Determination of tetrodotoxin by liquid chromatography coupled with electrospray ion-trap mass spectrometry

Two methods for tetrodotoxin analysis using liquid chromatography coupled with electrospray iontrap mass spectrometry (LC-ESI-MS) have been established with C,, reversed phase column and hydrophilic interaction liquid chromatography (HILIC) column, respectively. Sensitivity and reproducibility of the methods were compared. The method using C-18 column in selected ion monitoring (SIM) mode had a detection limit (S/N = 3) of 120 pg, and a good linearity of the calibration curve was obtained for tetrodotoxin (r = 0. 9992). High reproducibility of the method was observed, with a relative standard deviation (RSD) below 10%. The method using HILIC column in SIM mode and selected reaction monitoring (SRM) mode had detection limits (S/N = 3) of 15 and 3.75 pg, respectively. Good linearity of the calibration curves was obtained for tetrodotoxin (r = 0. 9996 and 0. 9998 in SIM and SRM mode, respectively). T he reproducibility was high in SIM mode but relatively poor in SRM mode. Based on the results, the method using HILIC column in SIM mode was suggested for the analysis of tetrodotoxin with LC-MS system.

Speciation Analysis of Organotin Compounds in Shellfish by Hyphenated Technique of High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry(HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds in the shellfish samples. Agilent TC-C-18 column was selected, mobile phase of the HPLC was CH3CN:H2O: CH3COOH = 65:23:12 (V/V), 0. 05% TEA, pH = 3.0 at flow rate 0.4 mL/min. Five mixed organotin standards from 100 mu g/L to 0. 5 mu g/L was used for the method evaluation. The experimental results indicate that the linearity (R-2) for each compound was over 0.998. The shellfish samples were treated by supersonic extraction with mobile phase for 30min. Four organotin compounds including dibutyltin (DBT), tributyltin (TBT), diphenyltin (DphT) and triphenyltin (TPhT) in shellfish samples were detected with method mentioned above. It was found that the domain compounds in the samples were tributyltin (TBT) and triphenyltin (TPhT). The recoveries test from the standard addition for trimethyltin (TMT tributyltin (TBT), and triphenyltin (TPhT) were, over 80%. However, the recoveries for diphenyltin (DPhT) and dibutyltin (DBT) were relatively low, 37.3% and 75.2% respectively. The reason might be attributed to the decomposition of those compounds during the extraction procedure. The further study on this subject is under the progress.

Analysis for Flavonoids in Bee Pollens by Capillary Electrophoresis

A capillary electrophoresis (CE) method has been developed for the determination of six bioactive flavonoids that are commonly found in health foods: hesperidin, hyperin, isorhamnetin, kaempferol, quercetin and rutin. The effects of several parameters, such as pH, buffer concentration, separation voltage and UV detector wavelength, were investigated to find the optimal conditions. Using a HbBCh-NaiB-iO? buffer (pH 9.2), the analytes can be separated within 8 min. The relative standard deviations of migration times in eight injections were between 0.77% and 0.93%, and those of the peak areas ranged from 3.8% to 8.6%. A high reproducibility and excellent linearity was observed over two orders of magnitude, with detection limits (S/N = 3) ranging from 0.34ug ml to 2.9ug ml for all the six analytes. Recoveries ranged from 80.4 % to 113.9 %. The new method is simple, reproducible and sensitive. No solid phase extraction for sample pretreatment is necessary. Analysis results are accurate in application to bee pollens.

HPLC-APCI-MS determination of free fatty acids in Tibet folk medicine Lomatogonium rotatum with fluorescence detection and mass spectrometric identification

A simple and sensitive method for the determination of free fatty acids (FFAs) using acridone-9-ethyl-p-toluenesulfonate (AETS) as a fluorescence derivatization reagent by high performance liquid chromatography (HPLC) has been developed. Free fatty acid derivatives were separated on an Eclipse XDB-C-8 column with a good baseline resolution and detected with the fluorescence of which excitation and emission wavelengths of derivatives were set at lambda(ex) 404 and lambda(em) 440 nm, respectively. Identification of 19 fatty acid derivatives was carried out by online post-column mass spectrometry with an atmospheric pressure chemical ionization (APCI) source under positive-ion detection mode. Nineteen FFAs from the extract of Lomatogonium rotatum are sensitively determined. The results indicate that the plant Lomatogonium rotatum is enriched with an abundance of FFAs and FFAs of higher contents, which mainly focus on even carbon atoms, C-14, C-16, and C-18. The validation of the method including linearity, repeatability, and detection limits was examined. Most linear correlation coefficients for fatty acid derivatives are > 0.9989, and detection limits (at signal-to-noise of 3: 1) are 12.3-43.7 fmol. The relative standard deviations (RSDs) of the peak areas and retention times for 19 FFAs standards are < 2.24% and 0.45%, respectively. The established method is rapid and reproducible for the separation determination of FFAs from the extract of Lomatogonium rotatum with satisfactory results.

Determination of five pharmacologically active compounds extracted from Rhodiola for natural product drug discovery with HPLC-APCI-MS

A rapid and sensitive liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS) assay for the determination of five pharmacologically active compounds (PAC) extracted from the traditional Chinese medicine, Rhodiola , namely salidroside, tyrosol, rhodionin, gallic acid, and ethyl gallate has been developed. In this method, PAC could be baseline separated and detected with DAD at 275 nm. The validation of the method, including sensitivity, linearity, repeatability, and recovery, was examined. The linear calibration curves were acquired with correlation coefficient >0.999 and the limits of detection LOD (at a signal-to-noise ratio=3:1) were between 0.058 and 1.500 mu mol/L. It was found, that the amounts of PAC varied with different species of Rhodiola . The established method is rapid and reproducible for the separation of five natural pharmacologically active compounds from extracts of Rhodiola with satisfactory results.

基于非线性修正的多线阵像机的空间定位

介绍了一种基于多线阵像机构成的视觉空间定位系统.该系统利用线阵像机的快速性与高分辨率的特点,采用了非平行空间投影面相交定位的基本原理,利用几何投影关系定位求解的方法,实现了多线阵像机视觉系统的空间定位.并提出了多线阵像机的神经网络非线性修正方法,使修正后的PSD能在较宽的位置范围内输出高线性度的信号.实验结果表明,基于非线性修正的多线阵像机位姿测量系统简化了立体视觉空间定位计算的复杂性,在定位精度、定位范围和采样速度上均达到了良好效果.

PSD空间定位的非线性误差补偿模型及归一化

PSD是一种高分辨率、实时性好的光电位置敏感器件,因而具有广泛应用的前景.但在光照度变化条件下,输出信号存在非线性飘移,因而影响了作为位置检测传感器的检测精度,尤其在3D测量时适用性受到了限制.针对这个问题,提出了一种PSD位置传感器的非线性误差补偿方法.该方法针对目标的空间距离变化所产生的PSD输出非线性飘移,采用归一化模型进行误差修正,很大程度上改进了PSD的输出一致性,使基于PSD的3D测量系统性能得以提高.

三柔索吊床机构设计与运动学分析

研制了一种有重力约束的三索控制的柔索吊床机构来模拟船体海面上的运动。为了解三柔索吊床机构的运动特性 ,对其进行了运动学建模与仿真。仿真结果表明 ,台面倾角在 0°～ 30 0°变化时 ,台面不碰撞立柱 ,且柔索伸缩长度与台面倾斜角度接近于线性变化。本文所做的工作对吊床平台避免撞击立柱、缩小吊床立柱布置空间、提高空间利用率 ,以及为吊床的运动控制提供了理论依据

有缆水下机器人主动升沉补偿控制研究

针对母船的升沉运动影响有缆水下机器人的释放与回收的工程实际需求,提出了利用液压绞车降低中继器的升沉速度来实现水下机器人主动升沉补偿控制的方法,来提高水下机器人释放与回收的安全性能。建立液压绞车的数学模型并设计主动升沉补偿前馈控制器。水下机器人主动升沉补偿实验表明液压系统的非线性降低了液压绞车主动升沉补偿前馈控制的升沉补偿效率。针对液压绞车的非线性特性,设计了液压绞车主动升沉补偿预测控制算法,仿真实验表明基于液压系统参数辨识的液压绞车主动升沉补偿预测控制可以得到较高的升沉补偿效率。

谐波驱动系统的特性及控制策略研究

谐波传动有很多优点，在机器人驱动中经常被使用．但谐波传动也有一些缺点，如柔性等因素影响负载端轨迹跟踪精度．本文系统地分析了谐波传动系统的动力学特性，建立了包括电机转子惯量在内的动力学模型，疽对系统进行全面实验研究的基础上总结出谐波传动系统中存在的问题，采用相应的基于传感器的控制策略克服存在的问题，提高系统的响应性能．从理论分析和实验结果证实了提出方法的可行性。

基于三坐标测量机激光拼焊板材直线度研究

利用高精度三坐标测量机扫描功能,充分获得焊接板材端面线性三维数据坐标值,采用基于最小二乘法而建立的理想直线数学模型来评定直线度误差,并与实际采用塞尺法进行对比,结果发现采用三坐标测量更能详尽地反应整个焊接边缘直线度真实情况,节省大量的数据处理时间,且数据更加准确可靠,并在实际激光焊接中获得良好激光焊缝,同时直观地给出了焊接板材边缘线性特征,为剪板机刀具调整提供了方向与位置。

黄土高原中部60万年来黄土—古土壤序列有机碳同位素研究

Vegetation is very sensitive to climate change. Carbon isotopes in paleosol have been widely used to contruct the propotion of plants using C3 and C4 photosynthetic pathways. δ13C of Loess organic matter were analyzed on the loess- paleosols samples from Jingchuan sections and Luochuan S4—S5 sequence. This paper presents a long carbon isotope time series, covering the last 600kyr. δ13C record of Loess organic matter in Jingchuan is correlated with marine oxygen isotope records. Basing on former research work, this paper discusses temperature, rainfall and P CO2 effect on δ13Corg value. In the interglacial periods, carbon isotope is more sensitive than other proxies and indicates several climate fluctuations. The main conclusions are as follows: 1. Obtained δ13C composition from paleosols and loess sediments in Jingchuan range of -20.0‰ to -24.6‰, the maximum biomass of C4 is 35%, indicating a C3 and C4 mixed steppe with C3 dominated. C4 plant is not always expansion during paleosols periods. The minimum values of Jingchuan section appeared in S4 soil, and the vegetation was almost pure C3 plant at that time. δ13Corg value in S5-2 is also lower than loess in S5, reaching the minimum valus of S5 soil. 2. PCO2 variation has little impact on δ13Corg value in interglacial periods for the last 600kyr. The correlation between δ13Corg value curve and magnetic susceptibility curve as proxy of summer monsoon in general, means summer monsoon drive C4 plant expansion during glacial and interglacial. 3. The lowerδ13Corg values in S4 and S5-2 appear at Jingchuan and Luochuan, suggest origin from woodland or C3 grassland. Whatever vegetation it is, indicate strengthened East Asian summer monsoon and increase of precipitation. C4 plant percentage is lower in S5-1 and S1 which have stronger summer monsoon, than S0 and S2. And it also indicates increase of precipitation.δ13Corg values has not always non-linearity correlation with summer monsoon. 4. The maximum entroy spectral analysis of δ13C values of the last 600kyr indicates there is 21 kyr cycles in Loess sequence. It means that summer monsoon in the Chinese Loess Plateau also has the precession cycles like its origin low latitude.

超参数控制下的波阻抗约束反演

The seismic survey is the most effective geophysical method during exploration and development of oil/gas. As a main means in processing and interpreting seismic data, impedance inversion takes up a special position in seismic survey. This is because the impedance parameter is a ligament which connects seismic data with well-logging and geological information, while it is also essential in predicting reservoir properties and sand-body. In fact, the result of traditional impedance inversion is not ideal. This is because the mathematical inverse problem of impedance is poor-pose so that the inverse result has instability and multi-result, so it is necessary to introduce regularization. Most simple regularizations are presented in existent literature, there is a premise that the image(or model) is globally smooth. In fact, as an actual geological model, it not only has made of smooth region but also be separated by the obvious edge, the edge is very important attribute of geological model. It's difficult to preserve these characteristics of the model and to avoid an edge too smooth to clear. Thereby, in this paper, we propose a impedance inverse method controlled by hyperparameters with edge-preserving regularization, the inverse convergence speed and result would be improved. In order to preserve the edge, the potential function of regularization should satisfy nine conditions such as basic assumptions edge preservation and convergence assumptions etc. Eventually, a model with clear background and edge-abnormity can be acquired. The several potential functions and the corresponding weight functions are presented in this paper. The potential functionφLφHL andφGM can meet the need of inverse precision by calculating the models. For the local constant planar and quadric models, we respectively present the neighborhood system of Markov random field corresponding to the regularization term. We linearity nonlinear regularization by using half-quadratic regularization, it not only preserve the edge, and but also simplify the inversion, and can use some linear methods. We introduced two regularization parameters (or hyperparameters) λ2 and δ in the regularization term. λ2 is used to balance the influence between the data term and the transcendental term; δ is a calibrating parameter used to adjust the gradient value at the discontinuous position(or formation interface). Meanwhile, in the inverse procedure, it is important to select the initial value of hyperparameters and to change hyperparameters, these will then have influence on convergence speed and inverse effect. In this paper, we roughly give the initial value of hyperparameters by using a trend- curve of φ-(λ2, δ) and by a method of calculating the upper limit value of hyperparameters. At one time, we change hyperparameters by using a certain coefficient or Maximum Likelihood method, this can be simultaneously fulfilled with the inverse procedure. Actually, we used the Fast Simulated Annealing algorithm in the inverse procedure. This method overcame restrictions from the local extremum without depending on the initial value, and got a global optimal result. Meanwhile, we expound in detail the convergence condition of FSA, the metropolis receiving probability form Metropolis-Hasting, the thermal procession based on the Gibbs sample and other methods integrated with FSA. These content can help us to understand and improve FSA. Through calculating in the theoretic model and applying it to the field data, it is proved that the impedance inverse method in this paper has the advantage of high precision practicability and obvious effect.

电阻率测井反演方法应用研究

Formation resistivity is one of the most important parameters to be evaluated in the evaluation of reservoir. In order to acquire the true value of virginal formation, various types of resistivity logging tools have been developed. However, with the increment of the proved reserves, the thickness of interest pay zone is becoming thinner and thinner, especially in the terrestrial deposit oilfield, so that electrical logging tools, limited by the contradictory requirements of resolution and investigation depth of this kinds of tools, can not provide the true value of the formation resistivity. Therefore, resitivity inversion techniques have been popular in the determination of true formation resistivity based on the improving logging data from new tools. In geophysical inverse problems, non-unique solution is inevitable due to the noisy data and deficient measurement information. I address this problem in my dissertation from three aspects, data acquisition, data processing/inversion and applications of the results/ uncertainty evaluation of the non-unique solution. Some other problems in the traditional inversion methods such as slowness speed of the convergence and the initial-correlation results. Firstly, I deal with the uncertainties in the data to be processed. The combination of micro-spherically focused log (MSFL) and dual laterolog(DLL) is the standard program to determine formation resistivity. During the inversion, the readings of MSFL are regarded as the resistivity of invasion zone of the formation after being corrected. However, the errors can be as large as 30 percent due to mud cake influence even if the rugose borehole effects on the readings of MSFL can be ignored. Furthermore, there still are argues about whether the two logs can be quantitatively used to determine formation resisitivities due to the different measurement principles. Thus, anew type of laterolog tool is designed theoretically. The new tool can provide three curves with different investigation depths and the nearly same resolution. The resolution is about 0.4meter. Secondly, because the popular iterative inversion method based on the least-square estimation can not solve problems more than two parameters simultaneously and the new laterolog logging tool is not applied to practice, my work is focused on two parameters inversion (radius of the invasion and the resistivty of virgin information ) of traditional dual laterolog logging data. An unequal weighted damp factors- revised method is developed to instead of the parameter-revised techniques used in the traditional inversion method. In this new method, the parameter is revised not only dependency on the damp its self but also dependency on the difference between the measurement data and the fitting data in different layers. At least 2 iterative numbers are reduced than the older method, the computation cost of inversion is reduced. The damp least-squares inversion method is the realization of Tikhonov's tradeoff theory on the smooth solution and stability of inversion process. This method is realized through linearity of non-linear inversion problem which must lead to the dependency of solution on the initial value of parameters. Thus, severe debates on efficiency of this kinds of methods are getting popular with the developments of non-linear processing methods. The artificial neural net method is proposed in this dissertation. The database of tool's response to formation parameters is built through the modeling of the laterolog tool and then is used to training the neural nets. A unit model is put forward to simplify the dada space and an additional physical limitation is applied to optimize the net after the cross-validation method is done. Results show that the neural net inversion method could replace the traditional inversion method in a single formation and can be used a method to determine the initial value of the traditional method. No matter what method is developed, the non-uniqueness and uncertainties of the solution could be inevitable. Thus, it is wise to evaluate the non-uniqueness and uncertainties of the solution in the application of inversion results. Bayes theorem provides a way to solve such problems. This method is illustrately discussed in a single formation and achieve plausible results. In the end, the traditional least squares inversion method is used to process raw logging data, the calculated oil saturation increased 20 percent than that not be proceed compared to core analysis.

西藏高原草原化嵩草草甸生态系统呼吸及碳平衡

The soil respiration and net ecosystem productivity of Kobresia littledalei meadow ecosystem was investigated at Dangxiong grassland station, one grassland field station of Lhasa Plateau Ecosystem Research Station. Soil respiration and soil heterotrophic respiration were measured at the same time by using Li6400-09 chamber in growing season of year 2004. The response of soil respiration and its components, i.e. microbial heterotrophic respiration and root respiration to biotic and abiotic factors were addressed. We studied the daily and seasonal variation on Net Ecosystem carbon Exchange (NEE) measured by eddy covariance equipments and then the regression models between the NEE and the soil temperature. Based on the researches, we analyzed the seasonal variation in grass biomass and estimated NEE combined the Net Ecosystem Productivity with heterogeneous respiration and then assessed the whether the area is carbon source or carbon sink. 1.Above-ground biomass was accumulated since the grass growth started from May; On early September the biomass reached maximum and then decreased. The aboveground net primary production (ANPP) was 150.88 g m~" in 2004. The under-ground biomass reached maximum when the aboveground start to die back. Over 80% of the grass root distributed at the soil depth from 0 to 20cm. The underground NPP was 1235.04 g m"2.. Therefore annual NPP wasl.385X103kg ha"1, i.e.6236.6 kg C ha"1. 2. The daily variation of soil respiration showed single peak curve with maximum mostly at noon and minimum 4:00-6:00 am. Daily variations were greater in June, July and August than those in September and October. Soil respiration had strong correlation with soil temperature at 5cm depth while had weaker correlation with soil moisture, air temperature, surface soil temperature, and so on. But since early September the soil respiration had a obviously correlation with soil moisture at 5cm depth. Biomass had a obviously linearity correlation with soil respiration at 30th June, 20th August, and the daytime of 27th September except at 23lh October and at nighttime of 27th September. We established the soil respiration responding to the soil temperature and to estimate the respiration variation during monsoon season (from June through August) and dry season (May, September and October). The regression between soil respiration and 5cm soil temperature were: monsoon season (June through August), Y=0.592expfl()932\ By estimating , the soil daily respiration in monsoon season is 7.798gCO2m"2 and total soil respiration is 717.44 gCC^m" , and the value of Cho is 2.54; dry season (May, September and October), Y=0.34exp°'085\ the soil daily respiration is 3.355gCO2m~2 and total soil respiration is 308.61 gCC^m", and the value of Cho is 2.34. So the total soil respiration in the grown season (From May to October) is 1026.1 g CO2IT1"2. 3. Soil heterogeneous respiration had a strong correlation with soil temperature especially with soil temperature at 5cm depth. The variation range in soil heterogeneous respiration was widely. The regression between soil heterogeneous respiration and 5cm soil temperature is: monsoon season, Y=0.106exp ' 3x; dry season, Y=0.18exp°"0833x.By estimating total soil heterotrophic respiration in monsoon season is 219.6 gCC^m"2, and the value of Cho is 3.78; While total soil heterogeneous respiration in dry season is 286.2 gCCbm"2, and the value of Cho is 2.3. The total soil heterotrophic respiration of the year is 1379.4kg C ha"1. 4. We estimated the root respiration through the balance between soil respiration and the soil heterotrophic respiration. The contribution of root respiration to total respiration was different during different period: re-greening period 48%; growing period 69%; die-back period 48%. 5. The Ecosystem respiration was relatively strong from May to October, and of which the proportion in total was 97.4%.The total respiration of Ecosystem was 369.6 g CO2 m" .we got the model of grass respiration respond to the soil temperature at 5cm depth and then estimated the daytime grass respiration, plus the nighttime NEE and daytime soil respiration. But when we estimated the grass respiration, we found the result was negative, so the estimating value in this way was not close. 6. The estimating of carbon pool or carbon sink. The NPP minus the soil heterogeneous respiration was the NEE, and it was 4857.3kg C o ha"1, which indicated that the area was the carbon sink.