Electrochemical study of the interfacial characteristics of redox-active viologen thiol self-assembled monolayers

The electrochemical behavior of the electroactive self-assembled monolayers (SAMs) of thiol-functionalized viologen, CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is a viologen group, on the gold electrodes is examined by cyclic voltammetry and electrochemical a.c. impedance. A monolayer of viologen is immobilized on the gold electrode surface via the Au-S bond and the normal potentials corresponding to the two successive one-electron transfer processes of the viologen active centers are -310 mV and -652 mV (vs. Ag/AgCl) in 0.1 mol l(-1) phosphate buffer solution (pH 6.96) respectively. These results suggest that the viologen SAMs are stable and well-behaved monolayers. The experimental impedance data corresponding to different forms of viologen group have been fitted to equivalent electrical circuits, and the surface capacitances and resistances have been given. The heterogenous electron transfer rates of the first and the second redox processes are 7.57 s(-1) and 1.49 s(-1) respectively through a.c. impedance.

KINETIC-STUDY OF ELECTROCATALYTIC REDUCTION OF HYDROGEN-PEROXIDE AT IRON(III) PORPHYRIN MODIFIED GLASSY-CARBON ELECTRODE IN ALKALINE-MEDIUM USING THE ROTATION-SCAN METHOD

Reduction of hydrogen peroxide at a glassy carbon (GC) electrode modified with sigma-bonded pyrrole iron(III) octaethylporphyrin complex, (OEP)Fe(Pyr), was studied by cyclic voltammetry and a rotating disk electrode. In 0.1N NaOH solution, it is shown that such an (OEP)Fe(Pyr)/GC electrode has a significant catalytic activity towards hydrogen peroxide reduction (E(D) = -0.80 V, k = 0.066 cm s(-1)); however, the electrode stability is low. The deactivation is observed when the reaction charge (Q) is passing through the (OEP)Fe(Pyr)/GC disk electrode. A linear rotation scan method is applied to study the kinetic process by determining the disk electrochemical response (i(D)) to rotation rate (omega) at a definite disk potential (E(D)). Considering that the number of adsorbed electroreduced catalyst molecules (Red) varies according to the disk potential, a factor theta(= Gamma(Red)/(Gamma(Red) + Gamma(Ox))) is introduced to describe the electrode surface area fraction for electroreduced species. The obtained Koutecky-Levich equation is applicable whatever the potential is.

ELECTROCHEMISTRY, SPECTROELECTROCHEMISTRY OF (TPP)CO IN THE PRESENCE OF OH-ANIONS

In the presence of OH- anions, electrochemical redox reactions of cobalt tetraphenylporphyrin (TPP)Co were investigated in EtCl2 solution by thin-layer cyclic voltammetry and spectroelectrochemistry. In the pressence of OH-, OH- was axially coordinated to

STUDIES OF SPINEL LICRXMN2-XO4 FOR SECONDARY LITHIUM BATTERY

X-ray and electrochemical studies of spinel-related manganese chromium oxides, LiCrxMn2-xO4 (0 less-than-or-equal-to x less-than-or-equal-to 1) were carried out in a lithium nonaqueous cell. X-ray diffraction spectra indicated that the substitution of manganese in LiMn2O4 by trivalent transition metals (Cr3+) cause the linear decrease of lattice parameter with the x in the LiCrMn2-xO4. Some discharge-capacity loss was obtained due to the lattice contraction of LiCrMn2-xO4, but it has a better rechargeability than LiMn2O4. Cyclic voltammetry and electrochemical impedance experiments have shown that the excellent rechargeability of LiCrxMn2-xO4 may be attributed to the good reversibility of the change in its crystal structure for the insertion and extraction of lithium ions.

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 STUDY OF CHOLINE DERIVATIVES TRANSFER ACROSS THE LIQUID LIQUID INTERFACE

Transfer behaviors across the water/nitrobenzene interface were studied for five choline derivatives by chronopotentiometry with linear current scanning, cyclic voltammetry and differential pulse voltammetry. The irreversible hydrolysis reactions coupled to the phase transfer of ions across the water/nitrobenzene interface were observed. The Gibbs energies of the transfer of choline derivatives show the effects of an additive constitution on hydrophobic property of the medicine.

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

A NOVEL DESIGN OF LIGHT-TRANSPARENT GOLD-MINIGRID THIN-LAYER FTIR SPECTROELECTROCHEMICAL CELL WITH VERTICAL CONFIGURATION

A Teflon bridge/edge-eliminator is designed to connect a glass container and a light-transparent gold-minigrid NaCl thin-layer cell to form a vertically configured in-situ FTIR spectroelectrochemical cell. The bridge/edge-eliminator sets an internal reference point for accurate potential control. The size of the thin-layer chamber is 5 X 5 X 0.11mm. A 1900-omega formal resistance of the thin-layer cell was measured in CH2Cl2/0.1 M TBAP solution. Well defined thin-layer cyclic voltammograms and IR spectral changes for ferrocene oxidation were obtained.

天津滨海新区软土不同含砂量的强度特征研究

Based on the features of soft soil in Tianjing Coastal New Developing Area, this kind of soil with different content of sand was researched systematically, according to the indoor experiment, about its characteristics of strength and deformation. The main results are summarized in the following: Firstly, on the basis of geological engineering investigation, the systemic experiments about the physical characteristics were conducted. The test soil samples were taken from the gray and gray-yellow silty soft soil which was formatted by near-shore marine sediment and marine-continental interactive sediment. The original condition of the sample soil was in saturation and the basic indexes are: liquid limit36.1%, plastic limit 18.8%, plasticity index. Then, the condensation characteristics of the soft soil were analyzed through high-pressure consolidation tests. The results show that，in various loading serials, the coefficient of compressibility under P=100kPa and 200kPa are all larger than 0.5MPa-1. So the sample soil is a kind of high-compressibility soil. Secondly, triaxial strength of undisturbed soil and remoulded soil was researched by using triaxial test. The types of stress-strain curve of both undisturbed and remoulded soil are the stress stabilization and softening type, which show the specific plastic character. Furthermore, the cohesion and friction angle of undisturbed soil changes, when the ambient pressure is different, instead of a stable value for all time; the cohesion and friction angle of remoulded soil changes with the compactness and sand-carrying capacity which is wholly higher than undisturbed soil. At last, the stress-strain results of both undisturbed and remoulded soil were normalized by using the ambient pressure as the normalization factor. The results show that, there are all some normalization characters in both undisturbed and remoulded soil, however, the feature of normalization of undisturbed soil is worse than the remoulded ones. The main reason is that the undisturbed samples are worse in equality and the unavoidable disturb through the process of sampling and experiments will also make them can not put up good normalization. Therefore, it is feasible to normalize the soil in Tianjing Coastal New Developing Area with the ambient pressure as normalization factor.

大别山岩石圈有效弹性厚度初步研究

As powerful tools to study the lithosphere dynamics, the effective elastic thickness (Te) as well as the envelope of yielding stress of lithosphere have been attracted great attention of geoscientists in the past thirty years. The oceanic lithosphere, contrary to the continental lithosphere, has more fruits for its simple structures and evolution process. In continent, the lithosphere commonly is complex and variable in the rheological, thermal structures, and has a complicated history. Therefore, the application of the effective elastic thickness in continent is still a subject to learn in a long time. Te, with the definition of the thickness of an elastic plate in theory flexured by the equal benging of the real stress in the lithosphere plate (Turcotte, 1982), marks the depth of transition between elastic and fluid behaviors of rocks subjected to stress exceeding 100 MPa over the geological timescales (McNutt, 1990). There are three methods often adapted: admittance or isostatic response function, coherence and forwarding. In principle, the models of Te consist of thermal-rheological, non-linear Maxwell, non-linear work hardening and rheological layered models. There is a tentative knowledge of Te that it is affected by the following factors: crustal thickness, crust-mantle decoupling, plate bending, boundary conditions of plate (end forces and bending moments), stress state, sedimentary layer, faulting effect, variation in the mountain belts' strike, foreland basin, inheritance of tectonic evolution, convection of mantle, seismic depth and lithosphere strength. In this thesis, the author introduces the geological sketch of the Dabie collisional orogenic belt and the Hefei Basin. The Dabie Mts. is famous for the ultra-high pressure metamorphism. The crustal materials subducted down to the depth of at least 100 km and exhumed. So that the front subjects arise such as the deeply subduction of continent, and the post-collisional crust-mantle interaction. In a geological journey at June of 1999, the author found the rarely variolitic basaltic andesite in the Dabie Mts. It occurs in Susong Group, near Zhifenghe Countryside, Susong County, Anhui Province. It is just to the south of the boundary between the high-grade Susong melange and the ultra-high grade South Dabie melange. It has a noticeable knobby or pitted appearance in the surface. The size of the varioles is about 1-4 mm. In hand-specimen and under microscope, there are distinct contacts between the varioles and the matrice. The mineralogy of the varioles is primarily radiate plagioclase, with little pyroxene, hornblende and quartz. The pyroxene, hornblende and quartz are in the interstices between plagioclase. The matrix is consisted of glass, and micro-crystals of chlorite, epidote and zoisite. It is clearly subjected and extensive alteration. The andesite has an uncommon chemical composition. The SiO_2 content is about 56.8%, TiO_2 = 0.9%, MgO = 6.4%, (Fe_2O_3)_(Total) = 6.7% ～ 7.6%, 100 Mg/(Mg+Fe) = 64.1 ～ 66.2. Mg# is significantly high. The andesite has higher abundances of large-lithophile trace elements (e.g. K, Ba, Sr, LREE), e.g. La/Nd = 5.56-6.07, low abundances of high-strength-field elements (HFSE, e.g. Ta, Nb, P, Ti), particularly Ta and Nb strongly depleted. These are consistent with the characteristics of subducted-related magmas (Pearcce, 1982; Sun and McDonaugh, 1989). In the spider diagram of trace elements, from Ce to right hand, the abundances of elements decrease quickly, showing a characteristic of the continental margins (Pearce, 1982). There has a strongly enrichment of light-rare-earth elements, with a significant diffraction of REEs (the mean value of (La/Yb)_N is 32.84). No Eu anomaly, but there are anomaly high (La/Yb)_N = 28.63-36.74, (La/Y)_N = 70.33 - 82.84. The elements Y and Yb depleted greatly, Y < 20 ppm, Y_N = 2.74-2.84, Yb_N = 2.18 - 2.35. From the La-(La/Sm) diagram, the andesite is derived from partial melting. But the epsilone value of Nd is -18.7 ～ -19.2, so that the material source may be the mantle materials affected by the crustal materials. The Nd model age is 1.9 Ga indicating that the basaltic andesite was resulted from the post-collisional crust-mantle interaction between the subducted Yangze carton and the mantle of Sino-Korea carton. To obtain the Te of the lithosphere beneath the Dabie Mts. and the Hefei Basin, the author applies the coherence method in this thesis. The author makes two topography-gravity profiles (profiles 7~(th) and 9~(th)) across the Dabie Mts. and the Hefei Basin, and calculates the auto-coherence, across coherence, power spectrum, across power spectrum of the topography and gravity of the two profiles. From the relationships between the coherence and the wave-number of profiles. From the relationships between the coherence and the wave-number of profiles 7~(th) and 9~(th), it is obtained that the characteristic wavelengths respectively are 157 km and 126 km. Consequently the values of effective elastic thickness are 6.5 km and 4.8 km, respectively. However, the Te values merely are the minimum value of the lithosphere because the coherencemethod in a relative small region will generate a systemic underestimation. Why there is a so low Te value? In order to check the strength of the lithosphere beneath the Dabie Mts., the authore tries to outline the yielding-stress envelope of the lithosphere. It is suggested that the elastic layers in the crust and upper mantle are 18 km and 35 km, respectively. Since there exist a low viscosity layer about 3-5 km thickness, so it is reasonable that the decoupling between the crust and mantle occurred. So the effective thickness of the lithosphere can be estimated from the two elastic layers. Te is about 34 km. This is the maximum strength of the lithosphere. We can make an approximately estimation about the strength of the lithosphere beneath the Dabie Mts.: Te is about 20-30 km. The author believes that the following factors should be responsible for the low Te value: (1) the Dabie Mts. has elevated strongly since K_3-J_1. The north part of the Dabie Mts. elevates faster than the south part today; (2) there occur large active striking faults in this area. And in the east, the huge Tan-Lu striking fault anyway tends to decrease the lithosphere strength; (3) the lithosphere beneath the Dabie Mts. is heter-homogeneous in spatio-temporal; (4) the study area just locates in the adjacent region between the eastern China where the lithosphere thickness is significantly reduced and the normal western China. These factors will decrease the lithosphere strength.

东营凹陷辛镇复杂断块油藏形成机制和剩余油分布规律研究

In this paper, the complex faulted-block oil reservoir of Xinzhen area in Dongying depression is systematically studied from basic conditions forming faulted-block oil and gas reservoir integrating geology, seismic, logging and reservoir engineering information and computer; guided by petroleum geology, geomechanics, structural geology and geophysics and other theories. Based on analysis of background condition such as regional strata, structure and petroleum geology, structural research on geometry, kinemaitcs and dynamics, oil-controlling fault research on the seal features, sealing mechanism and sealing pattern, and research on enrichment rules and controlling factors of complex faulted-block oil reservoir are carried out to give out the formation mechanics of oil reservoir of Xinzhen complex faulted-block oil reservoir. As a result, the reservoir formation pattern is established. At the same time, through dissecting the characteristics and hydrocarbon enrichment law of complex faulted-block oil reservoir, and studying its distribution law of remaining oil after entering extra high water-cut period, a set of technologies are formed to predict complex faulted-block oil reservoir and its remaining oil distribution and to enhance oil recovery (EOR). Based on the time relationship between migration of hydrocarbon and trap formation, accumulating period of Xinzhen oil reservoir is determined. The formation of Xinzhen anticlinal trap was prior to the primary migration. This is favorable to formation of Xinzhen anticlinal hydrocarbon reservoir. Meanwhile, because anticline top caving isn't at the sane time as that of moving or faulted-trap forming inner anticline, oil and gas migrated many times and Xinzhen complex faulted-block oil reservoir formed from ES_3~(upper) to EG. Accumulating law and controlling factors of complex faulted-block reservoir are analyzed from many aspects such as regional structure background controlling hydrocarbon accumulating, plastic arch-open structure controlling oil-bearing series and reservoir types, sealing-opening of fault controlling hydrocarbon distribution and structure pattern controlling enriched trap types. Also, we established the structure pattern in Xinzhen a'ea: the arch-open of underlying strata cause expanding fracture. The main block groups developed here are shovel-like normal fault block group in the north area of Xinzhen and its associated graben block group. Block groups dominate the formation and distribution of reservoirs. We studied qualitatively and quantitatively the sealing characteristics, sealing history and sealing mechanism of faults, too. And, the sealing characteristics are evaluated and the distribution pattern of hydrocarbon controlled by faults is researched. Due to movement intensity of big faults, deep falling of downthrown block, high degree of repture and development of fracture, shallow layers close to the downthrown block of secondary faults are unfavorable to hydrocarbon accumulation. This is confirmed by the exploration practice in Xinzhen anticline. In terms of the downthrown blocks of sencondary contemporaneous faults lied in the south and north area of Xinzhen, hydrocarbon is poor close to fracture belt, while it is relatively abundant in tertiary companion faults. Because of long-term movement of faults that control hydrocarbon, fi'om ES3 to EG, six set of oil-bearing series formed. And their opening causes the inhomogeneity in hydrocarbon abundance among each block--in two flanks of anticline reservoirs are abundant while in the axial area, oil and gas are sporadic. There the sealing characteristics control oil-bearing area of oil/gas accumulation and the height of oil reservoir. Longitudinally, oil and gas are enriched in dip-flat areas in mid-plane of faults. It is established that there are four types of accumulating patterns in complex faulted-block oil reservoirs in Xinzhen. The first is accumulating pattern of lithologic oil reservoirs in E~S_3~(mid-lowwer), that is, self-generating-self-reserving-self-covering lithologic trap pattern. The second is drag-anticline accumulating pattern in Xinzhen. The structure traps are drag anticlines formed by the contemporaneous faults of the second basement in the north of Xinzhen, and the multiple source rocks involve Ek_2, Es_4, Es_3 and Es_1 members. The reservoirs are fluvial-delta sandstones of the upper member of Shahejie formation and Guantao formation, covered by regional thick mudstone of the upper member of Guantao formation and MingHuazhen formation. The third is the accumulating pattern of reverse listric fault, the third-degree fault of Xinzhen anticline limb and the reservoirs form reservoir screened by reverse listric faults. The forth is accumulating pattern of crossing faults which form closing or semi-closing faulted-blocks that accumulate hydrocarbon. The technologies of predicting remaining oil in complex faulted-block reservoir during the mid and late development stage is formed. Remaining oil in simple large faulted-blocks enriches in structural high, structural middle, structural low of thick bottom water reservoirs, points near bent edge-fault oftertiary faults and part the fourth ones with big falling displacement, microstructure high place of oil-sandbodies and areas where local well pattern isn't perfect. While that in small complex faulted-blocks enriches near small nose, small high point, angle of small faults, small oil-bearing faulted-blocks without well and areas with non-perfect well pattern. The technologies of enhancing recovery factor in complex faulted-block reservoir during the mid and late development stage is formed as follows: fine reservoir description, drilling adjust wells, designing directional wells, sub-dividing layer series of development, improving flooding pattern, changing water-injection direction and enhancing swept volume, cyclic waterflooding and gas-injection, etc. Here, directional wells include directional deflecting wells, lateral-drilling wells, lateral-drilling horizontal wells and horizontal wells. The results of this paper have been used in exploration and development of Shengli oilfield, and have achieved great social and economic profit, especially in predicting distribution of complex faulted-block reservoir, remaining oil distribution during middle and late stage of development, and in EOR. Applying the achievement of fault-closure research, new hydrocarbon-bearing blocks are discovered in flanks of Dongying central uplift and in complex blocks with proved reserves 15 million tons. With the study of remaining oil distribution law in complex faulted-block reservoirs, recovery factors are increased greatly in Dongxin, Xianhe and Linpan complex faulted-block reservoirs and accumulated oil production increment is 3 million tons.

Dissolution kinetics of octadecanethiolate monolayers electro-adsorbed on Au(1 1 1)

Monolayers of octadecanethiolate on Au(1 1 1) surface were formed under electrochemical control. The influence of the formation time on the reductive desorption process was studied by cyclic voltammetry and chronoamperometry. When the formation time is increased, the reductive desorption peak observed on the voltammograms is significantly shifted in the negative direction, while the cathodic charge is only slightly affected. This behaviour is attributed to a higher degree of organisation of the monolayers for longer formation times, highlighting the role of defect sites in promoting the dissolution. A good agreement was found between our experimental chronoamperograms and theoretical models describing the dissolution process by a shrinkage mechanism. It is demonstrated that a reorganisation process takes place, consisting in the merging of small condensed domains into larger ones. This annealing phenomenon is time and potential dependent, the largest condensed domains being obtained for the longest formation times and least negative potentials. © 2008 Elsevier B.V. All rights reserved.

Comparison of pattern detection methods in microarray time series of the segmentation clock.

While genome-wide gene expression data are generated at an increasing rate, the repertoire of approaches for pattern discovery in these data is still limited. Identifying subtle patterns of interest in large amounts of data (tens of thousands of profiles) associated with a certain level of noise remains a challenge. A microarray time series was recently generated to study the transcriptional program of the mouse segmentation clock, a biological oscillator associated with the periodic formation of the segments of the body axis. A method related to Fourier analysis, the Lomb-Scargle periodogram, was used to detect periodic profiles in the dataset, leading to the identification of a novel set of cyclic genes associated with the segmentation clock. Here, we applied to the same microarray time series dataset four distinct mathematical methods to identify significant patterns in gene expression profiles. These methods are called: Phase consistency, Address reduction, Cyclohedron test and Stable persistence, and are based on different conceptual frameworks that are either hypothesis- or data-driven. Some of the methods, unlike Fourier transforms, are not dependent on the assumption of periodicity of the pattern of interest. Remarkably, these methods identified blindly the expression profiles of known cyclic genes as the most significant patterns in the dataset. Many candidate genes predicted by more than one approach appeared to be true positive cyclic genes and will be of particular interest for future research. In addition, these methods predicted novel candidate cyclic genes that were consistent with previous biological knowledge and experimental validation in mouse embryos. Our results demonstrate the utility of these novel pattern detection strategies, notably for detection of periodic profiles, and suggest that combining several distinct mathematical approaches to analyze microarray datasets is a valuable strategy for identifying genes that exhibit novel, interesting transcriptional patterns.

Stabilization of zinc electrodes with a conducting polymer

The reversibility of zinc anode in alkaline medium was enhanced by electrostatic deposition of a conducting polymer (polypyrrole). Electropolymerization of pyrrole onto zinc in aqueous medium using an organic acid as dopant is feasible and preferred as zinc is less corrosive in this medium. The structure of the polymer film was analyzed by FT-IR spectroscopy and scanning electron microscopy. The effect of the polypyrrole deposit on the zinc electrode was studied by cyclic voltammetry and charge–discharge cycling.

Spontaneous transitions in the coordination of a whole body task

This paper describes an example of spontaneous transitions between qualitatively different coordination patterns during a cyclic lifting and lowering task. Eleven participants performed 12 trials of repetitive lifting and lowering in a ramp protocol in which the height of the lower shelf was raised or lowered I cm per cycle between 10 and 50 cm. Two distinct patterns of coordination were evident: a squat technique in which moderate range of hip, knee and ankle movement was utilised and ankle plantar-flexion occurred simultaneously with knee and hip extension; and a stoop technique in which the range of knee movement was reduced and knee and hip extension was accompanied by simultaneous ankle dorsi-flexion. Abrupt transitions from stoop to squat techniques were observed during descending trials, and from squat to stoop during ascending trials. Indications of hysteresis was observed in that transitions were more frequently observed during descending trials, and the average shelf height at the transition was 5 cm higher during ascending trials. The transitions may be a consequence of a trade-off between the biomechanical advantages of each technique and the influence of the lift height on this trade-off. (C) 2001 Elsevier Science B.V. All rights reserved.