Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (C) 2003 Elsevier B.V. All rights reserved.

基于I-Match算法的垃圾邮件过滤研究

电子邮件(Electronic Mail，E-Mail)是目前使用最广泛的互联网应用。随着互联网络以惊人的速度增长，电子邮件成为发布恶意信息的一个重要途径，垃圾邮件已经成为危害互联网络的最大毒瘤。针对方式多样的垃圾邮件技术，垃圾邮件过滤系统往往也需要综合多种过滤技术以提高系统的有效性。其中摘要技术已经成为重要的垃圾邮件过滤方法之一：通过摘要技术判断一个邮件和已知垃圾邮件的相似度，从而对邮件进行分类。判断一个垃圾邮件过滤算法是否有效，要综合考虑算法的召回率、准确率以及时间性能。I-Match算法通过摘要值的精确匹配来判断两个邮件文本内容是否相似，算法在效率方面表现突出。但是I-Match算法在实际的应用中还存在很多问题，其中包括字典生成制约算法的性能以及面对攻击时算法表现出的鲁棒性不足。因此，优化算法的字典生成过程以及提高算法的鲁棒性成了算法应用于实际系统的两个重要问题。本文的主要工作包含以下内容： 对垃圾邮件进行相似性分析，包括垃圾邮件相似性的起因、垃圾邮件在时间和内容两方面所表现出的相似性特征。垃圾邮件体现出的相似性特征是使用摘要算法进行垃圾邮件过滤的必要条件之一。 改进I-Match算法的字典生成过程。提出利用特征的互信息作为特征选择依据改进字典生成过程，并对比几种不同的特征选择方式对算法性能的影响。 分析I-Match算法的鲁棒性以及几种I-Match改进算法对算法鲁棒性的提升，在实际的邮件语料上对各种改进算法进行评测，并综合分析各个算法的实用性。 完成了KSpam系统原型，以插件的形式综合多种邮件过滤方法，并给出了I-Match算法在KSpam系统中的实现方案。同时，系统实现了一种新式的邮件自动回收功能，有效减少邮件管理员的邮件语料收集工作。

Grafting acrylic acid onto polypropylene by reactive extrusion with pre-irradiated PP as initiator

In this paper, the modification of polypropylene (PP) with acrylic acid (AA) by reactive extrusion using pre-irradiated PP (rPP) as initiator was investigated. It was found the relatively high graft degree (Gd) and slight degradation of modified PP was obtained when 20 wt% rPP was used. This result can be explained in terms of effective concentration of free radicals.

Preparation and Characterization of Melt Grafting 2-acrylamido-2-methyl-1-propanesulfonic Acid onto Pre-Irradiated Linear Low Density Polyethylene

Linear low density polyethylene (LLDPE) was functionalized with 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) by using -ray pre-irradiation in air in a twin-screw extruder. Fourier-transformed infrared spectroscopy (FT-IR) and electron spectroscopy for chemical analysis (ESCA) were used to characterize the formation of LLDPE-g-AMPS copolymers. The content of AMPS in LLDPE-g-AMPS was determined by using element analysis instrument. The effects of concentrations of monomer, reaction temperature and pre-irradiation dose on degree of grafting were investigated. The critical surface tension of LLDPE-g-AMPS was measured by using contact angle method. The influences of the degree of grafting on crystallization properties were studied by using DSC. Compared with neat LLDPE, the crystallization temperature increased about 4C, and crystallinity decreased with increasing degree of grafting. Crystallization rates of grafted LLDPE were faster than that of plain LLDPE at the same crystallization temperature.

The preparation of high activity DMFC Pt/C electrocatalysts using a pre-precipitation method

It is suggested that a Pt/C cathodic catalyst for the direct methanol fuel cell (DMFC) can be prepared with a pre-precipitation method, in which, H2PtCl6 is precipitated onto the carbon black as (NH4)(2)PtCl6 before H2PtCl6 is reduced to Pt. The electrocatalytic activity of this Pt/C-A catalyst for oxygen reduction is excellent because the Pt/C catalyst prepared with this pre-precipitation method possesses a small average particle size, low relative crystalinity and a large electrochemically active surface area. In addition, the pre-precipitation method is simple and economical and it can be used to prepare a Pt/C catalyst on a large scale.

Electrochemical H2S sensor with H2SO4 pre-treated Nafion membrane as solid polymer electrolyte

It is reported for the first time that the performance of the electrochemical H2S sensor with the Nation membrane pre-treated with the concentrated H2SO4 as the solid electrolyte is much more stable than that for the sensor with the Nation membrane without H2SO4 pretreatment. The sensitivity of the sensor is about 2.92 muA/ppm. The response time of the sensor is about 9 s. The detection limit is about 0.1 ppm. Therefore, this kind of the electrochemical H2S gas sensor may be desirable for the practical application.

Self-assembly of the pre-formed inclusion complexes between cyclodextrins and alkanethiols on gold electrodes

A new kind of self-assembled monolayer (SAM) formed in aqueous solution through the pre-formed inclusion complexes (abbreviated CD . C-n) between alpha-, beta-cyclodextrins (CDs) and alkanethiols (CH3(CH2)(n-1)SH, n = 10, 14 and 18) was prepared successfully on gold electrodes. High-resolution H-1 NMR was used to confirm the formation of CD . C-n. X-ray photoelectron spectroscopy, cyclic voltammetry and chronoamperometry were used to characterize the resulting SAMs (denoted as M-CD . Cn). It was found that M-CD . Cn were more stable against repeated potential cycling in 0.5 M H2SO4 than SAMs of CH3(CH2)(n-1)SH (denoted as M-Cn), with a relative sequence of Mbeta-CD . Cn > Malpha-CD . Cn > M-Cn. In addition, an order of blocking the electron transfer between gold electrodes and redox couples (both Fe(CN)(6)(3-) and Ru(NH3)(6)(3+)) in solution, M-CD . C10 > M-CD . C14 > M-CD . C18, was observed. A plausible explanation is provided to elucidate some of the observations. (C) 1997 Elsevier Science S.A.

Simultaneous determination of monoamine and amino acid neurotransmitters in rat endbrain tissues by pre-column derivatization with high-performance liquid chromatographic fluorescence detection and mass spectrometric identification

A sensitive and efficient method for simultaneous determination of glutamic acid (Glu), gamma-amino-butyric acid (GABA), dopamine (DA), 5-hydroxytryptamine (5-HT) and 5-hydroxyindole acetic acid (5-HIAA) in rat endbrains was developed by high-performance liquid chromatography (HPLC) with fluorescence detection and on-line mass spectrometric identification following derivatization with 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC). Different parameters which influenced derivatization and separation were optimized. The complete separation of five neurotransmitter (NT) derivatives was performed on a reversed-phase Hypersil BDS-C-18 column with a gradient elution. The rapid structure identification of five neurotransmitter derivatives was carried out by on-line mass spectrometry with electrospray ionization (ESI) source in positive ion mode, and the BCEOC-labeled derivatives were characterized by easy-to-interpret mass spectra. Stability of derivatives, repeatability, precision and accuracy were evaluated and the results were excellent for efficient HPLC analysis. The quantitative linear range of five neurotransmitters were 2.441-2 x 10(4) nM, and limits of detection were in the range of 0.398-1.258 nM (S/N = 3:1). The changes of their concentrations in endbrains of three rat groups were also studied using this HPLC fluorescence detection method. The results indicated that exhausting exercise could obviously influence the concentrations of neurotransmitters in rat endbrains. The established method exhibited excellent validity, high sensitivity and convenience, and provided a new technique for simultaneous analysis of monoamine and amino acid neurotransmitters in rat brain. (C) 2008 Elsevier B.V. All rights reserved.

Determination of aliphatic amines from soil and wastewater of a paper mill by pre-column derivatization using HPLC and tandem mass spectrometry (HPLC-MS/MS)

A pre-column derivatization method for the sensitive determination of aliphatic amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by HPLC with fluorescence detection and APCI/NIS identification in positive-ion mode has been developed. The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by the 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent, BCEOC, that could easily and quickly label amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M + H](+) with APCI/MS in positive-ion mode. The collision induced dissociation of the protonated molecular ion formed characteristic fragment ions at m/z 264.1, m/z 246.0 and m/z 218.1, corresponding to the cleavages of CH2CH2O-CO, CH2CH2-OCO, and N-CH2CH2O bonds. Studies on derivatization conditions demonstrated that excellent derivatization yields close to 100% were observed with a 3 to 4-fold molar reagent excess in acetonitrile solvent, in the presence of borate buffer (pH 9.0) at 40 degrees C for 10 min. In addition, the detection responses for BCEOC derivatives were compared with those obtained with CEOC and FMOC as labeling reagents. The ratios I-BCEOC/I-CEOC and I-BCEOC/I-FMOC were, respectively, 1.40-2.76 and 1.36-2.92 for fluorescence responses (here, I was the relative fluorescence intensity). Separation of the amine derivatives had been optimized on an Eclipse XDB-C-8 column. Detection limits calculated from an 0.10 pmol injection, at a signal-to-noise ratio of 3, were 18.65-38.82 fmol (injection volume 10 mu L for fluorescence detection. The relative standard deviations for intraday determination (n = 6) of standard amine derivatives (50 pmol) were 0.0063-0.037% for retention times and 3.36-6.93% for peak areas. The mean intra-and inter-assay precision for all amines were <5.4% and 5.8%, respectively. The recoveries of amines ranged from 96 to 113%. Excellent linear responses were observed with correlation coefficients of >0.9994. The established method provided a simple and highly sensitive technique for the quantitative analysis of trace amounts of aliphatic amines from biological and natural environmental samples.

Pre-column derivatization of amines with 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate followed by LC-fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCl-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH](+) under APCl in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of l(BCIC)/l(CEOC) and l(BCIC)/l(FMOC) are, respectively, 1.23-3.14 and 1.25-3.08 for fluorescent (FL) responses (here, l is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C-8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6-37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV < 7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997.

胜利勘探数据中心及勘探辅助决策系统研究

In the paper through extensive study and design, the technical plan for establishing the exploration database center is made to combine imported and self developed techniques. By research and repeated experiment a modern database center has been set up with its hardware and network having advanced performance, its system well configured, its data store and management complete, and its data support being fast and direct. Through study on the theory, method and model of decision an exploration decision assistant schema is designed with one decision plan of well location decision support system being evaluated and put into action. 1. Study on the establishment of Shengli exploration database center Research is made on the hardware configuration of the database center including its workstations and all connected hardware and system. The hardware of the database center is formed by connecting workstations, microcomputer workstations, disk arrays, and those equipments used for seismic processing and interpretation. Research on the data store and management includes the analysis of the contents to be managed, data flow, data standard, data QC, data backup and restore policy, optimization of database system. A reasonable data management regulation and workflow is made and the scientific exploration data management system is created. Data load is done by working out a schedule firstly and at last 200 more projects of seismic surveys has been loaded amount to 25TB. 2. Exploration work support system and its application Seismic data processing system support has the following features, automatic extraction of seismic attributes, GIS navigation, data order, extraction of any sized data cube, pseudo huge capacity disk array, standard output exchange format etc. The prestack data can be accessed by the processing system or data can be transferred to other processing system through standard exchange format. For supporting seismic interpretation system the following features exist such as auto scan and store of interpretation result, internal data quality control etc. the interpretation system is connected directly with database center to get real time support of seismic data, formation data and well data. Comprehensive geological study support is done through intranet with the ability to query or display data graphically on the navigation system under some geological constraints. Production management support system is mainly used to collect, analyze and display production data with its core technology on the controlled data collection and creation of multiple standard forms. 3. exploration decision support system design By classification of workflow and data flow of all the exploration stages and study on decision theory and method, target of each decision step, decision model and requirement, three concept models has been formed for the Shengli exploration decision support system including the exploration distribution support system, the well location support system and production management support system. the well location decision support system has passed evaluation and been put into action. 4. Technical advance Hardware and software match with high performance for the database center. By combining parallel computer system, database server, huge capacity ATL, disk array, network and firewall together to create the first exploration database center in China with reasonable configuration, high performance and able to manage the whole data sets of exploration. Huge exploration data management technology is formed where exploration data standards and management regulations are made to guarantee data quality, safety and security. Multifunction query and support system for comprehensive exploration information support. It includes support system for geological study, seismic processing and interpretation and production management. In the system a lot of new database and computer technology have been used to provide real time information support for exploration work. Finally is the design of Shengli exploration decision support system. 5. Application and benefit Data storage has reached the amount of 25TB with thousand of users in Shengli oil field to access data to improve work efficiency multiple times. The technology has also been applied by many other units of SINOPEC. Its application of providing data to a project named Exploration achievements and Evaluation of Favorable Targets in Hekou Area shortened the data preparation period from 30 days to 2 days, enriching data abundance 15 percent and getting information support from the database center perfectly. Its application to provide former processed result for a project named Pre-stack depth migration in Guxi fracture zone reduced the amount of repeated process and shortened work period of one month and improved processing precision and quality, saving capital investment of data processing of 30 million yuan. It application by providing project database automatically in project named Geological and seismic study of southern slope zone of Dongying Sag shortened data preparation time so that researchers have more time to do research, thus to improve interpretation precision and quality.

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.

Synthesis of nanometric-size magnesium nitride by the nitriding of pre-activated magnesium powder

Magnesium nitride (Mg3N2) was synthesized by the reaction of magnesium in the highly reactive form (Mg*) with nitrogen at 450 degrees C under normal pressure. The effect of doping with nickel dichloride on the nitridation of Mg* was investigated. Differential thermal analysis (DTA) of Mg* systems and transmission electron microscopy (TEM) measurement of the product formed were carried out. TEM measurement showed that the particle size of the Mg3N2 synthesized was in the nanometric range. The dependence of nitridation of the NiCl2-doped Mg* on temperature was investigated at temperatures ranging from 300 to 500 degrees C. The nitridation of NiCl2-doped Mg* could occur even at temperature as low as 300 degrees C. (C) 1999 Kluwer Academic Publishers.