Renewable-surface amperometric nitrite sensor based on sol-gel-derived silicomolybdate-methylsilicate-graphite composite material

A new type of silicomolybdate-methylsilicate-graphite composite material was prepared by the sol-gel technique and used for the fabrication of an amperometric nitrite sensor. The silicomolybdic anion acts as a catalyst, the graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. Cyclic voltammetry, square-wave voltammetry and chronoamperometry were employed to characterize the sensor. The amperometric nitrite sensor exhibited a series of good properties: high sensitivity (1.771 mu A mmol(-1) dm(3)), a short response time (7 s), remarkable long-term stability and especially reproducibility of surface renewal in the event of electrode surface fouling.

Investigation into self-assembled monolayers of a polyether dendron thiol: Chemisorption, kinetics, and patterned surface

Different sizes of Frechet-type dendrons with a thiol group at the focal point were synthesized, well characterized, and used as building blocks for the preparation of self-assembled monolayers (SAMs) on metal surfaces. From the studies of the kinetic process of dendron thiol self-assembling on gold, it is shown that the dendron thiol assembling proceeds with different adsorption rates depending on the assembly time. In contrast to normal alkanethiols forming highly molecular structures on metal surfaces, the SAMs of polyether dendron form patterned surfaces with nanometer-sized features and in long-range order. It is found that the patterned stripes are closely related to the size of the dendron, and the patterned stripes can be improved by thermal annealing.

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified class slide: A strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

Potential-induced transformation for surfactant aggregates on a metal surface

Surfactant adsorption on metal surfaces has been used to limit the activity of the electrode surface and to stabilize colloidal clusters and nanoparticles in solution, but the adsorption and relative potential-induced structure change of the surfactant were not known. Here, the adsorption of sodium dodecyl sulfate (SDS) on a Au(111) surface under potential control was investigated by in situ scanning tunneling microscopy (STM). The STM images showed that the morphology of SDS on Au(111) was changed from a hemi-cylindrical micellar monolayer to a compact and uniform bilayer through control of the potential. The transition between the hemimicellar monolayer and the compact bilayer is not reversed after a period of time. The model of potential-induced transformation for SDS aggregates on Au(111) was established. (C) 2001 Elsevier Science B.V. All rights reserved.

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

INVESTIGATION OF CETYLPYRIDINIUM BROMIDE ADSORPTION AT A GLASSY-CARBON ELECTRODE SURFACE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

The adsorption of cationic surfactant cetylpyridinium bromide (CPB) on a glassy carbon (GC) electrode surface has been studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. A fine adsorption isotherm of CPB molecules from an aqueous solution containing 0.10 M KBr has been obtained over the range of (1.00-8.00) x 10(-5) M. From theoretical calculation and experimental data, adsorption of CPB on the GC electrode surface shows four distinct orientations and three large orientation transitions. Compared with the ordinary isotherm, the differential isotherm is more characteristic and would be suitable for the study of orientation transitions of organic compounds. With a theoretical treatment of the adsorption isotherm, four orientations of adsorbed CPB on a GC electrode surface coincide with the Frumkin-Langmuir type. From adsorption parameters the Frumkin-Langmuir equations, the adsorption free energy and, therefore, the equilibrium constants of orientation transitions of the CPB molecule can be obtained.

Neural network retrieval of ocean surface parameters from SSM/I data

A new algorithm based on the multiparameter neural network is proposed to retrieve wind speed (WS), sea surface temperature (SST), sea surface air temperature, and relative humidity ( RH) simultaneously over the global oceans from Special Sensor Microwave Imager (SSM/I) observations. The retrieved geophysical parameters are used to estimate the surface latent heat flux and sensible heat flux using a bulk method over the global oceans. The neural network is trained and validated with the matchups of SSM/I overpasses and National Data Buoy Center buoys under both clear and cloudy weather conditions. In addition, the data acquired by the 85.5-GHz channels of SSM/I are used as the input variables of the neural network to improve its performance. The root-mean-square (rms) errors between the estimated WS, SST, sea surface air temperature, and RH from SSM/I observations and the buoy measurements are 1.48 m s(-1), 1.54 degrees C, 1.47 degrees C, and 7.85, respectively. The rms errors between the estimated latent and sensible heat fluxes from SSM/I observations and the Xisha Island ( in the South China Sea) measurements are 3.21 and 30.54 W m(-2), whereas those between the SSM/ I estimates and the buoy data are 4.9 and 37.85 W m(-2), respectively. Both of these errors ( those for WS, SST, and sea surface air temperature, in particular) are smaller than those by previous retrieval algorithms of SSM/ I observations over the global oceans. Unlike previous methods, the present algorithm is capable of producing near-real-time estimates of surface latent and sensible heat fluxes for the global oceans from SSM/I data.

Generation of internal and surface waves by seafloor movement in a two layer fluid system

Internal and surface waves generated by the deformations of the solid bed in a two layer fluid system of infinite lateral extent and uniform depth are investigated. An integral solution is developed for an arbitrary bed displacement on the basis of a linear approximation of the complete description of wave motion using a transform method (Laplace in time and Fourier in space) analogous to that used to study the generation of tsunamis by many researchers. The theoretical solutions are presented for three interesting specific deformations of the seafloor; the spatial variation of each seafloor displacement consists of a block section of the seafloor moving vertically either up or down while the time-displacement history of the block section is varied. The generation process and the profiles of the internal and surface waves for the case of the exponential bed movement are numerically illustrated, and the effects of the deformation parameters, densities and depths of the two layers on the solutions are discussed. As expected, the solutions derived from the present work include as special cases that obtained by Kervella et al. [Theor Comput Fluid Dyn 21:245-269, 2007] for tsunamis cased by an instantaneous seabed deformation and those presented by Hammack [J Fluid Mech 60:769-799, 1973] for the exponential and the half-sine bed displacements when the density of the upper fluid is taken as zero.

The effects of random surface waves on the steady Ekman current solutions

The response of near-surface current profiles to wind and random surface waves are studied based on the approach of Jenkins [1989. The use of a wave prediction model for driving a near surface current model. Dtsch. Hydrogr. Z. 42,134-149] and Tang et al. [2007. Observation and modeling of surface currents on the Grand Banks: a study of the wave effects on surface currents. J. Geophys. Res. 112, C10025, doi:10.1029/2006JC004028]. Analytic steady solutions are presented for wave-modified Ekman equations resulting from Stokes drift, wind input and wave dissipation for a depth-independent constant eddy viscosity coefficient and one that varies linearly with depth. The parameters involved in the solutions can be determined by the two-dimensional wavenumber spectrum of ocean waves, wind speed, the Coriolis parameter and the densities of air and water, and the solutions reduce to those of Lewis and Belcher [2004. Time-dependent, coupled, Ekman boundary layer solutions incorporating Stokes drift. Dyn. Atmos. Oceans. 37, 313-351] when only the effects of Stokes drift are included. As illustrative examples, for a fully developed wind-generated sea with different wind speeds, wave-modified current profiles are calculated and compared with the classical Ekman theory and Lewis and Belcher's [2004. Time-dependent, coupled, Ekman boundary layer solutions incorporating Stokes drift. Dyn. Atmos. Oceans 37, 313-351] modification by using the Donelan and Pierson [1987. Radar scattering and equilibrium ranges in wind-generated waves with application to scatterometry. J. Geophys. Res. 92, 4971-5029] wavenumber spectrum, the WAM wave model formulation for wind input energy to waves, and wave energy dissipation converted to currents. Illustrative examples for a fully developed sea and the comparisons between observations and the theoretical predictions demonstrate that the effects of the random surface waves on the classical Ekman current are important, as they change qualitatively the nature of the Ekman layer. But the effects of the wind input and wave dissipation on surface current are small, relative to the impact of the Stokes drift. (C) 2008 Elsevier Ltd. All rights reserved.

Physical mechanism and numerical simulations of surface layer temperature inversion in tropical ocean

The one-dimensional Kraus-Turner mixed layer model improved by Liu is developed to consider the effect of salinity and the equations of temperature and salinity under the mixed layer. On this basis, the processes of growth and death of surface layer temperature inversion is numerically simulated under different environmental parameters. At the same time, the physical mechanism is preliminarily discussed combining the observations at the station of TOGA-COARE 0 degrees N, 156 degrees E. The results indicate that temperature inversion sensitively depends on the mixed layer depth, sea surface wind speed and solar shortwave radiation, etc., and appropriately meteorological and hydrological conditions often lead to the similarly periodical occurrence of this inversion phenomenon.

Comparison of nonlinear and linear PCA on surface wind, surface height, and SST in the South China Sea

We compared nonlinear principal component analysis (NLPCA) with linear principal component analysis (LPCA) with the data of sea surface wind anomalies (SWA), surface height anomalies (SSHA), and sea surface temperature anomalies (SSTA), taken in the South China Sea (SCS) between 1993 and 2003. The SCS monthly data for SWA, SSHA and SSTA (i.e., the anomalies with climatological seasonal cycle removed) were pre-filtered by LPCA, with only three leading modes retained. The first three modes of SWA, SSHA, and SSTA of LPCA explained 86%, 71%, and 94% of the total variance in the original data, respectively. Thus, the three associated time coefficient functions (TCFs) were used as the input data for NLPCA network. The NLPCA was made based on feed-forward neural network models. Compared with classical linear PCA, the first NLPCA mode could explain more variance than linear PCA for the above data. The nonlinearity of SWA and SSHA were stronger in most areas of the SCS. The first mode of the NLPCA on the SWA and SSHA accounted for 67.26% of the variance versus 54.7%, and 60.24% versus 50.43%, respectively for the first LPCA mode. Conversely, the nonlinear SSTA, localized in the northern SCS and southern continental shelf region, resulted in little improvement in the explanation of the variance for the first NLPCA.

Geochemical characteristics of nitrogen in the southern Yellow Sea surface sediments

Roles and distributions of various forms of nitrogen in biogeochemical cycling in the southern Yellow Sea surface sediments were investigated. The southern Yellow Sea could be divided into three regions (I, II and III) according to the proportion of fine-grained sediment in > 65%, 35-65% and < 35%, respectively. The ratios of different forms of nitrogen contents between each two of the three regions indicated that the nitrogen contents increased with the proportion of fine-grained sediment increasing. The quanta of exchangeable forms of nitrogen were similar in the three regions, while their releasing time increased from regions I to III, indicating that the cycle of nitrogen in fine-grained sediments was shorter than that in coarse-grained sediments. Nitrogen burial fluxes were also similar in these regions, while the burial efficiency increased from regions I to III. The highest burial efficiency was 30.21% in region III, indicating that more than 70% of nitrogen in the southern Yellow Sea surface sediments could be released to take part in biogeochemical recycling. When all the four forms of exchangeable nitrogen (nitrogen in ion exchangeable form (IEF-N), nitrogen in weak acid extractable form (WAEF-N), nitrogen in strong alkali extractable form (SAEF-N) and nitrogen in strong oxidant extractable form (SOEF-N)) were released to take part in recycling, their potential contributions were 80% (SOEF-N), 11% (IEF-N), 6% (SAEF-N), 3% (WAEF-N) respectively, which showed that SOEF-N was the predominant one, and its contribution to biogeochemical cycling was the highest. (c) 2004 Elsevier B.V. All rights reserved.

Shape-Time Photography

We introduce a new method to describe, in a single image, changes in shape over time. We acquire both range and image information with a stationary stereo camera. From the pictures taken, we display a composite image consisting of the image data from the surface closest to the camera at every pixel. This reveals the 3-d relationships over time by easy-to-interpret occlusion relationships in the composite image. We call the composite a shape-time photograph. Small errors in depth measurements cause artifacts in the shape-time images. We correct most of these using a Markov network to estimate the most probable front surface, taking into account the depth measurements, their uncertainties, and layer continuity assumptions.

Temporal Surface Reconstruction

This thesis investigates the problem of estimating the three-dimensional structure of a scene from a sequence of images. Structure information is recovered from images continuously using shading, motion or other visual mechanisms. A Kalman filter represents structure in a dense depth map. With each new image, the filter first updates the current depth map by a minimum variance estimate that best fits the new image data and the previous estimate. Then the structure estimate is predicted for the next time step by a transformation that accounts for relative camera motion. Experimental evaluation shows the significant improvement in quality and computation time that can be achieved using this technique.