Simple preparation method of multilayer polymer films containing Pd nanoparticles

A simple route to the fabrication of multilayer films containing Pd nanoparticles is described. Following layer-by-layer assembly of PdCl42- and polycation, QPVP-Os (a quaternized poly(4-vinylpyridine) complexed with [Os(bpy)(2)Cl](2+/+)), on 4-aminobenzoic acid-modified glassy carbon electrodes, the three-dimensional Pd nanoparticle multilayer films are directly formed on electrode surfaces via electrochemical reduction of PdCl42- sandwiched between polymers. The growth of PdCl42- is easy on electrode surfaces by electrostatic interaction, and the assembly processes are monitored by cyclic voltammetry and UV-vis spectroscopy. The depth profile analyses by X-ray photoelectron spectroscopy verify the constant composition of the Pd nanoparticle multilayer films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 3-7 mn. The resulting Pd nanoparticle multilayer-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen and oxidation of hydrazine compounds in aqueous solution.

Two dimensional nuclear magnetic resonance analysis of ruthenium-(4,4'-dimethyl-2,2'-bipyridine)(2) (2,2'-bipyridine-4,4'-dicarboxylic acid) (PF6)(2)

The (1) H and C-13 NMR spectra are reported for Ru(4, 4'-dimethyl-2,2'-bipyridene)(2) (2,2'-bipyridine-4,4'-dicarboxylic acid) (PF6)(2) that can be used as a new electrochemiluminescent probe in immunoasssay and nucleic acid hybridization assay. Because of the effect ol:Ru atom ligands and complex steric configuration, it is difficult to attribute spectra of the title molecular, By using 2D (1) H-(1) H COSY and (1) H-C-13 HETCOR method, the proton and C-13 NMR spectra are assigned completely, which provides a satisfactory method to quantitative and qualitative, analysis of the title moleculer in the further study.

attB site disruption in marine Actinomyces sp M048 via DNA transformation of a site-specific integration vector

An efficient conjugation method has been developed for the marine Actinomyces sp. isolate M048 to facilitate the genetic manipulation of the chandrananimycin biosynthesis gene cluster. A phi C31-derived integration vector pIJ8600 containing oriT and attP fragments was introduced into strain M048 by bi-parental conjugation from Escherichia coli ET12567 to strain M048. Transformation efficiency was (6.38 +/- 0.41) x 10(-5) exconjugants per recipient spore. Analysis of eight exconjugants showed that the plasmid pIJ8600 was stably integrated at a single chromosomal site (attB) of the Actinomyces genome. The DNA sequence of the attB was cloned and shown to be conserved. The results of antimicrobial activity analysis indicated that the insertion of plasmid pIJ8600 seemed to affect the biosynthesis of antibiotics that could strongly inhibit the growth of E. coli and Mucor miehei (Tu284). HPLC-MS analysis of the extracts indicated that disruption of the attB site resulted in the complete abolition of chandrananimycin A-C production, proving the identity of the gene cluster. Instead of chandrananimycins, two bafilomycins were produced through disruption of the attB site from the chromosomal DNA of marine Actinomyces sp. M048.

Wave generation by the falling rock in the two-dimensional wave tank

Wave generation by the falling rock in the two-dimensional wave tank is experimentally and numerically studied, where the numerical model utilizes the boundary element method to solve the fully nonlinear potential flow theory. The wave profiles at different times are measured in the laboratory, which are also used to test the numerical model. Comparisons show that the experimental and numerical results are in good agreement, and the numerical model can be used to simulate the wave generation due to the submarine rock falling. Further numerical tests on the influences of the rock size, density, initial position and the falling angle on the wave elevation of the generated waves are performed, respectively. The results show that the size and density of the rock have strong effects on the maximum elevation of the generated wave, while the effects of the initial position and the falling angle of the rock are also significant. When the size or the density of the rock increases, the maximum elevation of the generated wave increases. The same effect on the generated wave would be produced if the initial position of the rock becomes closer to the surface, or the falling angle between the falling route and the vertical direction turns larger. In addition, the present numerical tests reveal that the submarine rock falling provides a new generation method for the breaking wave in the wave tank.

海洋微藻产生溶解有机物及东海溶解有机物三维荧光特征研究

本文通过胶州湾围隔实验、微藻培养实验研究了海洋微藻产生溶解有机物的三维荧光特性，并初步利用经验正交函数对三维荧光光谱图进行了主成分分析，通过东海取样研究了东海荧光溶解有机物的时空分布特征，并对荧光溶解有机物的来源进行了分析。得到了一些初步结论： 胶州湾围隔实验中不同营养盐培养结果表明浮游植物可产生类蛋白和类腐殖质荧光，类蛋白荧光峰由类酪氨酸(tyrosine-like)荧光峰和类色氨酸(tryptophan-like)荧光峰组成，主要位置为Exmax/Emmax=270nm/290~310nm，Exmax/Emmax= 270~290/320~350的荧光峰强度比较弱；在Exmax/Emmax=250~260/380~480nm(A峰)、Exmax/Emmax=310~320/380~420nm(C峰)和Exmax/Emmax=330~350/420~480nm(M峰)位置均出现零散的类腐殖质荧光峰，其中以A峰为主。类酪氨酸荧光强度明显高于类腐殖质荧光强度。浮游植物量降低时，类酪氨酸荧光强度与叶绿素a浓度呈明显的负相关。硅藻和甲藻产生的类酪氨酸和类色氨酸荧光强度之间具有较好的相关性，两者来源相似, 并且甲藻与硅藻相比能够产生更多的类蛋白荧光物质。不同环境下类腐殖质混合物的组分比例不同，甲藻生长环境下相对于硅藻具有较低的A:C比值。 在实验室培养中肋骨条藻（Skeletonema costatum）、塔玛亚历山大藻（Alexandrium tamarense）、微小亚历山大藻（Alexandrium mimutum）、锥状斯氏藻（Scrippsiella trochoidea）、东海原甲藻（Prorocentrum donghaiense）及海洋原甲藻（Prorocentrum micans）的实验结果表明，微藻在生长过程中产生出荧光溶解有机物，中肋骨条藻为代表的硅藻主要产生类腐殖质荧光物质，而甲藻在指数增长期主要产生类蛋白荧光物质。进入消亡期后类蛋白荧光和类腐殖质荧光强度迅速增大，原因可能是衰老、死亡藻细胞的破碎释放出大量的荧光有机物质所致，此外还有细菌对非荧光有机物进一步降解。塔玛亚历山大藻、微小亚历山大藻、东海原甲藻及海洋原甲藻的类蛋白荧光强度在消亡后期由于细菌降解或光降解等因素而降低。同属微藻产生的荧光物质相似，例如塔玛亚历山大藻与微小亚历山藻、东海原甲藻与海洋原甲藻，但具体荧光峰位置有所不同。利用经验正交函数能够对三维荧光光谱谱图进行主成份分析。 在利用三维荧光光谱法研究长江口海域台风前后不同站位荧光溶解有机物荧光特性及分布特征的结果表明，长江口海区主要的荧光溶解有机物荧光峰为T峰、S峰和A峰。风前和风后的类色氨酸分别来源于相似物质。风前，在表层浮游植物能够产生类蛋白荧光物质，而底层类蛋白荧光物质不受浮游植物的影响，长江冲淡水能够带来部分类蛋白荧光物质；表层的类腐殖质不受浮游植物的影响，而底层的浮游植物在降解过程中能够产生一部分类腐殖质，并且长江冲淡水对表层和底层的类腐殖质来源均有很大贡献。风后，表层的类色氨酸与叶绿素a浓度不呈相关性，而底层却呈正相关，另外表层和底层的类色氨酸均受到长江冲淡水的影响；表层和底层的类腐殖质与叶绿素a均没有相关性，但受陆源影响显著，长江冲淡水能带来类腐殖质。

基于匹配追踪方法的地震信号时频分析研究

Seismic signal is a typical non-stationary signal, whose frequency is continuously changing with time and is determined by the bandwidth of seismic source and the absorption characteristic of the media underground. The most interesting target of seismic signal’s processing and explaining is to know about the local frequency’s abrupt changing with the time, since this kind of abrupt changing is indicating the changing of the physical attributes of the media underground. As to the seismic signal’s instantaneous attributes taken from time-frequency domain, the key target is to search a effective, non-negative and fast algorithm time-frequency distribution, and transform the seismic signal into this time-frequency domain to get its instantaneous power spectrum density, and then use the process of weighted adding and average etc. to get the instantaneous attributes of seismic signal. Time-frequency analysis as a powerful tool to deal with time variant non-stationary signal is becoming a hot researching spot of modern signal processing, and also is an important method to make seismic signal’s attributes analysis. This kind of method provides joint distribution message about time domain and frequency domain, and it clearly plots the correlation of signal’s frequency changing with the time. The spectrum decomposition technique makes seismic signal’s resolving rate reach its theoretical level, and by the method of all frequency scanning and imaging the three dimensional seismic data in frequency domain, it improves and promotes the resolving abilities of seismic signal vs. geological abnormal objects. Matching pursuits method is an important way to realize signal’s self-adaptive decomposition. Its main thought is that any signal can be expressed by a series of time-frequency atoms’ linear composition. By decomposition the signal within an over completed library, the time-frequency atoms which stand for the signal itself are selected neatly and self-adaptively according to the signal’s characteristics. This method has excellent sparse decomposition characteristics, and is widely used in signal de-noising, signal coding and pattern recognizing processing and is also adaptive to seismic signal’s decomposition and attributes analysis. This paper takes matching pursuits method as the key research object. As introducing the principle and implementation techniques of matching pursuits method systematically, it researches deeply the pivotal problems of atom type’s selection, the atom dictionary’s discrete, and the most matching atom’s searching algorithm, and at the same time, applying this matching pursuits method into seismic signal’s processing by picking-up correlative instantaneous messages from time-frequency analysis and spectrum decomposition to the seismic signal. Based on the research of the theory and its correlative model examination of the adaptively signal decomposition with matching pursuit method, this paper proposes a fast optimal matching time-frequency atom’s searching algorithm aimed at seismic signal’s decomposition by frequency-dominated pursuit method and this makes the MP method pertinence to seismic signal’s processing. Upon the research of optimal Gabor atom’s fast searching and matching algorithm, this paper proposes global optimal searching method using Simulated Annealing Algorithm, Genetic Algorithm and composed Simulated Annealing and Genetic Algorithm, so as to provide another way to implement fast matching pursuit method. At the same time, aimed at the characteristics of seismic signal, this paper proposes a fast matching atom’s searching algorithm by means of designating the max energy points of complex seismic signal, searching for the most optimal atom in the neighbor area of these points according to its instantaneous frequency and instantaneous phase, and this promotes the calculating efficiency of seismic signal’s matching pursuit algorithm. According to these methods proposed above, this paper implements them by programmed calculation, compares them with some open algorithm and proves this paper’s conclusions. It also testifies the active results of various methods by the processing of actual signals. The problems need to be solved further and the aftertime researching targets are as follows: continuously seeking for more efficient fast matching pursuit algorithm and expanding its application range, and also study the actual usage of matching pursuit method.

基于广义Lippmann-Schwinger方程的地震波场模拟算法与应用

In the last several decades, due to the fast development of computer, numerical simulation has been an indispensable tool in scientific research. Numerical simulation methods which based on partial difference operators such as Finite Difference Method (FDM) and Finite Element Method (FEM) have been widely used. However, in the realm of seismology and seismic prospecting, one usually meets with geological models which have piece-wise heterogeneous structures as well as volume heterogeneities between layers, the continuity of displacement and stress across the irregular layers and seismic wave scattering induced by the perturbation of the volume usually bring in error when using conventional methods based on difference operators. The method discussed in this paper is based on elastic theory and integral theory. Seismic wave equation in the frequency domain is transformed into a generalized Lippmann-Schwinger equation, in which the seismic wavefield contributed by the background is expressed by the boundary integral equation and the scattering by the volume heterogeneities is considered. Boundary element-volume integral method based on this equation has advantages of Boundary Element Method (BEM), such as reducing one dimension of the model, explicit use the displacement and stress continuity across irregular interfaces, high precision, satisfying the boundary at infinite, etc. Also, this method could accurately simulate the seismic scattering by the volume heterogeneities. In this paper, the concrete Lippmann-Schwinger equation is specifically given according to the real geological models. Also, the complete coefficients of the non-smooth point for the integral equation are introduced. Because Boundary Element-Volume integral equation method uses fundamental solutions which are singular when the source point and the field are very close，both in the two dimensional and the three dimensional case, the treatment of the singular kernel affects the precision of this method. The method based on integral transform and integration by parts could treat the points on the boundary and inside the domain. It could transform the singular integral into an analytical one both in two dimensional and in three dimensional cases and thus it could eliminate the singularity. In order to analyze the elastic seismic wave scattering due to regional irregular topographies, the analytical solution for problems of this type is discussed and the analytical solution of P waves by multiple canyons is given. For the boundary reflection, the method used here is infinite boundary element absorbing boundary developed by a pervious researcher. The comparison between the analytical solutions and concrete numerical examples validate the efficiency of this method. We thoroughly discussed the sampling frequency in elastic wave simulation and find that, for a general case, three elements per wavelength is sufficient, however, when the problem is too complex, more elements per wavelength are necessary. Also, the seismic response in the frequency domain of the canyons with different types of random heterogeneities is illustrated. We analyzed the model of the random media, the horizontal and vertical correlation length, the standard deviation, and the dimensionless frequency how to affect the seismic wave amplification on the ground, and thus provide a basis for the choice of the parameter of random media during numerical simulation.

三维油藏数值模拟正反演算法研究

The dynamic prediction of complex reservoir development is one of the important research contents of dynamic analysis of oil and gas development. With the increase development of time, the permeabilities and porosities of reservoirs and the permeability of block reservoir at its boundaries are dynamically changing. How to track the dynamic change of permeability and porosity and make certain the permeability of block reservoir at its boundary is an important practical problem. To study developing dynamic prediction of complex reservoir, the key problem of research of dynamic prediction of complex reservoir development is realizing inversion of permeability and porosity. To realize the inversion, first of all, the fast forward and inverse method of 3-dimension reservoir simulation must be studied. Although the inversion has been widely applied to exploration and logging, it has not been applied to3-dimension reservoir simulation. Therefore, the study of fast forward and inverse method of 3-dimension reservoir simulation is a cutting-edge problem, takes on important realistic signification and application value. In this dissertation, 2-dimension and 3-dimension fluid equations in porous media are discretized by finite difference, obtaining finite difference equations to meet the inner boundary conditions by Peaceman's equations, giving successive over relaxation iteration of 3-dimension fluid equations in porous media and the dimensional analysis. Several equation-solving methods are compared in common use, analyzing its convergence and convergence rate. The alternating direction implicit procedure of 2-dimension has been turned into successive over relaxation iteration of alternating direction implicit procedure of 3-dimension fluid equations in porous media, which possesses the virtues of fast computing speed, needing small memory of computer, good adaptability for heterogeneous media and fast convergence rate. The geological model of channel-sandy reservoir has been generated with the help of stochastic simulation technique, whose cross sections of channel-sandy reservoir are parabolic shapes. This method makes the hard data commendably meet, very suit for geological modeling of containing complex boundary surface reservoir. To verify reliability of the method, theoretical solution and numerical solution are compared by simplifying model of 3-dimension fluid equations in porous media, whose results show that the only difference of the two pressure curves is that the numerical solution is lower than theoretical at the wellbore in the same space. It proves that using finite difference to solve fluid equations in porous media is reliable. As numerical examples of 3-dimension heterogeneous reservoir of the single-well and multi-well, the pressure distributions have been computed respectively, which show the pressure distributions there are clearly difference as difference of the permeabilities is greater than one order of magnitude, otherwise there are no clearly difference. As application, the pressure distribution of the channel-sandy reservoir have been computed, which indicates that the space distribution of pressure strongly relies on the direction of permeability, and is sensitive for space distributions of permeability. In this dissertation, the Peaceman's equations have been modified into solving vertical well problem and horizontal well problem simultaneously. In porous media, a 3D layer reservoir in which contain vertical wells and horizontal wells has been calculated with iteration. For channel-sandy reservoir in which there are also vertical wells and horizontal wells, a 3D transient heterogeneous fluid equation has been discretized. As an example, the space distribution of pressure has been calculated with iteration. The results of examples are accord with the fact, which shows the modification of Peaceman's equation is correct. The problem has been solved in the space where there are vertical and horizontal wells. In the dissertation, the nonuniform grid permeability integration equation upscaling method, the nonuniform grid 2D flow rate upscaling method and the nonuniform grid 3D flow rate upscaling method have been studied respectively. In those methods, they enhance computing speed greatly, but the computing speed of 3D flow rate upscaling method is faster than that of 2D flow rate upscaling method, and the precision of 3D flow rate upscaling method is better than that of 2D flow rate upscaling method. The results also show that the solutions of upscaling method are very approximating to that of fine grid blocks. In this paper, 4 methods of fast adaptive nonuniform grid upscaling method of 3D fluid equations in porous media have been put forward, and applied to calculate 3D heterogeneous reservoir and channel-sandy reservoir, whose computing results show that the solutions of nonuniform adaptive upscaling method of 3D heterogeneous fluid equations in porous media are very approximating to that of fine grid blocks in the regions the permeability or porosity being abnormity and very approximating to that of coarsen grid blocks in the other region, however, the computing speed of adaptive upscaling method is 100 times faster than that of fine grid block method. The formula of sensitivity coefficients are derived from initial boundary value problems of fluid equations in porous media by Green's reciprocity principle. The sensitivity coefficients of wellbore pressure to permeability parameters are given by Peaceman's equation and calculated by means of numerical calculation method of 3D transient anisotropic fluid equation in porous media and verified by direct method. The computing results are in excellent agreement with those obtained by the direct method, which shows feasibility of the method. In the dissertation, the calculating examples are also given for 3D reservoir, channel-sandy reservoir and 3D multi-well reservoir, whose numerical results indicate: around the well hole, the value of the sensitivity coefficients of permeability is very large, the value of the sensitivity coefficients of porosity is very large too, but the sensitivity coefficients of porosity is much less than the sensitivity coefficients of permeability, so that the effect of the sensitivity coefficients of permeability for inversion of reservoir parameters is much greater than that of the sensitivity coefficients of porosity. Because computing the sensitivity coefficients needs to call twice the program of reservoir simulation in one iteration, realizing inversion of reservoir parameters must be sustained by the fast forward method. Using the sensitivity coefficients of permeability and porosity, conditioned on observed valley erosion thickness in wells (hard data), the inversion of the permeabilities and porosities in the homogeneous reservoir, homogeneous reservoir only along the certain direction and block reservoir are implemented by Gauss-Newton method or conjugate gradient method respectively. The results of our examples are very approximating to the real data of permeability and porosity, but the convergence rate of conjugate gradient method is much faster than that of Gauss-Newton method.

Deconvolution of overlapped peaks based on the exponentially modified Gaussian model in comprehensive two-dimensional gas chromatography

Comprehensive two-dimensional gas chromatography (GC x GC) has attracted much attention for the analys is of complex samples. Even with a large peak capacity in GC x GC, peak overlapping is often met. In this paper, a new method was developed to resolve overlapped peaks based on the mass conservation and the exponentially modified Gaussian (EMG) model. Linear relationships between the calculated sigma, tau of primary peaks with the corresponding retention time (t(R)) were obtained, and the correlation coefficients were over 0.99. Based on such relationships, the elution profile of each compound in overlapped peaks could be simulated, even for the peak never separated on the second-dimension. The proposed method has proven to offer more accurate peak area than the general data processing method. (c) 2005 Elsevier B.V. All rights reserved.

Comparison of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and gas chromatography-mass spectrometry for the analysis of tobacco essential oils

A sample of tobacco essential oil was analyzed using gas chromatography-mass spectrometry (GUMS)and comprehensive two-dimensional gas chromatography coupled to a time-of-flight mass spectrometry (GC x GC/TOFMS), respectively. In the GUMS analysis, serially coupled columns were used. By comparing the GUMS results with GC x GC/TOFMS result,,, many more components in the essential oil could be found within the two-dimensional separation space of GC x GC. The quantitative determination of components in the essential oil was performed by GC x GC with flame ionization detection (FID), using a method of multiple internal standards calibration, (c) 2005 Elsevier B.V. All rights reserved.

Quantitative determination of compounds in tobacco essential oils by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry

A quantitative analysis of the individual compounds in tobacco essential oils is performed by comprehensive two-dimensional gas chromatography (GC x GC) combined with flame ionization detector (FID). A time-of-flight mass spectrometer (TOF/MS) was coupled to GC x GC for the identification of the resolved peaks. The response of a flame ionization detector to different compound classes was calibrated using multiple internal standards. In total, 172 compounds were identified with good match and 61 compounds with high probability value were reliably quantified. For comparative purposes, the essential oil sample was also quantified by one-dimensional gas chromatography-mass spectrometry (GC/MS) with multiple internal standards method. The results showed that there was close agreement between the two analysis methods when the peak purity and match quality in one-dimensional GC/MS are high enough. (c) 2005 Elsevier B.V. All rights reserved.

Separation and detection of compounds in Honeysuckle by integration of ion-exchange chromatography fractionation with reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis

A hyphenated method for the isolation and identification of components in a traditional Chinese medicine of Honeysuckle was developed. Ion-exchange chromatography (IEC) was chosen for the fractionation of Honeysuckle extract, and then followed by concentration of all the fractions with rotary vacuum evaporator. Each of the enriched fractions was then further analyzed by reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer (RPLC-APCI/MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) with matrix of oxidized carbon nanotubes, respectively. It can be noted totally more than 117 components were detected by UV detector, APCI/MS and MALDI-TOF/MS in Honeysuckle extract except the, 145 components identified by MALDI-TOF/MS alone with this integrated approach, and 7 of them were preliminary identified according to their UV spectra and mass spectra performed by APCI/MS and MALDI-TOF/MS, respectively. The obtained analytical results not only indicated the approach of integration IEC fractionation with RPLC-APCI/MS and MALDI-TOF/MS is capable of analyzing complex samples, but also exhibited the potential power of the mass spectrometer in detection of low-mass compounds, such as traditional Chinese medicines (TCMs) and complex biological samples. (c) 2005 Elsevier B.V. All rights reserved.