Development of a sensitive fluorescent derivatization reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) and its application for determination of amino acids from seeds and bryophyte plants using high-performance liquid chromatography with fluorescence detection and identification with electrospray ionization mass spectrometry

A pre-column derivatization method for the sensitive determination of amino acids and peptides using the tagging reagent 1,2-benzo-3,4dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives was carried out by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS/MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent BCEOC. BCEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. The derivatives showed an intense protonated molecular ion corresponding m/z (M + H)(+) under electrospray ionization (ESI) positive-ion mode with an exception being Tyr detected at negative mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 246.2 corresponding to the cleavage of C-O bond of BCEOC molecule. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3-4-fold molar reagent excess. Derivatives exhibit strong fluorescence and extracted detzvatization solution with n-hexane/ethyl acetate (10:1, v/v) allows for the direct injection with no significant interference from the major fluorescent reagent degradation by-products, such as 1,2-benzo-3,4-dihydrocarbazole-9-ethanol (BDC-OH) (a major by-product), mono- 1,2-benzo-3,4-dihydrocarbazole-9-ethyl carbonate (BCEOC-OH) and bis-(1,2-benzo-3,4-dihydrocarbazole-9-ethyl) carbonate (BCEOC)(2). In addition, the detection responses for BCEOC derivatives are compared to those obtained with previously synthesized 2-(9-carbazole)-ethyl chloroformate (CEOC) in our laboratory. The ratios AC(BCEOC)/AC(CEOC) = 2.05-6.51 for fluorescence responses are observed (here, AC is relative fluorescence response). Separation of the derivatized peptides and amino acids had been optimized on Hypersil BDS C-18 column. Detection limits were calculated from 1.0 pmol injection at a signal-to-noise ratio of 3, and were 6.3 (Lys)-177.6 (His) fmol. The mean interday accuracy ranged from 92 to 106% for fluorescence detection with mean %CV < 7.5. The mean interday precision for all standards was < 10% of the expected concentration. Excellent linear responses were observed with coefficients of > 0.9999. Good compositional data could be obtained from the analysis of derivatized protein hydrolysates containing as little as 50.5 ng of sample. Therefore, the facile BCEOC derivatization coupled with mass spectrometry allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids and peptides from biological and natural environmental samples. (c) 2005 Elsevier B.V. All rights reserved.

基于多特征模糊聚类的图像融合方法

首先利用模糊C-均值聚类算法在多特征形成的特征空间上对图像进行区域分割,并在此基础上对区域进行多尺度小波分解;然后利用柯西函数构造区域的模糊相似度,应用模糊相似度及区域信息量构造加权因子,从而得到融合图像的小波系数;最后利用小波逆变换得到融合图像·采用均方根误差、峰值信噪比、熵、交叉熵和互信息5种准则评价融合算法的性能·实验结果表明,文中方法具有良好的融合特性·

大港油田复杂断块油气藏评价技术研究与应用

In this paper, in view of characteristics and appraisal difficulty of complicate fault block reservoir, based on the theory of reservoir geology, tectonic geology, sequence stratigraphy, logging geology and sedimentology, according to related multidisciplinary data, such as geological, geophysical, logging and testing, taking 3D seismic acquisition processing, delicate structure interpretation, fine reservoir prediction, reservoir engineering and logging evaluation as research methods, on the basis of comprehensive geologic research, innovative appraisal thinking of complicate fault block reservoir is probed into, reservoir evaluation technology series of different reservoirs were created, and appraisal circuit of complicate fault block reservoir was proposed. According to the research on main controlling factors of hydrocarbon and concentration and concealing laws of Dagang exploration area, family assemble patterns of complicate fault block reservoir were proposed firstly, such as twinning, juxtaposed, overlying, concurrent, connected in series and so on, so theory basement was provided to reservoir evaluation. Taking into account of difficulties of low signal to noise ratio and border identification of lithologic trap of complicate fault block reservoir, in the middle of seismic data acquisition, double focusing layout and optimization technology were adopted, geophysical model was set up, and best observation system was ascertained. During object processing, matching processing technology of removing time difference, phase difference, energy difference and frequency spectrum difference generated by different blazing and receiving elements was studied. Imagery, low amplitude structure and identification of subtle lithologic reservoir was interpreted reasonably. On the basis of characteristics and technical description analysis of structural, structural--lithologic and lithologic reservoirs, innovative appraisal thinking of these reservoirs was formatted, appraisal circuit of complicate fault block reservoir was proposed, and this method could be used in other similar oilfields

AVO分析与地震资料叠前储层预测技术

In this paper we base on the anisotropic theory and Zoeppritz function of the transmission theory and the law of amplitude versus offset simplify seismic reflection coefficient of different media, analyze the characteristic of the gas or oil saturated stratum or the VTI and HTI models. Discuss the P wave reflection relationship and the meanings of the different parameters. We use measured parameters of a reservoir to simulate the characteristic of the reservoir, study the different effects of stratum saturated with gas or oil and analyze the characteristic of the seismic response of different models which change with different incident angles and different azimuths. Using the field data of logs ,analyze the rock property parameters, build the relationship of logs and parameters by Gassmann theory or empirical function. Calculate the density and the shear modulus and bulk modulus, reconstruct the log curves, calculate shear wave logs and correlate the logs affected by mud and other environmental factors. Finally perform the relationship of the seismic data log of saturated stratum and enhance the ability and reliability in reservoir prediction. Our aim is by the prestack seismic processing to get high solution and amplitude preserved seismic data. Because in incident angle gathers or azimuthal gathers, the low signal to noise ratio and low different covers affect the result of the prestack reservoir prediction. We apply prestack noise erase, cell regularization process and relatively amplitude preservation in the high solution seismic process routine to preserve the characteristic of stratum response, and erase the effects of the noise. In this paper we finished prestack invertion in the BYT survey and fractured reservoir depiction in MB survey. By the invertion and multiple attributes crossplot. we can get the stratum profiles and oil indicator profiles which can predict the distribution of the reservoir and oil. In the MB survey, we get orientation and density of fractured reservoir by the azimuthal seismic amplitude and depict the potential oil and gas reservoir. Prestak invertion works better in distinguishing oil and reservoir.

北部湾盆地迈陈凹陷地震勘探方法研究

Maichen Depression lie between Leizhou Peninsula and Qiongzhou Strait. Oil and gas have been discovered in Weixinan Depression, Wushi Depression and Fushan Depression, which pertain to a same basin — North Sea Basin along with Maichen Depression.Jiangsu Oil started exploration at 2002. The first well began to drill at November, 2004 after gravity survey, electric method prospecting and 2D seismic exploration had been finished. Generating rock and hydrocarbon shows have been verified by the drilling. Low yield oil stream has been tested. And we started 3D seismic exploration at November, 2005. My thesis topic came from the actual needs of our exploration in the Maichen Depression. In the thesis, I give emphasis to analyse the own seismic geologic conditions of Maichen Depression. By real tests, we choosed the means to overcome or weaken the unfavorably impress owing to the own coditions in Maichen Depression. Finally, we obtained the usable seismic data. 1. Owing to the multiphase eruptive rock during the Quaternary Period, the near surface layers are very inhomogeneous. By simultaneous testing at same point with short refraction, uphole surveys of radial source and of surface source, the most appropriate method had been sorted out. Radial source uphole survey has been regarding the best practicable means in the complex area. Accurate surficial geology was very helpful to choosing of acquirement means and parameters. Basically the appropriate method of seismic acquirement has been built at Maichen area. 2. The seismic primary data has many, very strong and complex noise. By noise characteristic analysis in different domain, many means of denoising had been paralleled individual and joint application researched. As a result, the pre-stack multidomain joint denoise flow was the appropriate method. It can improve the seismic signal-to-noise ratio. 3. The problem of seismic static correction at Maichen Depression is very conspicuous. Many static correction methods had been tested individual and joint researched. The seismic data quality has been improved after choosing the appropriate combination of static correction flows. 4. Although the above-mentioned process are resultful, the seismic profile quality is just passable. Some reflector continuity and fault zone imagery are ambiguity. So it was the useful method to reduce the structural ambiguity during seismic interpretation that built-up geologic model in accord with real geologic character by areal structure study upon backbone seismic profiles. In the same way, traps have been assessed and drill targets have been selected.

利用接收函数方位变化研究地壳各向异性

Because of its sensitivity to the velocity discontinuity of the earth, receiver function technique has become a routine procedure used to probe interior structure of the earth. Receiver functions contain anisotropic information of the earth’s interior, however, traditional receiver function techniques such as migration imaging and waveform inversion method, which are based on isotropic media assumption, can not effectively extract the anisotropy information contained in the azimuth variation pattern. Only by using the anisotropic media, e.g. a model with symmetric axis of arbitrary orientation, computing the response, can we obtain the detailed anisotropy information hidden in the radial and transversal receiver function. Focusing on the receiver function variation pattern changing wtih different back azimuths, we introduced different kinds of symmetric systems of seismic anisotropy used often, and summarized some possible causes of anisotropy formation. We show details about how to calculate the response of a stratified anisotropy model with symmetric axis of arbitrary orientation. We also simulated receiver functions among different models and analyzed how the changing of anisotropic parameters influence the azimuth variation pattern of receiver functions. The anisotropy study by receiver function analysis was applied to Taihang Mountain Range (TMR) in North China in this thesis. The maximum entropy spectrum deconvolution technique was used to extract radial and transversal receiver functions from the waveforms of 20 portable seismic stations deployed in TMR. Considering the signal-to-noise ratio and the azimuth coverage, we got the variation pattern of receiver functions for 11 stations. After carefully analyzing the pattern of the receiver functions that we got, we obtained the reliable evidence on the existence of anisotropy in the shallow crust in TMR. Our results show that, although the thickness of the upper crustal layer is only about 1 km, the layer shows a strong anisotropy with magnitude of 8~15%; in the deeper of crust, the magnitudes of anisotropy is about 3%~5%, showing a pattern with fast-symmetric-axis. The crust anisotropy beneath TMR in North China obtained in this study also shows a significant difference in both the lateral and vertical scale, which might imply a regional anisotropy characteristic in the studied region.

复杂地质条件下高精度地震勘探技术研究与应用-以泌阳凹陷为例

In order to carry out high-precision three-dimensional "integration" for the characteristics of the secondary seismic exploration for Biyang Depression, in the implementation process, through a combination of scientific research and production, summed up high-precision seismic acquisition, processing and interpretation technologies suitable for the eastern part of the old liberated areas, achieved the following results: 1. high-precision complex three-dimensional seismic exploration technology series suitable for shallow depression Biyang block group. To highlight the shallow seismic signal, apply goal-based observing system design, trail from the small panel to receive and protect the shallow treatment of a range of technologies; to explain the use of three-dimensional visualization and coherent combination of full-body three-dimensional fine interpretation identification of the 50-100 m below the unconformity surface and its formation of about 10 meters of the distribution of small faults and improve the small block and stratigraphic unconformity traps recognition. 2. high-precision series of three-dimensional seismic exploration technology suitable for deep depression Biyang low signal to noise ratio of information. Binding model using forward and lighting technology, wide-angle observation system covering the design, multiple suppression and raise the energy of deep seismic reflection processing and interpretation of detailed, comprehensive reservoir description, such as research and technology, identified a number of different types of traps. 3. high-precision seismic exploration technology series for the southern Biyang Depression high steep three-dimensional structure. The use of new technology of seismic wave scattering theory and high-precision velocity model based on pre-stack time migration and depth migration imaging of seismic data and other high-precision processing technology, in order to identify the southern steep slope of the local structure prediction and analysis of sandstone bedrock surface patterns provide a wealth of information.

隐伏金矿床预测中的地震勘探险方法

Based on brief introduction of seismic exploration and it's general developing situation, the seismic exploration method in field work implementation and some problems frequently encountered in field, which should be pay attention to, are analyzed in detail. The most economic field work techniques are emphasized. Then the seismic data processing flow and it's interpretation technique about the processing results are presented. At last four examples of seismic prospecting in gold deposits are showed. The main conclusions of our research are: 1. Seismic prospecting technique is a very efficient method in the prediction of concealed gold deposits. With appropriate application, it can absolutely reflect the detail underground geological structure in the condition of rugged area and complicated geological environment. 2. The field geometry should be designed and changed according to different kinds of objective exploration depth and ground situation. The best field implementing parameters which include offset, the distance between two adjacent traces, the quantity of dynamite and the depth of hole for explosion, should be determined with examination. Only this way, the high quality original seismic data can be gotten. 3. In seismic data processing, the edition of invalid trace and source gather, signal enhancement, velocity analysis and migration are the key steps. It has some different points with conventional processing and needs a new processing flow and methods which is suitable to the data acquired in rugged area and complicated geological environment. 4. The new common reflection area stacking method in crooked line data processing is an efficient method to improve the signal to noise ratio of seismic data The innovations of our research work are: 1. In the areas which were considered to be forbidden zone, we implement the seismic exploration in several gold deposits in China through our application. All acquire distinguished effects. This show the seismic exploration method is a new effective method in the prediction of concealed gold deposits. 2. We developed a set of seismic field work techniques and data processing which is suitable to complex environment, especially find a effective method in stacking and noise elimination in crooked line data processing. 3. In the field of seismic profile interpretation, through our research work, we are convinced of that: in different kinds of geological condition, the seismic reflection character are not same. For example the lava, the intrusion rock and sediment layers are different in the character of reflection structure and strength. So we accumulate some experience about seismic data interpretation in the area of gold deposits.

两种超微细矿物粉体材料的制备及应用研究

Superfine mineral materials are mainly resulted from the pulverization of natural mineral resources, and are a type of new materials that can replace traditional materials and enjoy the most extensive application and the highest degree of consumption in the present day market. As a result, superfine mineral materials have a very broad and promising prospect in terms of market potential. Superfine pulverization technology is the only way for the in-depth processing of most of the traditional materials, and is also one of the major means for which mineral materials can realize their application. China is rich in natural resources such as heavy calcite, kaolin, wollastonite, etc., which enjoy a very wide market of application in paper making, rubber, plastics, painting, coating, medicine, environment-friendly recycle paper and fine chemical industries, for example. However, because the processing of these resources is generally at the low level, economic benefit and scale for the processing of these resources have not been realized to their full potential even up to now. Big difference in product indices and superfine processing equipment and technologies between China and advanced western countries still exists. Based on resource assessment and market potential analysis, an in-depth study was carried out in this paper about the superfine pulverization technology and superfine pulverized mineral materials from the point of mineralogical features, determination of processing technologies, analytical methods and applications, by utilizing a variety of modern analytical methods in mineralogy, superfine pulverization technology, macromolecular chemistry, material science and physical chemistry together with computer technology and so on. The focus was placed on the innovative study about the in-depth processing technology and the processing apparatus for kaolin and heavy calcite as well as the application of superfine products. The main contents and the major achievements of this study are listed as follows: 1. Superfine pulverization processing of mineral materials shall be integrated with the study of their crystal structures and chemical composition. And special attention shall be put on the post-processing technologies, rather than on the indices for particle size, of these materials, based on their fields of application. Both technical feasibility and economic feasibility shall be taken into account for the study about superfine pulverization technologies, since these two kinds of feasibilities serve as the premise for the industrialized application of superfine pulverized mineral materials. Based on this principle, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in this study, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in this study. Heavy calcite and kaolin are two kinds of superfine mineral materials that enjoy the highest consumption in the industry. Heavy calcite is mainly applied in paper making, coating and plastics industries, the hard kaolin in northern China is mainly used in macromolecular materials and chemical industries, while the soft kaolin in southern China is mainly used for paper making. On the other hand, superfine pulverized heavy calcite and kaolin can both be used as the functional additives to cement, a kind of material that enjoys the biggest consumption in the world. A variety of analytical methods and instruments such as transmission and scanning electron microscopy, X-ray diffraction analysis, infrared analysis, laser particle size analysis and so on were applied for the elucidation of the properties and the mechanisms for the functions of superfine mineral materials as used in plastics and high-performance cement. Detection of superfine mineral materials is closely related to the post-processing and application of these materials. Traditional detection and analytical methods for superfine mineral materials include optical microscopy, infrared spectral analysis and a series of microbeam techniques such as transmission and scanning electron microscopy, X-ray diffraction analysis, and so on. In addition to these traditional methods, super-weak luminescent photon detection technology of high precision, high sensitivity and high signal to noise ratio was also utilized by the author for the first time in the study of superfine mineral materials, in an attempt to explore a completely new method and means for the study of the characterization of superfine materials. The experimental results are really exciting! The innovation of this study is represented in the following aspects: 1. In this study, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in an innovative way, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in the industrialized production process*. Moreover, a new modification technology and related directions for producing the chemicals were invented, and the modification technology was even awarded a patent. 2. The detection technology of super-weak luminescent photon of high precision, high sensitivity and high signal to noise ratio was utilized for the first time in this study to explore the superfine mineral materials, and the experimental results can be compared with those acquired with scanning electron microscopy and has demonstrated its unique advantages. It can be expected that further study may possibly help to result in a completely new method and means for the characterization of superfine materials. 3. During the heating of kaolinite and its decomposition into pianlinite, the diffraction peaks disappear gradually. First comes the disappearance of the reflection of the basal plane (001), and then comes the slow disappearance of the (hkl) diffraction peaks. And this was first discovered during the experiments by the author, and it has never before reported by other scholars. 4. The first discovery of the functions that superfine mineral materials can be used as dispersants in plastics, and the first discovery of the comprehensive functions that superfine mineral materials can also be used as activators, water-reducing agents and aggregates in high-performance cement were made in this study, together with a detailed discussion. This study was jointly supported by two key grants from Guangdong Province for Scientific and Technological Research in the 10th Five-year Plan Period (1,200,000 yuan for Preparation technology, apparatus and post-processing research by using sub-micron superfine pulverization machinery method, and 300,000 yuan for Method and instruments for biological photon technology in the characterization of nanometer materials), and two grants from Guangdong Province for 100 projects for scientific and technological innovation (700,000 yuan for Pilot experimentation of superfine and modified heavy calcite used in paper-making, rubber and plastics industry, and 400,000 yuan for Study of superfine, modified wollastonite of large length-to-diameter ratio).

Determination of alcohols by high-performance liquid chromatography with fluorimetric detection after pre-column derivatisation with carbazole-9-N-acetic acid and chromatographic behaviour of alcoholic derivatives

Alcohols were derivatised to their carbazole-9-N-acetic acid (CRA) esters with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC . HCl) as the dehydrating agent. Studies on derivatisation 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. The retention behaviour of alcohol derivatives was investigated by varying mobile phase compositions (ACN-water and MeOH-water). The parameters from the equation log k'=A-BX were evaluated by retention data of derivatives using an isocratic elution with different mobile phases. The results indicated that the parameters derived allowed computation of retention factors in good agreement with experiments. At the same time, a general equation was derived that makes possible predictions of partition coefficient in binary mobile phases with different proportions of organic solvent to water based on some simple regression analysis. The LC separation for the derivatised alcohols containing higher carbon alcohols showed good reproducibility on a reversed-phase C-18 column with gradient elution. The detection limits (excitation at 335 nm, emission at 360 nm) for derivatised alcohols (signal-to-noise ratio=3:1) were in the range of 0.1-0.4 pg per injection. (C) 2001 Elsevier Science B.V. All rights reserved.

On-line concentration of proteins in pressurized capillary electrochromatography coupled with electrospray ionization-mass spectrometry

Pressurized capillary electrochromatography (pCEC) and electrospray ionization-mass spectrometry (ESI-MS) have been hyphenated for protein analysis. Taken cytochrome c, lysozyme, and insulin as samples, the limits of detection (LODs) for absolute concentrations are 10(-11) mol (signal-to-noise ratio S/N = 3) with relative standard deviations (RSDs) of retention time and peak area, respectively, of less than 1.7% and 4.8%. In order to improve the detection sensitivity, on-line concentration by field-enhanced sample-stacking effect and chromatographic zone-sharpening effect has been developed, and parameters affecting separation and detection, such as pH and electrolyte concentration in the mobile phase, separation voltage, as well as enrichment voltage and time, have been studied systematically. Under the optimized conditions, the LODs of the three proteins could be decreased up to 100-fold. In addition, the feasibility of such techniques has been further demonstrated by the analysis of modified insulins at a concentration of 20 mu g/mL.

A collinear light-emitting diode-induced fluorescence detector for capillary electrophoresis

A novel fluorescence detector based on collinear scheme using a brightness light-emitting diode emitting at 470 nm as excitation source is described. The detector is assembled by all-solid-state optical-electronic components and Coupled with capillary electrophoresis using on-column detection mode. Fluorescein isothiocyanate (FITC) and FITC-labeled amino acids and small molecule peptide as test analyte were used to evaluate the detector. The concentration limit of detection for FITC-labeled phenylalanine was 10 nM at a signal-to-noise ratio (S/N) of 3. The system exhibited good linear responses in the range of 1 x 10(-7) to 2 x 10(-5) M (R-2 = 0.999). (c) 2004 Elsevier B.V. All rights reserved.

一种制作掺Yb相移光纤光栅激光器的实验方案

采用遮挡法引入相移制作了掺Yb相移光纤光栅(PS-FBG)。在制作光栅的过程中,将其作为激光器的谐振腔,通过监测激光器的输出功率来确定相移大小。当激光器的输出功率开始下降时,停止曝光,此时引入的相移为π/2。为了使光栅的特性尽快稳定下来需要对光栅进行退火,这将导致引入的相移小于π/2。为了弥补退火过程中引起的相移降低,需要对退火后的光栅进行二次曝光,以使光栅的相移恢复π/2。利用该方法制作了一只光纤光栅激光器。当抽运功率为100 mW时,获得了25 mW的输出功率,信噪比(SNR)为60 dB。在1 h内

Complex Transition of Double-Diffusive Convection in a Rectangular Enclosure with Height-to-Length Ratio Equal to 4: Part I

This is the first part of direct numerical simulation (DNS) of double-diffusive convection in a slim rectangular enclosure with horizontal temperature and concentration gradients. We consider the case with the thermal Rayleigh number of 10^5, the Pradtle number of 1, the Lewis number of 2, the buoyancy ratio of composition to temperature being in the range of [0,1], and height-to-width aspect ration of 4. A new 7th order upwind compact scheme was developed for approximation of convective terms, and a three-stage third-order Runge-Kutta method was employed for time advancement. Our DNS suggests that with the buoyancy ratio increasing form 0 to 1, the flow of transition is a complex series changing fromthe steady to periodic, chaotic, periodic, quasi-periodic, and finally back to periodic. There are two types of periodic flow, one is simple periodic flow with single fundamental frequency (FF), and another is complex periodic flow with multiple FFs. This process is illustrated by using time-velocity histories, Fourier frequency spectrum analysis and the phase-space rajectories.

Resolution and noise in ghost imaging with classical thermal light

The resolution and classical noise in ghost imaging with a classical thermal light are investigated theoretically. For ghost imaging with a Gaussian Schell model source, the dependences of the resolution and noise on the spatial coherence of the source and the aperture in the imaging system are discussed and demonstrated by using numerical simulations. The results show that an incoherent source and a large aperture will lead to a good image quality and small noise.