镉（Ⅱ）－2－（2－苯并噻唑偶氮）－5－二甲氨基苯甲酸配合物的吸附伏安法研究及应用

镉（Ⅱ）－２－（２－苯并噻唑偶氮）－５－二甲氨基苯甲酸配合物的吸附伏安法研究及应用徐素君，施清照，张培敏，吴念慈（杭州大学化学系３１００２８）关键词：２－（２－苯并噻唑偶氮）－５－二甲氨基苯甲酸（ＢＴＡＭＢ），镉，吸附伏安法杂环偶氮试剂的极谱性质及其...     

1，2，4－三嗪类化合物的研究（ⅩⅫ）──咪唑并－（5，4－e）－1，2，4－三嗪衍生物的合成

１，２，４－三嗪类化合物的研究（ⅩⅫ）──咪唑并－（５，４－ｅ）－１，２，４－三嗪衍生物的合成沙耀武，蔡孟深（北京医科大学药学院，北京，１０００８３）关键词乙二脒腙，原甲酸三乙酯，１，２，４－三嗪，咪唑并－（５，４－ｅ）－１，２，４－三嗪天然碱基拮抗...     

镍（Ⅱ）与2－（5－溴－2－吡啶偶氮）－5－二甲氨基苯胺显色反应的研究及铝合金中镍的测定

本文研究了新显色剂２－（５－溴－２－吡啶偶氮）－５－二甲氨基苯胺与镍（Ⅱ）的反应条件。试验结果发现，在阴离子表面活性剂十二烷基硫酸钠存在下，在ｐＨ５．２～６．５范围内，试剂与镍（Ⅱ）形成稳定的２∶１配合物。其最大吸收波长在５７０ｎｍ处，表观摩尔吸光系数为１．２４×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。镍（Ⅱ）浓度在０～０．４μｇ·ｍＬ￣（－１）之间符合比尔定律。以硫脲和氟化按作掩蔽剂，可消除Ｃｕ￣（２＋）、Ｐｄ￣（２＋）、Ｆｅ￣（３＋）等离子的干扰。所拟方法用于铝合金中微量镍的测定，结果满意。     

1－苯基－3－甲基－4－苯甲酰基－5－吡唑啉酮（HPMBP）与金属离子配合物的结构研究──（Ⅲ）La（pmbp）_3（H_2O）_2的合成与晶体结构

报道标题化合物Ｌａ（ＰＭＢＰ）_３（Ｈ_２Ｏ）_２，Ｈｐｍｂｐ＝Ｃ_（１７）Ｈ_（１４）Ｎ_２Ｏ_２的合成及晶体结构，晶体属于单斜晶系，空间群Ｃ２／ｃ，晶体学数据：ａ＝２４．７４４（５），ｂ＝１６．３２５（６），ｃ＝２５．８７１（５），β＝１０５．４４（３）°，Ｖ＝１００７３（２）３，Ｍ_ｒ＝１００６，Ｚ＝８，Ｄ_ｘ＝１．３２８ｇ／ｃｍ~（－３），μ＝９．０４２ｃｍ~（－１），Ｆ（０００）＝４０９４。最终偏离因子Ｒ＝０．０４９，Ｒ_ｗ＝０．０５９。分子中Ｌａ（Ⅲ）与８个氧原子配位形成三角十二面体构型，Ｌａ－Ｏ平均键长为２．４９６（２）。     

新显色剂5－NO_2－PADAP与镍的显色反应研究

本文研究了新显色剂２－（５－ＮＯ２－２－吡啶偶氨）－５－二乙氨基酚（５－ＮＯ２－ＰＡＤＡＰ）与镍的显色反应及分光光度测定镍，在ＰＨ３．５乙醇水溶液中，镍与５－ＮＯ２－ＰＡＤＡＰ形成稳定的深色配合物，最大吸收在５６５ｕｍ处，摩尔吸光系数为．１．５７×１０５Ｌ·ｍｏｌ（－１）·ｃｍ（－１），镍在０～１２μｇ／２５ｍＬ范围内服从比尔定律，用此法测定钢铁及茶叶中的微量镍，结果令人满意。     

新显色剂2－（5－硝基－2－吡啶偶氮）－5－二甲氨基苯胺与钯显色反应的研究及其应用

用新合成的偶氮试剂２－（５－硝基－２－吡啶偶氮）－５－二甲氨基苯胺（５－ＮＯ＿２－ＰＡＤＭＡ）研究了光度法测定他的反应条件。结果表明，在０．４５～１．２ｍｏｌ／Ｌ盐酸介质中，钯与试剂形成稳定的蓝色配合物，其最大吸收波长位于６２１ｎｍ处，表观摩尔吸收系数为９．４×１０￣４Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），配合成的组成为Ｐｄ：５－ＮＯ＿２－ＰＡＤＭＡ＝１：２，钯浓度在０～１０μｇ／１０ｍＬ范围内符合比尔定律。本方法是目前测定钯的高灵敏度和高选择性体系之一。用于含钯分子筛及二次合金管理样－８８中微量钯的测定，结果满意。     

2-(3,5-二氯-2-吡啶偶氮)-5-二甲氨基苯胺与铂(Ⅳ)显色反应的研究

研究了２－（３，５－二氯－２－吡啶偶氮）－５－二甲氨基苯胺（３，５－ｄｉＣｌ－ＰＡＤＭＡ）与铂（Ⅳ）的显色反应及铂配合物的质子化行为。结果表明，在０．０４～０．４８ｍｏｌ／Ｌ的Ｈ２ＳＯ４溶液中，于加热的条件下，试剂可与铂（Ⅳ）形成稳定的１∶２绿蓝色ＰｔＬ２Ｈ２＋２配合物，其最大吸收波长位于６３４ｎｍ，表观摩尔吸光系数为９．７３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，桑德尔灵敏度为０．００２μｇ·ｃｍ－２。铂配合物的三级质子化常数分别为：ｌｇＫａ１＝３．９１，ｌｇＫａ２＝－２．２１，ｌｇＫａ３＝－３．３７。较大量的常见金属离子及除钯、钌外的其它贵金属离子不干扰测定。利用Ｐｔ，Ｐｄ与试剂反应所需的温度差异，可以用差减法消除微量Ｐｄ的干扰．铂（Ⅳ）浓度在每１０ｍＬ０～７．５μｇ范围内符合比尔定律。所拟方法用于二次合金管理样－８８及催化剂中微量铂的测定，结果满意。     

2－氯／2－甲磺酰基－5－（2－苯基－4－喹啉基）－1，3，4－噁二唑化合物的合成及其亲核取代的研究

借处理２－羟基－５－（２－苯基－４－喹啉基）－１，３，二唑同ＰＣｌ＿５／ＰＯＣｌ＿３之间的反应合成了２－氯－５－（２－苯基－４－喹啉基）－１，３，４－二唑（３）和通过２－基－５－（２－苯基－４－喹啉基）－１，３，４－二唑的甲基化，然后氧化制得２－甲磺酰基－５－（２－苯基－４－喹啉基）－１，３，４－二唑（６）．并分别研究了３和６同胺、叠氮及肼的反应，得到２，５－二取代的二唑新衍生物．初步观察了部分化合物的抗菌活性．     

3－苯基－5－取代苯氨基－6－甲基－1，2，4－三嗪的合成

３－苯基－５－取代苯氨基－６－甲基－１，２，４－三嗪的合成陆忠娥，曾润生，席海涛（苏州大学化学系，苏州，２１５００６）关键词硫代苯甲酰胺，α－乙酰基硫代甲酰苯胺，Ｎ＇－氨基苯甲脒，３－苯基－５－取代苯氨基－６－甲基－１，２，４－三嗪１，２，４－三嗪类...     

N-芳基-5-芳基-2-呋喃甲酰胺和N-5-芳基-2-呋喃甲酰基-N′-芳氧基乙酰基肼的合成及生物活性的研究

５－芳基－２－呋喃甲酸及其衍生物具有调节植物生长等作用［４］．我们通过大量的实验，选用ＰＴＣ法，利用５－芳基－２－呋喃甲酰氯与芳胺和芳氧基乙酰肼反应，合成了新化合物Ⅱ和Ⅳ：ＲＣＯＣｌＯ（Ⅰ）ＡｒＮＨ２／ＰＥＧ－４００→ＲＣＯＮＨＡｒ（Ⅱ）ＯＮａＯＨ／...     

Comparative analysis of the conformational profile of substance P using simulated annealing and molecular dynamics

The present study describes an extensive conformational search of substance P using two different computational methods. On the one hand, the peptide was studied using the iterative simulated annealing, and on the other, molecular dynamics simulations at 300 and 400 K. With the former method, the peptide was studied in vacuo with a dielectric constant of 80, whereas using the latter study the peptide was studied in a box of TIP3P water molecules. Analysis of the results obtained using both methodologies was carried out using an in-house methodology using a cluster analysis method based on information theory. Comparison of the two sampling methodologies and the different environment used in the calculations is also analyzed. Finally, the conformational motifs that are characteristic of substance P in a hydrophilic environment are presented and compared with the experimental results available in the literature.     

微柱液相色谱和电化学检测法测定鼠脑微透析液中神经传递物质

报道了使用微柱色谱和电化学检测器测定鼠脑微透析液中神经传递物质的方法。儿茶酚胺，５－羟色胺和代谢物的检测限为 ０． １～０． ５ ｐｇ。含有乙酰胆碱酯酶和胆碱氧化酶的柱后反应器使分离后的乙酰胆碱和胆碱转化成过氧化氢．再用铂电极或过氧化物酶修饰过的玻碳电极检测过氧化氢。乙酰胆碱的检测限当使用怕电极时是５０× １０－１５ｍｏｌ，当使用酶修饰电极时是１０×１０－１５ｍｏｌ。     

A comparative study of the correction of systematic errors in the quantitation of pyrethroids in vegetables using calibration curves prepared using standards in pure solvent

A comparative study of two mathematical approaches was performed in order to correct systematic errors due to the presence of the unexpected interferences which appear when the quantitation of the analyte in real samples is carried out with calibration curves built using standards in pure solvent. These methods consisted in the establishment of different mathematical expressions which transform the concentration (Cs) obtained using calibration graphs built using pure solvent into the corrected concentration (C(M)) that should be obtained if the quantitation is carried out with calibration curves built using standards dissolved in blank matrix extracts. In the two approaches the correction is performed from the results of an intermediate precision study which was carried out using both calibration graphs (prepared using pure solvent and blank matrix extract). By using ANCOVA to compare the slope of both solvent-based and matrix-matched calibration graphs, matrix effect was found in the determination of deltamethrin in tomato and acrinathrin in tomato and pepper. In these cases, both approaches led to good results.     

A comparison of the consistency of proteome quantitation using two-dimensional electrophoresis and shotgun isobaric tagging in Escherichia coli cells

An important consideration in the measurement of quantitative changes in protein expression is the consistency of the observations for a given technique as well as the reproducibility of the experiment. A quantitative assessment of the technical and biological variability is crucial to avoid erroneous inferences and conclusions. Two methods for measuring quantitative changes in protein expression are two-dimensional electrophoresis (2-DE) and shotgun proteomics of isobaric-tagged samples using iTRAQ reagents. An assessment of changes in Escherichia coli protein expression in response to rhsA induction demonstrates that half of the quantified protein expression ratios have a coefficent of variation (CV) less than 0.31 using 2-DE and less than 0.24 using isobaric tags; whereas 95% of the quantified protein expression ratios have a CV less than 0.81 using 2-DE and less than 0.53 using isobaric tags. The selective removal of outlier data points from the shotgun method using Grubb's and Rosner's statistical outlier tests improves the consistency of the quantitation data obtained.     

数学模拟方法研究导电剂形貌对锂离子电池高倍率放电性能的影响

制备了正极中只含有一种导电剂(KS-6或Super-P)的锂离子电池,比较了它们的倍率放电性能并对放电过程进行了模拟。以Super-P为正极导电剂的电池15C放电容量为1C容量的84.3%,以KS-6为正极导电剂的电池15C放电容量为1C容量的21.8%,前者的倍率放电性能明显优于后者。数学模拟结果显示,以KS-6为导电剂的正极的Bruggeman系数为3.1,以Super-P为导电剂的正极的Bruggeman系数为2.76,前者明显大于后者,认为这是由于KS-6的片状形貌使其容易相互平行排列造成的。大电流放电时,以KS-6为导电剂的正极中出现了电解质耗竭而导致该区域内电化学反应停止的现象,从而导致电池放电容量急剧降低。     

DECREASED HOST CELL REACTIVATION OF UV-IRRADIATED ADENOVIRUS 5 BY FIBROBLASTS FROM COCKAYNE'S SYNDROME PATIENTS

Abstract— Over a period of 5 years, we performed 29 experiments in which survival curves of UV-irradiated adenovirus were determined using fibroblast strains from 10 normal persons and from 7 persons having Cockayne's syndrome. In all of these, the survival of UV-irradiated adenovirus 5 was less when assayed using monolayers of fibroblasts from Cockayne's syndrome patients than from normal persons. Survival curves using normal fibroblasts were, within error, straight lines on a log survival vs. linear fluence plot. Survival curves obtained using Cockayne's syndrome fibroblasts showed 2 components: an initial sensitive component, reflecting the behavior of approx. 75% of the infected cells, followed by a component having normal sensitivity. In the 28 experiments that were considered reliable, 58 curves were done using Cockayne's fibroblasts, 41 using normal human fibroblasts. Although experimental variation was encountered, there was no individual case in which sensitivity as measured using Cockayne's was equal to (or less than) the sensitivity measured using normal fibroblasts.     

True moving bed electrophoresis using stepped electric field gradients

True moving bed electrophoresis has been shown to be an effective technique for the bench-scale separation of enantiomers, and it is desired to increase the maximum possible throughput attainable with the process by using electric field gradients. Homatropine enantiomer separations were performed and results using a stepped electric field gradient were compared to those using a traditional non-gradient separation. In order to accomplish this, a newly designed stator was constructed for use with the Vortex-Stabilized Electrophoresis Apparatus that has three sets of electrode housings, one set at both ends and one in the middle of the chamber. There were several problems related to the membranes used at the middle electrode. The dialysis membranes were permeable to the homatropine enantiomers, and while a switch to anion exchange membranes prevented the permeation of the homatropine, this caused a pH shift that interrupted binding to the hydroxypropyl-ss-cyclodextrin chiral selector. These problems prevented any meaningful data from being collected using homatropine enantiomers, and due to this, a proof of concept study was conducted using two bovine proteins. The separations using fluorescein-labeled BSA and bovine hemoglobin showed that a 63% increase in the maximum processing rate was attainable. The maximum throughput using the non-gradient process was 30.6 mg/h and the maximum was 50.0 mg/h using an electric field gradient that was 10% lower than the non-gradient field in section II and 10% higher in section III.     

An efficient conversion of nitroaromatics and aromatic amines to tertiary amines in one-pot way

Reductive alkylation and reductive methylation of aromatic primary amines with carbonyls and 37% formaldehyde using decaborane in one-pot way gave the corresponding tertiary amines in high yields. The reaction condition was extended for the reduction of nitroaromatic using decaborane and Pd/C followed by the reductive alkylation and reductive methylation using decaborane to give the corresponding tertiary amines in high yields.     

GC-MS method development and validation for anabolic steroids in feed samples

A GC-MS method for the determination of AAS used as growth promoting agents using SIM in piglet feed samples has been developed and validated, using testosterone as internal standard. The formation of volatile steroid derivatives was carried out by derivatization with N-methyl-N-(trimethylsilyl)trifluoroacetamide. The optimum separation was achieved using a Zebron ZB-5 column under a gradient temperature elution, allowing the separation of steroids in 18 min. The required sample treatment process was discussed. A leaching using ACN, saponification using a binary NaOH/MgCl2 solution, and LLE using ethyl acetate were finally selected. Method validation has been carried out according to the Commission Decision 2002/657/EC criteria established for quantitative confirmatory methods. The extraction efficiencies, CCalpha and CCbeta for these compounds were in the ranges 78-98%, 10-21 and 18-35 mug/kg, respectively. The repeatability and the within-laboratory reproducibility at 1, 1.5, and 2 CCbeta concentration levels were smaller than 8.2, 7.5, and 5.8% and 12.2, 9.5, and 7.5%, respectively. Accuracy was in the 99-103% range. The robustness was evaluated using the Youden robustness test. The proposed method was applied to the analysis of steroids spiked in different kinds of animal feed samples with satisfactory results.     

Influence of peak-broadening and interdetector volume error on size-exclusive chromatographic analysis with dual viscometric-concentration detection using the universal calibration method

The effect of peak-broadening and error in interdetector volume on the local calibration curve and experimental molecular-mass averages obtained by size-exclusion chromatography (SEC) with dual concentration/viscosity detection, and determination of molecular mass using the universal calibration (UC) method, is theoretically examined using a polymer sample with a molecular-mass distribution (MMD) approximated by the log-normal function. Although peak-broadening is often neglected, its effect on the slope of the local calibration curve and, consequently, on the experimentally obtained values of the weight-to-number average ratio is large. To obtain the right values of these parameters, a numerical correction is usually recommended. While using the UC method, the relationships between the extent of peak broadening, calibration slopes and interdetector volume are complex and can contribute to the occurrence of undiscovered errors. For this reason, an understanding of this problem, using a model, is necessary. The results of the UC method are compared with those obtained using dual-detection with known Mark-Houwink-Kuhn-Sakurada parameters (MHKS method), light-scattering (LS)/concentration detection as well as with the results obtained using conventional calibration. Due to peak-broadening, the slope of a local calibration curve and the weight-to-number average ratio, (Mw/Mn)", obtained using the UC method, increase compared to the theoretical values, whereas they decrease using the MHKS or LS methods. The increase when using the UC method is even larger compared to evaluation using conventional calibration. The effect of the error in interdetector volume on the slopes of local calibrations and the weight-to-number average ratios is opposite in the UC method to that found using the MHKS and LS methods.