HOPG) electrode were observed by in situ electrochemical scanning tunnelling microscopy (ECSTM) in dilute H2SO4 solution with atomic resolution. With potential cycling between -0.1 V and 1.8 V vs. Ag/AgCl (sat. KCI), some atoms on the top layer of HOPG protrude out of the base plane, and the graphite lattice of these protrusions is still intact but is strained and expanded. With further potential cycling, some protrusions coalesced and some grew larger, and an anomalous superperiodic feature was observed (spacing 90 Angstrom with a rotation 30 degrees relative to atomic corrugations) which superimposed on the atomic corrugation of HOPG. On the topmost of these protrusions, some atoms form oxides and others are still resolved by the ECSTM image. With potential cycling between -0.1 V and + 2.0 V vs. Ag/AgCl (sat. KCl), damage to freshly cleaved HOPG surface is more serious and fast, some ridges are observed, the atomic structure of the HOPG surface is partially and then completely damaged due to the formation of oxide. We also found that anodic oxidation occurred nonuniformly on the surface of HOPG near defects during potential cycling.

EPITAXIAL BEHAVIOR OF HDPE ON THE BOUNDARY OF HIGHLY ORIENTED IPP SUBSTRATES

The epitaxial crystallization behavior of high-density polyethylene on the boundary of highly oriented isotactic polypropylene (iPP) substrates has been investigated by means of atomic force microscopy (AFM) and transmission electron microscopy (TEM). The results obtained from AFM and TEM indicate that the epitaxial nucleation of HDPE on the highly oriented iPP substrates occurs earlier than that in the pure HDPE phase, i.e., homogeneous nucleation. Therefore the epitaxially grown HDPE lamellae can grow across the boundary of the iPP substrate into the HDPE spherulitic phase with the epitaxial orientation relationship remaining.

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.

STM OF FOLDED AND UNFOLDED HEMOGLOBIN MOLECULES ELECTROCHEMICALLY DEPOSITED ON HIGHLY ORIENTED PYROLYTIC-GRAPHITE

The structural characterization of folded and unfolded haemoglobin has been performed by scanning tunnelling microscopy (STM) for the first time. STM images show an oval-shaped pattern for the folded structure of this protein, and moreover two dimers consisting of one haemoglobin molecule can be clearly discerned. The dimensions of a folded molecule were determined as 6.4 x 5.4 x 0.7 nm(3), which are in good agreement with the known size obtained from X-ray analysis. We have found that unfolding of haemoglobin molecules on the surface of highly oriented pyrolytic graphite (HOPG) can be achieved by electrochemical deposition. The STM analysis indicates clearly that the tertiary structure of the protein was lost by electrochemical deposition, and most of the haemoglobin molecules were almost fully extended and exhibited a twisted rope-like or a rod-like aggregated structure. Our investigation demonstrates the capability of the electrochemical method in denaturing this redox protein and in preparing stable biological samples for use in STM imaging.

HIGHLY SENSITIVE AND SELECTIVE DETERMINATION OF RIBOFLAVIN BY FLOW-INJECTION ANALYSIS USING PARALLEL DUAL-CYLINDER MICROELECTRODES

A novel wall-jet cell with parallel dual cylinder (PDC) microelectrodes was constructed and used for flow injection analysis (FLA). The detector takes the advantages of ''redox recycling'' between bipotentiostated microcylinder electrodes (- 0.4 V/SCE an

DSC AND C-13 NMR-STUDIES OF ETHYLENE-PROPENE COPOLYMERS PREPARED BY A HIGHLY-ACTIVE AND STEREOSPECIFIC CATALYST

Ethylene-propene copolymers (EPR) were synthesized at different feed compositions using a highly active and isospecific MgCl2-supported Ti-based catalyst. The thermal behavior of EPR was studied by differential scanning calorimetry, the heterogeneity by f

INFLUENCE OF ESTER GROUP-SIZE IN PMAS ON BETA-PHASE CRYSTALLIZATION OF PVF2 IN HIGHLY ORIENTED FILMS OF PVF2/PMAS BLENDS

Influence of ester group size in polymethacrylates (PMAs) , including PMMA, PEMA and PBMA, on beta phase crystallization of poly(vinylidene fluoride) (PVF2) in highly oriented films of PVF2/PMAs=80/20 blends has been investigated by FTIR and TEM. The melt-drawn films of pure PVF2 consist of highly oriented lamellae, in which the alpha phase is predominant. Adding a given amount of PMAs (20 wt%) into PVF2 results in formation of fibrillar crystals and increase of relative amount of the beta phase. The influence extent is in order of PMMA > PEMA > PBMA, regarding the ester group size in the PMAs.

EPITAXIAL CRYSTALLIZATION OF TRANS-1,4-POLYBUTADIENE ON HIGHLY ORIENTED ISOTACTIC POLY(PROPYLENE) FILMS

Epitaxial crystallization of trans-1,4-polybutadiene (PBD) on highly oriented isotactic poly(propylene) (iPP) has been investigated at different crystallization temperatures and rates. From electron microscopy and electron diffraction, it is confirmed that epitactic growth of the low-temperature modification (monoclinic) with microcrystals of PBD on the iPP films takes place with their chain directions about +/- 50-degrees apart. No epitaxial relationship occurs between the high-temperature modification (hexagonal) of PBD and the iPP substrate. Thermal analyses of PBD-PP layered films indicate that the epitaxy has an important effect on the formation of the high-temperature modification of PBD.

EFFECT OF MOLECULAR-WEIGHT OF PMMA ON BETA PHASE CRYSTALLIZATION IN HIGHLY ORIENTED PVF2 FILMS

Polyvinylidene fluoride (PVF_2) exhibits at least four crystalline phases (α, β, γ, and δ). Among them, β phase is the most important one because it is directly related to the piezoand pyro-electric activities of PVF_2. In recent years, more attention has been paid to the β

MEASUREMENT AND CALCULATION OF SPONTANEOUS EMISSION BRANCHING RATIOS, RELATIVE OSCILLATOR-STRENGTHS, TRANSITION-PROBABILITIES AND LEVEL LIFETIMES FOR ATOMIC URANIUM

We propose a laser induced sensitized fluorescence spectrometry for measuring the spontaneous emission branching ratios o?the transitions from the ten levels 5f36d7s7p-7M7, 5f36d7s7p-7L6, 5f37s27p-5K6, 5f26d27s2 - 5L7, 5f46d7s - 7L6, (17,070cm-1)-5L6, 5f26d27s2-5K6, 6d7s7p-7L5, 5f36d7s7p-7K5 and 5f26d27s2-5I5 to the ground state of atomic uranium (UI) for the first time. Their relative oscillator strengths have been measured by means of hollow cathode discharge (HCD) emission spectrometry. The radiative...