DIRECT ELECTRON-TRANSFER REACTION OF HEMEPROTEINS PROMOTED BY METHYLENE-BLUE MODIFIED ELECTRODE

The heterogeneous electron transfer reaction of hemeproteins including hemoglobin, myoglobin and cytochrome C at Pt mesh electrode adsorbed methylene blue has been investigated. Thin-layer spectroelectrochemical technique was used for observing the electron transfer processes of three kinds of proteins, and the corresponding electrode rate constants were measured.

STUDY OF THE ELECTRODE PROCESS OF HEMOGLOBIN AT A POLYMERIZED AZURE A FILM ELECTRODE

The electrochemically polymerized azure A film electrode is reported. The resulting film on a platinum electrode surface was analyzed with electron spectroscopy for chemical analysis (ESCA). The heterogeneous electron transfer processes of hemoglobin at the polymerized azure A film electrode have been investigated using in situ UV-visible spectroelectrochemistry. The formal potential (E-degrees') and electron transfer number (n) of hemoglobin were calculated as E = 0.088 V versus NHE (standard deviation +/- 0.5, N = 4) and n = 1.8 (standard deviation +/- 0.5, N = 4). Exhaustive reduction and oxidation electrolysis are achieved in 80 and 380 seconds, respectively, during a potential step between -0.3 and +0.3 V. A formal heterogeneous electron-transfer rate constant (k(sh)) of 3.54(+/- 0.12) X 10(-6) cm/s and a transfer coefficient (alpha) of 0.28(+/- 0.01) were obtained by cyclic voltabsorptometry, which indicated that the poly-azure A film electrode is able to catalyze the direct reduction and oxidation of hemoglobin.

STUDY ON ELECTRODE PROCESS OF MYOGLOBIN AT A POLYMERIZED AZURE A FILM ELECTRODE

The electrochemically polymerized azure A film electrode was firstly reported in this paper. A quasi-reversible electrode processes of myoglobin with the formal heterogeneous electron transfer rate constant (k(sh)) of 1.73 x 10(-4) cm.s-1 at the polymerized azure A modified electrode have been achieved using in-situ UV-visible spectroelectrochemistry. The adsorption of myoglobin on the polymerized azure A film electrode surface was confirmed by XPS. With simultaneously studying of cyclic voltammetry and in-situ cyclic voltabsorptometry, the attribution of the voltammetry responses of myoglobin at the film electrode has been studied. The mechanism for the heterogeneous electron transfer of myoglobin at the polymerized azure A film modified electrode has been proposed as well.

Electrochemical recognition of alkali metal ions at the micro-water 1,2-dichloroethane interface using a calix[4]arene derivative

In this paper, a calix[4]arene derivative, 5,11,17,23-butyl-25,26,27,28-tetra-(ethanoxycarbonyl)-methoxy-calix[4]arene (L), is investigated as a host to recognize alkali metal ions (Li+, Na+, K+, Rb+ and Cs+) at the interface between two immiscible electrolyte solutions (ITIES). Well-defined cyclic voltammograms are obtained at the micro- and nano-water \ 1,2-dichloroethane (W \ DCE) interfaces supported at micro- and nano-pipets.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Studies of ferrocene derivative diffusion and heterogeneous kinetics in polymer electrolyte by using microelectrode voltammetry

The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.

On The Cyclic Bending Behaviour Of A Hard Coating On A Ductile Substrate With Periodic Surface Hardened Regions

A cyclic bending experiment is designed to investigate the interface fracture behaviour of a hard chromium coating on a ductile substrate with periodic surface hardened regions. The unique deflection pattern of the vertical cracks after they run through the coating and impinge at the interface is revealed experimentally. A simple double-layer elastic beam model is adopted to investigate the interfacial shear stresses analytically. A FE model is employed to compute the stresses of the tri-phase structure under a single round of bending, and to investigate the effect of the loading conditions on the deflection pattern of the vertical cracks at the interface. (C) 2008 Elsevier Ltd. All rights reserved.

Stability Of Adhesion Clusters And Cell Reorientation Under Lateral Cyclic Tension

This work is motivated by experimental observations that cells on stretched substrate exhibit different responses to static and dynamic loads. A model of focal adhesion that can consider the mechanics of stress fiber, adhesion bonds, and substrate was developed at the molecular level by treating the focal adhesion as an adhesion cluster. The stability of the cluster under dynamic load was studied by applying cyclic external strain on the substrate. We show that a threshold value of external strain amplitude exists beyond which the adhesion cluster disrupts quickly. In addition, our results show that the adhesion cluster is prone to losing stability under high-frequency loading, because the receptors and ligands cannot get enough contact time to form bonds due to the high-speed deformation of the substrate. At the same time, the viscoelastic stress fiber becomes rigid at high frequency, which leads to significant deformation of the bonds. Furthermore, we find that the stiffness and relaxation time of stress fibers play important roles in the stability of the adhesion cluster. The essence of this work is to connect the dynamics of the adhesion bonds (molecular level) with the cell's behavior during reorientation (cell level) through the mechanics of stress fiber. The predictions of the cluster model are consistent with experimental observations.

Centrifuge modeling of suction bucket foundations for platforms under ice-sheet-induced cyclic lateral loadings

This paper presents the results of a series of centrifuge model tests performed to study the behavior of suction bucket foundations for a tension leg platform in the Bohai Bay, China. The target lateral loadings were from ice-sheet-induced structural vibrations at a frequency of 0.8-1.0 Hz. The results indicate that excess pore water pressures reach the highest values within a depth of 1.0-1.5 in below the mud line. The pore pressures and the induced settlement and lateral displacement increase with the amplitude of the cyclic loading. Two failure modes were observed: liquefaction in early excitations and settlement-induced problems after long-term excitations. (c) 2006 Elsevier Ltd. All rights reserved.

Fracture behavior of axisymmetrical bars under high triaxial stress and large strain cyclic loading

Axisymmetric notched bars with notch roots of large and small radii were tested under large strain cyclic loading. The main attention is focused on the fracture behaviour of steels having cycles to failure within the range 1-100. Our study shows that a gradual transition from a static ductile nature to one of fatigue cleavage can be observed and characterized by the Coffin-Manson formula in a generalized form. Both the triaxial tensile stress within the central region of specimens and static damage caused by the first increasing load have effects on the final failure event. A generalized cyclic strain range parameter DELTAepsilon is proposed as a measure of the numerous factors affecting behaviour. Fractographs are presented to illustrate the behaviour reported in the paper.

Post-cyclic Strength Degradation of Undisturbed and Remolded Marine Silty Clay

A series of static and cyclic-static tri-axial compression tests under consolidated-undrained conditions are carried out to study the characteristics of post-cyclic strength of the undisturbed and the remolded samples of marine silty clay. It is found that the post-cyclic monotonic strength decreases if the cyclic strain or pore pressure is over a certain value. The maximum degradation is 10% for undisturbed samples while 70% for remolded ones. The relationship between normalized undrained shear strength and apparent overconsolidation ratio, which is determined by the excess pore pressure induced by cyclic loading, is also established. Static consolidated-undrained tests on overconsolidated remolded samples are also performed. It is proposed that the static consolidated-undrained tests may be substituted for the cyclic-static consolidated-undrained tests if the post-cyclic strength degradation of remolded silty clay is needed to be evaluated simply.

Cyclic Deformation Of Nanocrystalline And Ultrafine-Grained Nickel

The cyclic deformation behavior Of ultrafine-grained (UFG) Ni samples synthesized by the electrodeposition method was studied. Different from those made by severely plastic deformation, the UFG samples used in this study are characterized by large-angle grain boundaries. Behaviors from nanocrystalline Ni and coarse-grained Ni samples were compared with that Of Ultrafine-grained Ni. With in situ neutron diffraction. unusual evolutions of residual lattice strains as well as cyclic hardening and softening behavior were demonstrated during the cyclic deformation. The microstructural changes investigated by TEM are discussed with respect to the unusual lattice strain and cyclic hardening/softening. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Study on the Capacity Degradation of Bucket Foundation in Liquefied Sand Layer under Cyclic Loads

The capacity degradation of bucket foundation in liquefied sand layer under cyclic loads such as equivalent dynamic ice-induced loads is studied. A simplified numerical model of liquefied sand layer has been presented based on the dynamic centrifuge experiment results. The ice-induced dynamic loads are modeled as equivalent sine cyclic loads, the liquefaction degree in different position of sand layer and effects of main factors are investigated. Subsequently, the sand resistance is represented by uncoupled, non-linear sand springs which describe the sub-failure behavior of the local sand resistance as well as the peak capacity of bucket foundation under some failure criterion. The capacity of bucket foundation is determined in liquefied sand layer and the rule of capacity degradation is analyzed. The capacity degradation in liquefied sand layer is analyzed comparing with that in non-liquefied sand layer. The results show that the liquefaction degree is 0.9 at the top and is only 0.06 at the bottom of liquefied sand layer. The numerical results are agreement well with the centrifugal experimental results. The value of the degradation of bucket capacity is 12% in numerical simulating whereas it is 17% in centrifugal experiments.

Measurement of two-photon excitation cross-section of a new symmetric-type fluorene derivative

A new dye, 2,7-bis(4-methoxystyryl)-9,9-bis(2-ethylhexyl)-9H-fluorene, has been synthesized, which is a D-pi-D symmetrical-type fluorene derivative. The two-photon absorption (TPA) of this new dye has been experimentally studied by comparable two-photon-induced fluorescence method. This new dye has a TPA cross-section of 84 x 10(-50) cm(4) s/photon at 790 nm/13 fs. (c) 2004 Elsevier GmbH. All rights reserved.