Application of Ru(bpy)(3)(2+) in control and formation of gold surface nanostructure through oxidation-reduction cycling

It was studied that the nanostructure formed on a gold surface via a simple oxidation-reduction cycles (ORC) in 0.1 M KCl containing Ru(bpy)(3)(2+) with different concentrations. Atomic force microscopy (AFM) and energy-dispersed spectroscopy (EDS) were used to characterize the nanostructure formed on the gold surface. Sweep-step voltammetry and corresponding electroluminescence (ECL) response, in situ electrochemical quartz crystal microbalance (EQCM) measurement were used to monitor the ORC. procedure. It was found that the surface structure became more uniform in the presence of Ru(bpy)(3)(2+), and the surface roughness was decreasing with the increasing of Ru(bpY)(3)(2+) concentration, suggesting a simple and effective method to control the formation of nanostructure on the gold surface.

Crystallization behaviors of n-nonadecane in confined space: Observation of metastable phase induced by surface freezing

Crystallization and phase transition behaviors of n-nonadecane in microcapsules with a diameter of about 5 mu m were studied with the combination of differential scanning calorimetry ( DSC) and synchrotron radiation X-ray diffraction ( XRD). As evident from the DSC measurement, a surface freezing monolayer, which is formed in the microcapsules before the bulk crystallization, induces a novel metastable rotator phase ( RII), which has not been reported anywhere else. We argue that the existence of the surface freezing monolayer decreases the nucleating potential barrier of the RII phase and induces its appearance, while the lower free energy in the confined geometry turns the transient RII phase to a " long- lived" metastable phase.

Surface modification of poly(L-lactic acid) to improve its cytocompatibility via assembly of polyelectrolytes and gelatin

Poly(L-lactide) (PLLA) surface was modified via aminolysis by poly(allylamine hydrochloride) (PAH) at high pH and subsequent electrostatic self-assembly of poly(sodium styrenesulfonate) (PSS) and PAH, and the process was monitored by X-ray photoelectron spectroscopy (XPS) and contact angle measurement. These modified PLLAs were then used as charged substrates for further incorporation of gelatin to improve their cytocompatibility. The amphoteric nature of the gelatin was exploited and the gelatin was adsorbed to the negatively charged PLLA/PSS and positively charged PLLA/PAH at pH = 3.4 and 7.4, respectively. XPS and water contact angle data indicated that the gelatin adsorption at pH = 3.4 resulted in much higher surface coverage by gelatin than at pH = 7.4. All the modified PLLA surfaces became more hydrophilic than the virgin PLLA. Chondrocyte culture was used to test the cell attachment, cell morphology and cell viability on the modified PLLA substrates.

Determination of the interfacial acidity of the functional alkanethiols self-assembly membrane by capacitance measurement

The acid-base equilibrium of self-assembly monolayer(SAM) of mercaptopropionic acid on gold electrode was studied by capacitance titration. The change of capacitance was due to protonation and deprotonation of the modified electrode surface. This method can be used to measure pH value in solution and capacitance of solid/liquid on SAMs surface synchronously. The shift of pK(a) was observed during the experiment as previous reports. The factors that affect the capacitance measurement were discussed in detail.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Study on surface acid-base property of carboxylic acid-terminated self-assembled monolayers by cyclic voltammetry and electrochemical impedance spectroscopy

Cyclic voltammetry and electrochemical impedance spectroscopy were used to study the surface acid-base property of carboxylic acid-terminated self-assembled monolayers (SAMs). A carboxylic acid-terminated thiol, such as thioctic acid (1,2-dithiolane-3-pentanoic add), was self-assembled on gold electrodes. Electron transfer between the bulk solution and the SAM modified electrode was studied at different pH using Fe(CN)(6)(3-) as a probe. The surface pK(a) of thioctic acid was determined by cyclic voltammetry and electrochemical impedance spectroscopy to be 5.6 +/- 0.1 and 5.8 +/- 0.1, respectively. The method is compared with other methods of monolayer pK(a) measurement.

Covalent modification of a glassy carbon surface by 4-aminobenzoic acid and its application in fabrication of a polyoxometalates-consisting monolayer and multilayer films

4-Aminobenzoic acid (4-ABA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. X-ray photoelectron spectroscopy measurement proves the presence of 4-carboxylphenylamine monolayer on the GCE. The redox responses of various electroactive probes were investigated on the 4-ABA-modified GCE. Electron transfer to Fe(CN)(6)(3-) in solutions of various pHs was studied by both cyclic voltammetry and electrochemical impedance analysis on the modified electrode. Changes in the solution pH value result in the variation of the terminal group charge state, based on which surface pK(a) values are estimated. The 4-ABA-modified GCE was used as a suitable charged substrate to fabricate polyoxometalates-consisting (POM-consisting) monolayer and multilayer films through layer-by-layer assembly based on electrostatic attraction. Cyclic voltammetry shows the uniform growth of these three-dimensional multilayer films. Taking K10H3[Pr-(SiMo7W4O39)(2)]. H2O (abbreviated as Pr(SiMo7W4)(2)), for example, the preparation and electrochemical behavior of its monolayer and multilayer film had been investigated in detail. This modification strategy is proven to be a general one suitable for anchoring many kinds of POMs on the 4-ABA-modified GCE.

Study of Radiolaria in the surface sediments from the area east of Taiwan Island

The species and characteristics of Radiolaria in the surface sediments were systematcally investigated in the sea east of Taiwan Island. One hundred and seventy-eight species of Radiolaria (including 21 unidentified species) have been identified in the surface sediments, and they belong to 2 orders, 34 families and 101 genera. Among them there are 19 families, 70 genera, 134 species of Spumellaria and 15 families, 31 genera, 44 species of Nassellaria. Of the 178 species of Radiolaria, the individual number of Spumellaria amounts to 88.1% of the total individual number, and that of Nassellaria amounts to 11.9% of the total individual number. It is shown that most of the dominant species belong to the tropical and subtropical dominant species and are brought into the area mainly by the Kuroshio, and some affecting factors including the submarine topography, submarine sediments, upwelling current east of Taiwan Island and carbonate dissolution play a secondary role in forming the Radiolaria distributions.

A moored underwater energy conservation system for profiling measurement

There is a need to obtain the hydrologic data including ocean current, wave, temperature and so on in the South China Sea. A new profiling instrument which does not suffer from the damage due to nature forces or incidents caused by passing ships, is under development to acquire data from this area. This device is based on a taut single point mid-water mooring system. It incorporates a small, instrumented vertically profiling float attached via an electromechanical cable to a winch integral with the main subsurface flotation. On a pre-set schedule, the instrument float with sensors is winched up to the surface if there is no strip passing by, which is defined by an on-board miniature sonar. And it can be immediately winched down to a certain depth if the sonar sensor finds something is coming. Since, because Of logistics, the area can only be visited once for a long time and a minimum of 10 times per day profiles are desired, energy demands are severe. To respond to these concerns, the system has been designed to conserve a substantial portion of the potential energy lost during the ascent phase of each profile and subsequently use this energy to pull the instrument down. Compared with the previous single-point layered measuring mode, it is advanced and economical. At last the paper introduces the test in the South China Sea.

Variability of surface circulation in the South China Sea from satellite altimeter data

11-year satellite altimeter sea surface height (SSH) anomaly data from January 1993 to December 2003 are used to present the dominant spatial patterns and temporal variations of the South China Sea (SCS) surface circulation through Empirical Orthogonal Function (EOF) analysis. The first three EOF modes show the obvious seasonal variations of SSH in the SCS. EOF mode one is generally characterized by a basin-wide circulation. Mode two describes the double-cell basin scale circulation structure. The two cells were located off west of the Luzon Island and southeast of Vietnam, respectively. EOF mode three presents the mesoscale eddy structure in the western SCS, which develops into a strong cyclonic eddy rapidly from July to September. EOF mode one and mode three are also embedded with interannual signals, indicating that the SCS surface circulation variation is influenced by El Nino events prominently. The strong El Nino of 1997/98 obviously changed the SCS circulation structure. This study also shows that there existed a series of mesoscale eddies in the western SCS, and their temporal variation indicates intra-seasonal and interannual signals.

A new empirical model for retrieving sea surface salinity in L band

Sea surface salinity is a key physical parameter in ocean science. It is important in the ocean remote sensing to retrieve sea surface salinity by the microwave probe technology. Based on the in situ measurement data and remote sensing data of the Yellow Sea, we have built a new empirical model in this paper, which can be used to retrieve sea surface salinity of the Yellow Sea by means of the brightness temperature of the sea water at L-band. In this model, the influence of the roughness of the sea surface is considered, and the retrieved result is in good agreement with the in situ measurement data, where the mean absolute error of the retrieved sea surface salinity is about 0.288 psu. This result shows that our model has greater retrieval precision compared with similar models.

古龙咀周围海区沉积物粒度特征及海底地形变化

对古龙咀周围浅海区沉积物的粒度进行了测试与分析，结合相关的地质水文资料，探讨了海岸形态对沉积物粒度的影响。研究区表层沉积物平均粒径在海湾浅海区呈带状由岸向海变细，中等水深和岬角处分布着细粒区，向外海粒径相对变粗；除险岛湾砂质区外，分选差；偏态多数为正偏或近正态；整体峰形极窄，峰型多样。底质类型以粘土质粉砂和砂质粉砂为主，由东北经古龙咀岬角向西南形成S形粘土质粉砂分布带，险岛湾地区沉积物呈带状由砂逐渐过渡到粉砂。潮汐和波浪是本区沉积物输运的主要水动力，岬角的存在影响了沉积物粒度的分布。粒度趋势分析表明沉积物整体有向岬角汇聚的输运趋势。 对收集到基于1954年、1969年、1982年测量绘成的地形图水深数据进行数字化，结合2005年测量的水深数据，分别建立各时期DEM图，在此基础上分析研究区的地形特征。四个时期海底DEM呈现出大体一致的趋势，在险岛湾及白沙口海湾内为浅水区，水深值在-1～-4 m之间，深水区主要分布在南黄岛南端至古龙咀连线以南区域，呈扇形展布，水深由南黄岛两侧向中间逐渐加深，水深值在-10～ -17 m之间。从整体上看，研究区海底地形呈NW-SE方向逐渐加深。 将数字化后的水深数据统一校正到1956黄海高程系，分别建立DEM，运用GIS的栅格计算分析得出冲淤变化图。相关结果表明：1954～1969年研究区整体近岸为冲（险岛湾除外），离岸海域为淤；1969～1982年研究区总体处于弱淤积状态；1982-2005研究区海域近岸为淤，外海以弱冲刷状态为主。

地幔对流理论及其在解释地球物理观测的应用

With the improving of mantle convection theory, the developing of computing method and increasing of the measurement data, we can numerically simulate more clearly about the effects on some geophysical observed phenomenons such as the global heat flow and global lithospheric stress field in the Earth's surface caused by mantle convection, which is the primary mechanism for the transport of heat from the Earth's deep interior to its surface and the underlying force mechanism of dynamics in the Earth.Chapter 1 reviews the historical background and present research state of mantle convection theory.In Chapter 2, the basic conception of thermal convection and the basic theory about mantle flow.The effects on generation and distribution of global lithospheric stres s field induced by mantle flow are the subject of Chapter 3. Mantle convection causes normal stress and tangential stresses at the bottom of the lithosphere, and then the sublithospheric stress field induces the lithospheric deformation as sixrface force and results in the stress field within the lithosphere. The simulation shows that the agreement between predictions and observations is good in most regions. Most of subduction zones and continental collisions are under compressive. While ocean ridges, such as the east Pacific ridge, the Atlantic ridge and the east African rift valley, are under tensile. And most of the hotspots preferentially occur in regions where calculated stress is tensile. The calculated directions of the most compressive principal horizontal stress are largely in accord with that of the observation except for some regions such as the NW-Pacifie subduction zone and Qinghai-Tibet Plateau, in which the directions of the most compressive principal horizontal stress are different. It shows that the mantel flow plays an important role in causing or affecting the large-scale stress field within the lithosphere.The global heat flow simulation based on a kinematic model of mantle convection is given in Chapter 4. Mantle convection velocities are calculated based on the internal loading theory at first, the velocity field is used as the input to solve the thermal problem. Results show that calculated depth derivatives of the near surface temperature are closely correlated to the observed surface heat flow pattern. Higher heat flow values around midocean ridge systems can be reproduced very well. The predicted average temperature as a function of function of depth reveals that there are two thermal boundary layers, one is close to the surface and another is close to the core-mantle boundary, the rest of the mantle is nearly isothermal. Although, in most of the mantle, advection dominates the heat transfer, the conductive heat transfer is still locally important in the boundary layers and plays an important role for the surface heat flow pattern. The existence of surface plates is responsible for the long wavelength surface heat flow pattern.In Chapter 5, the effects on present-day crustal movement in the China Mainland resulted from the mantle convection are introduced. Using a dynamic method, we present a quantitative model for the present-day crustal movement in China. We consider not only the effect of the India-Eurasia collision, the gravitational potential energy difference of the Tibet Plateau, but also the contribution of the shear traction on the bottom of the lithosphere induced by the global mantle convection. The comparison between our results and the velocity field obtained from the GPS observation shows that our model satisfactorily reproduces the general picture of crustal deformation in China. Numerical modeling results reveal that the stress field on the base of the lithosphere induced by the mantle flow is probably a considerable factor that causes the movement and deformation of the lithosphere in continental China with its eflfcet focuing on the Eastern China A numerical research on the small-scale convection with variable viscosity in the upper mantle is introduced in Chapter 6. Based on a two-dimensional model, small-scale convection in the mantle-lithosphere system with variable viscosity is researched by using of finite element method. Variation of viscosity in exponential form with temperature is considered in this paper The results show that if viscosity is strongly temperature-dependent, the upper part of the system does not take a share in the convection and a stagnant lid, which is identified as lithosphere, is formed on the top of system because of low temperature and high viscosity. The calculated surface heat flow, topography and gravity anomaly are associated well with the convection pattern, namely, the regions with high heat flow and uplift correspond to the upwelling flow, and vice versa.In Chapter 7, we give a brief of future research subject: The inversion of lateral density heterogeneity in the mantle by minimizing the viscous dissipation.