Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and its application for determination of amines by high performance liquid chromatography with fluorescence detection and identification with mass spectroscopy/atmospheric pressure chemical ionization

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC-HCI) as the dehydrant with fluorescence detection has been developed. Amines were derivatized to their acidamides with labeling reagent 2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA). Studies on derivatization conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum at lambda(ex) 260nm and an emission maximum at lambda(em) 380nm. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by high-performance liquid chromatography. Identification of derivatives was carried out by online post-column mass spectrometry (LC/APCI-MS/MS) and showed an intense protonated molecular ion corresponding m/z [MH](+) under APCI in positive-ion mode. At the same time, the fluorescence properties of derivatives in various solvents or at different temperature were investigated. The method, in conjunction with a gradient elution, offered a baseline resolution of the common amine derivatives on a reversed-phase Eclipse XDB-C-8 column. LC separation for the derivatized amines showed good reproducibility with acetonitrile-water as mobile phase. Detection limits calculated from 0.78 pmol injection, at a signal-to-noise ratio of 3, were 3.1-18.2 fmol. The mean intra- and inter-assay precision for all amine levels were < 3.85% and 2.11%, respectively. Excellent linear responses were observed with coefficients of > 0.9996. The established method for the determination of aliphatic amines from real wastewater and biological samples was satisfactory. (c) 2006 Elsevier B.V. All rights reserved.

复杂条件地层滤波预测的理论与关键技术研究

The theory researches of prediction about stratigraphic filtering in complex condition are carried out, and three key techniques are put forward in this dissertation. Theoretical aspects: The prediction equations for both slant incidence in horizontally layered medium and that in laterally variant velocity medium are expressed appropriately. Solving the equations, the linear prediction operator of overlaid layers, then corresponding reflection/transmission operators, can be obtained. The properties of linear prediction operator are elucidated followed by putting forward the event model for generalized Goupillaud layers. Key technique 1: Spectral factorization is introduced to solve the prediction equations in complex condition and numerical results are illustrated. Key technique 2: So-called large-step wavefield extrapolation of one-way wave under laterally variant velocity circumstance is studied. Based on Lie algebraic integral and structure preserving algorithm, large-step wavefield depth extrapolation scheme is set forth. In this method, the complex phase of wavefield extrapolation operator’s symbol is expressed as a linear combination of wavenumbers with the coefficients of this linear combination in the form of the integral of interval velocity and its derivatives over depth. The exponential transform of the complex phase is implemented through phase shifting, BCH splitting and orthogonal polynomial expansion. The results of numerical test show that large-step scheme takes on a great number of advantages as low accumulating error, cheapness, well adaptability to laterally variant velocity, small dispersive, etc. Key technique 3: Utilizing large-step wavefield extrapolation scheme and based on the idea of local harmonic decomposition, the technique generating angle gathers for 2D case is generalized to 3D case so as to solve the problems generating and storing 3D prestack angle gathers. Shot domain parallel scheme is adopted by which main duty for servant-nodes is to compute trigonometric expansion coefficients, while that for host-node is to reclaim them with which object-oriented angle gathers yield. In theoretical research, many efforts have been made in probing into the traits of uncertainties within macro-dynamic procedures.

积分偏移的计算几何与并行实现

The Second Round of Oil & Gas Exploration needs more precision imaging method, velocity vs. depth model and geometry description on Complicated Geological Mass. Prestack time migration on inhomogeneous media was the technical basic of velocity analysis, prestack time migration on Rugged surface, angle gather and multi-domain noise suppression. In order to realize this technique, several critical technical problems need to be solved, such as parallel computation, velocity algorithm on ununiform grid and visualization. The key problem is organic combination theories of migration and computational geometry. Based on technical problems of 3-D prestack time migration existing in inhomogeneous media and requirements from nonuniform grid, parallel process and visualization, the thesis was studied systematically on three aspects: Infrastructure of velocity varies laterally Green function traveltime computation on ununiform grid, parallel computational of kirchhoff integral migration and 3D visualization, by combining integral migration theory and Computational Geometry. The results will provide powerful technical support to the implement of prestack time migration and convenient compute infrastructure of wave number domain simulation in inhomogeneous media. The main results were obtained as follows: 1. Symbol of one way wave Lie algebra integral, phase and green function traveltime expressions were analyzed, and simple 2-D expression of Lie algebra integral symbol phase and green function traveltime in time domain were given in inhomogeneous media by using pseudo-differential operators’ exponential map and Lie group algorithm preserving geometry structure. Infrastructure calculation of five parts, including derivative, commutating operator, Lie algebra root tree, exponential map root tree and traveltime coefficients , was brought forward when calculating asymmetry traveltime equation containing lateral differential in 3-D by this method. 2. By studying the infrastructure calculation of asymmetry traveltime in 3-D based on lateral velocity differential and combining computational geometry, a method to build velocity library and interpolate on velocity library using triangulate was obtained, which fit traveltime calculate requirements of parallel time migration and velocity estimate. 3. Combining velocity library triangulate and computational geometry, a structure which was convenient to calculate differential in horizontal, commutating operator and integral in vertical was built. Furthermore, recursive algorithm, for calculating architecture on lie algebra integral and exponential map root tree (Magnus in Math), was build and asymmetry traveltime based on lateral differential algorithm was also realized. 4. Based on graph theory and computational geometry, a minimum cycle method to decompose area into polygon blocks, which can be used as topological representation of migration result was proposed, which provided a practical method to block representation and research to migration interpretation results. 5. Based on MPI library, a process of bringing parallel migration algorithm at arbitrary sequence traces into practical was realized by using asymmetry traveltime based on lateral differential calculation and Kirchhoff integral method. 6. Visualization of geological data and seismic data were studied by the tools of OpenGL and Open Inventor, based on computational geometry theory, and a 3D visualize system on seismic imaging data was designed.

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.

内蒙古龙头山Ag-Pb-Zn多金属矿床成矿模式及找矿模型

The recent years research indicated that middle-south section of Da Hinggan Mountains metallogenic belt has two periods(Hercynian and Yanshanian) characteristics of metallogenesis, as well as the most of ore deposits in the area closely relate to Permian strata. Longtoushan ore deposit discovered in 2004 is an Ag-Pb-Zn polymetallic ore deposit born in Permian and located in the east hillside of the metallogenic belt, which has considerable resources potentials. It has important research value for its good metallogenic location and blank research history. Base on the detail field geology studies, the geology characteristics of "two stages and three kinds of metallogensis" has established. According to further work through geochemistry research including trace element, REE, S, Pb and Sr isotope, as well as petrography, microtemperature measurement, Laser Raman analysis and thermodynamics calculation of fluid inclusion, origin and characteristic of the ore-forming material and fluid has been discussed. And a new technology of single pellet Rb-Sr isochrones has been tried for dating its born time. Bae on above work, study of ore deposit comparison has been carried out, and metallogesis controlling factor and geological prospecting symbol have been summarized. Finally, metallogenic model and prospecting model have been established. According to above, the next step work direction has been proposed. Main achievement of the paper are listed as follow: 1.Longtoushan ore deposit has experienced two metallogenic periods including hot-water sedimentation period and hydrothermal reformation period. There are three kinds of metallizing phase: bedded(or near-bedded) phase, vein-shaped phase and pipe-shaped phase. The mian metallogenic period is hot-water sedimentation period. 2.Ore deposit geochemistry research indicated that the metal sulfides have charcateristic of hot-water sedimentation metallogensis, but generally suffered later hydrothermal transformation. The barite mineral isotope content is homogenous, showing the seabed hot-water sedimentation origin characteristic. Wall rock, such as tuff is one of metallogenic material origins. Both of Pb model age and Rb-Sr isochrone research older age value than that of strata, possibly for been influenced by hydrothermal transformation, and interfusion of ancient basis material. 3.There are two kinds of main metallogenic fluid inclusion in barite of the Longtoushan ore deposit, which are rich gas phase( C type) and liquid phase (D type). Their size is 2～7um, and principal components is H2O. Both kinds of fluid inclusion have freezing point temperature -7.1～-2.4℃ and -5.5～-0.3℃, salinity 4.0～10.6wt% and 0.5～8.5wt%, homogeneous temperature 176.8～361.6℃ and 101.4～279.9℃, which peak value around 270℃ and 170℃, respectively. Density of the ore-forming fluid is 0.73～0.97g/cm3, and metallogenic pressure is 62.3×105～377.9×105Pa. Above characteristic of the fluid inclusion are well geared to that of ore deposit originated in seabed hot-water sedimentation. 4.Through the comparison research, that Longtoushan ore deposit has main characteristic of hot-water sedimentation ore deposit has been indicated. Ore-forming control factor and prospecting symbol of it has been summarized, as well as metallogenic model and prospecting model. Next step work direction about prospecting has also been proposed finally.

人口统计信息空间可视化系统研究

Population research is a front area concerned by domestic and overseas, especially its researches on its spatial visualization and its geo-visualization system design, which provides a sound base for understanding and analysis of the regional difference in population distribution and its spatial rules. With the development of GIS, the theory of geo-visualization more and more plays an important role in many research fields, especially in population information visualization, and has been made the big achievements recently. Nevertheless, the current research is less attention paid to the system design for statistical-geo visualization for population information. This paper tries to explore the design theories and methodologies for statistical-geo-visualization system for population information. The researches are mainly focused on the framework, the methodologies and techniques for the system design and construction. The purpose of the research is developed a platform for population atlas by the integration of the former owned copy software of the research group in statistical mapping system. As a modern tool, the system will provide a spatial visual environment for user to analyze the characteristics of population distribution and differentiate the interrelations of the population components. Firstly, the paper discusses the essentiality of geo-visualization for population information and brings forward the key issue in statistical-geo visualization system design based on the analysis of inland and international trends. Secondly, the geo-visualization system for population design, including its structure, functionality, module, user interface design, is studied based on the concepts of theory and technology of geo-visualization. The system design is proposed and further divided into three parts: support layer, technical layer, user layer. The support layer is a basic operation module and main part of the system. The technical layer is a core part of the system, supported by database and function modules. The database module mainly include the integrated population database (comprises spatial data, attribute data and geographical features information), the cartographic symbol library, the color library, the statistical analysis model. The function module of the system consists of thematic map maker component, statistical graph maker component, database management component and statistical analysis component. The user layer is an integrated platform, which provides the functions to design and implement a visual interface for user to query, analysis and management the statistic data and the electronic map. Based on the above, China's E-atlas for population was designed and developed by the integration of the national fifth census data with 1:400 million scaled spatial data. The atlas illustrates the actual development level of the population nowadays in China by about 200 thematic maps relating with 10 map categories(environment, population distribution, sex and age, immigration, nation, family and marriage, birth, education, employment, house). As a scientific reference tool, China's E-atlas for population has already received the high evaluation after published in early 2005. Finally, the paper makes the deep analysis of the sex ratio in China, to show how to use the functions of the system to analyze the specific population problem and how to make the data mining. The analysis results showed that: 1. The sex ratio has been increased in many regions after fourth census in 1990 except the cities in the east region, and the high sex ratio is highly located in hilly and low mountain areas where with the high illiteracy rate and the high poor rate; 2. The statistical-geo visualization system is a powerful tool to handle population information, which can be used to reflect the regional differences and the regional variations of population in China and indicate the interrelations of the population with other environment factors. Although the author tries to bring up a integrate design frame of the statistical-geo visualization system, there are still many problems needed to be resolved with the development of geo-visualization studies.

Synthesis of chiral 3-acylcamphors

3-Acylcamphors were synthesized in moderate yields by the condensation of camphor with esters using sodium hydride as a base.

运用神经网络完成汉字句子的格角色分配

According to PDP theory, the author tries to use ANN method in sentence understanding. In input layer, distributed knowledge representation and integrate syntactic, semantic information (of the word in Chinese sentence) and context information are used to complete the case role assignment of six types of Chinese sentence by parallel processing. The model is a four-layer forward network, consisting of input layer, two hidden layers, and output layer(case role layer). In addition, the neural network method and the traditional symbol processing method used in natural language understanding is compared and analyzed, and a conclusion could be made: the neural network should be used as a powerful tool in this area.

Acid catalyzed synthesis of ordered bifunctionalized mesoporous organosilicas with large pore

Thiol-functionalized mesoporous ethane-silicas with large pore were synthesized by co-condensation of 1,2-bis(trimethoxy-sily)ethane (BTME) with 3-mercaptopropyltrimethoxysilane (MPTMS) using nonionic oligomeric polymer C1H (OCH(2)-CH(2))(10)OH (Brij-76) or poly(alkylene oxide) block copolymer (P123) as surfactant in acidic medium. The results of powder X-ray diffraction (XRD), nitrogen gas adsorption, and transmission electron microscopy (TEM) show that the resultant materials have well-ordered hexagonal mesoscopic structure with uniform pore size distributions. (29)Si MAS NNR, (13)C CP-MAS NMR. FT-IR, and UV Raman spectroscopies confirm the attachment of thiol functionalities in the mesoporous ethane-sificas. The maximum content of the attached thiol group (-SH) in the mesoporous framework is 2.48mmol/g. The ordered mesoporous materials are efficient Hg(2+) adsorbents with almost every -SH site accessible to Hg(2+). In the presence of various kinds of heavy metal ions such as Hg(2+), Cd(2+), Zn(2+), Cu(2+) and Cr(3+), the materials synthesized using poly(alkylene oxide) block cooollxmier (Pluronic 123) g(2+), as surfactant show almost similar affinity to Hg(2+), Cd(2+), and Cr(3+), while the materials synthesized using ofigomeric polymer C(18)H(37)(OCH(2)CH(2))(10)OH (Brij-76) as surfactant exhibit high selectivity to Hg(2+). (C) 2004 Elsevier Inc. All rights reserved.

Hybrid organic-inorganic phenyl monolithic column for capillary electrochromatography

A novel hybrid organic-inorganic silica-based monolithic column possessing phenyl ligands for reversed-phase (RP) capillary electrochromatography (CEC) is described. The monolithic stationary phase was prepared by in situ co-condensation of tetraethoxysilane (TEOS) with phenyltriethoxysilane (PTES) via a two-step catalytic sol-gel procedure to introduce phenyl groups distributed throughout the silica matrix for chromatographic interaction. The hydrolysis and condensation reactions of precursors were chemically controlled through pH variation by adding hydrochloric acid and dodecylamine, respectively. The structural property of the monolithic column can be easily tailored through adjusting the composition of starting sol solution. The effect of PTES/TEOS ratios on the morphology of the created stationary phases was investigated. A variety of neutral and basic analytes were used to evaluate the column performance. The CEC columns exhibited typical RP chromatographic retention mechanism for neutral compounds and had improved peak shape for basic solutes.

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyi)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO3H) by hydrogen peroxide (30 wt % H2O2). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH2CH2-concentrations in the mesoporous framework. The resultant materials were also investigated by Si-29 MAS and C-13 CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO3H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.

Catalytic steam reforming of ethanol to produce hydrogen and acetone

Steam reforming of ethanol over CuO/CeO2 was studied. Acetaldehyde and hydrogen were mainly produced at 260degreesC. At 380degreesC, acetone was the main product, and 2 mol of hydrogen was produced from 1 mol of ethanol. The formation of hydrogen accompanied by the production of acetone was considered to proceed through the following, consecutive reactions: dehydrogenation of ethanol to acetaldehyde. aldol condensation of the acetaldehyde, and the reaction of the aldol with the lattice oxygen [O(s)] on the catalyst to form a surface intermediate, followed by its dehydrogenation and decarboxylation. The overall reaction was expressed by2C(2)H(5)OH + H2O --> CH3COCH3 + CO2 + 4H(2). Ceria played an important role as an oxygen supplier. The addition of MgO to CuO/CeO2 resulted in the production of hydrogen at lower temperatures by accelerating aldol condensation. (C) 2004 Elsevier B.V. All rights reserved.