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■ Quantitative gas detection with semiconductor micro-sensors and chemometrics ■采用半导体微传感器和化学计量学的定量气体检测
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000140
P. Breuil, N. Perdreau, C. Pijolat
The sensitive element that we developed is a sintered tin dioxide bar (2.5 〈 0.5 〈 0.5 mm) [3]. It is stuck on an alumina substrate (Fig. 1) with an integrated heating system (20 to 500 °C). The variations of electric conductivity are due partly to a modification of the point defects of the semiconductor in the presence of oxidizing or reducing gases. But they are also related to the catalytic reactions of surface, in particular in the presence of organic gases or vapours [2,5]. The curves conductance-temperature G = f(T) of some sensors may be characteristic of the gases present in air (Fig. 2). It is then necessary that these data be acquired in decreasing temperature in order to avoid memory effects.
我们开发的敏感元件是烧结二氧化锡棒(2.5 < 0.5 < 0.5 mm)[3]。它被粘在氧化铝基板上(图1),带有集成加热系统(20至500°C)。电导率的变化部分是由于半导体的点缺陷在氧化性或还原性气体的存在下发生了改变。但它们也与表面的催化反应有关,特别是在有机气体或蒸汽存在的情况下[2,5]。某些传感器的电导-温度G = f(T)曲线可能是空气中存在的气体的特征(图2)。因此,有必要在降低温度时获取这些数据,以避免记忆效应。
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引用次数: 6
3D quantitative structure activity relationships with CoRSA. Comparative receptor surface analysis. Application to calcium channel agonists 与CoRSA的三维定量结构活性关系。比较受体表面分析。应用于钙通道激动剂
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000141
O. Ivanciuc, T. Ivanciuc, D. Cabrol-Bass
The in vitro or in vivo interaction between chemical compounds and their biological targets (transporters, receptors, ion channels, enzymes) can be efficiently predicted with the 3D QSAR models introduced in recent years. In this paper we describe CoRSA (comparative receptor surface analysis), a novel 3D QSAR algorithm that can be applied to compute structure-activity equations whenever the structure of the biological target is not known. Using the common steric and electrostatic features of the most active members of a series of compounds, CoRSA generates a virtual receptor model, represented as points on a surface complementary to the van der Waals surface of the set of compounds. The structural descriptors of the model are represented by the total interaction energies between each surface point of the virtual receptor and all atoms in a molecule. These descriptors are used in a partial least squares (PLS) data analysis to generate a structure-activity model. A highly significant CoRSA model was obtained for a set of compounds that act as calcium channel agonists for the guinea pig left atrium assay.
近年来引入的三维QSAR模型可以有效地预测化合物与其生物靶点(转运体、受体、离子通道、酶)在体内或体外的相互作用。在本文中,我们描述了CoRSA(比较受体表面分析),这是一种新的3D QSAR算法,可以在生物靶标结构未知的情况下计算结构-活性方程。利用一系列化合物中最活跃成员的共同空间和静电特征,CoRSA生成了一个虚拟受体模型,表示为与该化合物的范德华表面互补的表面上的点。该模型的结构描述符由虚拟受体的每个表面点与分子中所有原子之间的总相互作用能表示。这些描述符用于偏最小二乘(PLS)数据分析,以生成结构-活动模型。在豚鼠左心房实验中,获得了一组作为钙通道激动剂的化合物的高度显著的CoRSA模型。
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引用次数: 14
Influence of pH on the photodegradation kinetics under UV light of climbazole solutions pH对克里巴唑溶液紫外光降解动力学的影响
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000171
C. Couteau, M. Jadaud, F. Peigne, L. Coiffard
The objective of this research was to study the effect of pH on the photodegradation kinetics of 15.8 μg.ml-1 aqueous solutions of climbazole. A high-performance liquid chromatographic method for the quantification of climbazole after irradiation of aqueous solutions was carried out, using a RP-18 column with a acetonitrile - 0.05 M sodium perchlorate mobile phase. The detector was set at a wavelength of 220 nm. Calibration curve showed linear response in the interval 5 to 25 μg.ml-1. Photodegradation appeared to follow first-order kinetics and was found pH-dependent. The degradation rate constant was calcu- lated to be 10.5 〈 10-3, 9.9 〈 10-3 and 16.5 〈 10-3 min-1, respectively at pH 5, 7 and 9.
本研究的目的是研究pH对15.8 μg光降解动力学的影响。克里巴唑的Ml-1水溶液。采用RP-18色谱柱,以乙腈- 0.05 M高氯酸钠为流动相,建立了高氯酸钠水溶液辐照后的高效液相色谱定量方法。探测器的波长设置为220 nm。校正曲线在5 ~ 25 μg.ml-1范围内呈线性响应。光降解似乎遵循一级动力学,并发现ph依赖。在pH为5、7和9时,降解速率常数分别为10.5 < 10-3、9.9 < 10-3和16.5 < 10-3 min-1。
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引用次数: 12
EPR spin trapping of superoxide from nitric oxide synthase 一氧化氮合酶超氧化物的EPR自旋捕获
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000280487
J. Vasquez-Vivar, J. Joseph, H. Karoui, Hao Zhang, J. Miller, P. Martásek
15 N)- EMPO has significantly improved the sen- sitivity of superoxide detection by electron para- magnetic resonance (EPR). Unlike 5,5-dimethyl-1- pyrroline N-oxide (DMPO), a commonly used superoxide spin trap, both DEPMPO and EMPO form superoxide adducts that are persistent, which do not decay to the corresponding hydroxyl adduct. Using these new spin traps, the EPR-detection of superoxide is now straightfor- ward and more sensitive. These new superoxide traps in combination with the loop gap resonator technology have enabled us to demonstrate unequivocally the formation of superoxide from the endothelial and neuronal isoforms of nitric oxide synthase. Superoxide is formed at the oxy- genase domain of the enzyme by a calcium/ calmodulin dependent mechanism. The effect of tetrahydrobiopterin cofactor and NOS inhibitors on the release of superoxide is discussed.
15n)- EMPO显著提高了电子对磁共振(EPR)超氧化物检测的灵敏度。不像5,5-二甲基-1-吡啶n -氧化物(DMPO),一种常用的超氧化物自旋陷阱,DEPMPO和EMPO形成的超氧化物加合物是持久的,它不会衰变为相应的羟基加合物。使用这些新的自旋阱,超氧化物的epr检测现在是直接和更敏感的。这些新的超氧化物陷阱与环隙谐振器技术相结合,使我们能够明确地证明一氧化氮合酶的内皮和神经元异构体形成超氧化物。超氧化物通过钙/钙调素依赖机制在酶的氧合酶区域形成。讨论了四氢生物蝶呤辅助因子和NOS抑制剂对超氧化物释放的影响。
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引用次数: 8
■ Real-time measurement of free radical production using specific electrochemical sensors: new insight into the consequences of O 2 - and NO flux ■使用特定电化学传感器实时测量自由基产生:对o2和NO通量后果的新见解
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000280493
P. Manning, M. Cookson, C. Eggett, C. Tolias, S. Read, A. Hunter, M. Tsatmali, A. Thody, E. Hillhouse, P. Shaw, C. McNeil
Direct real-time electrochemical measurements have offered new insight into the importance of free radical interplay in a number of cellular models. Initially the interrelationship between O 2 - and NO generation in astrocytic, neuronal and mixed astrocytic/neuronal cell populations was examined. Results indicated a novel function for astrocytic nitric oxide synthase (cNOS) in regulating extracellular O 2 - production on rat astrocytes was assessed. Findings show that extracellular O 2 - generation initiated the production of NO by glial cells. Other findings facilitated by electrochemical measurements included the characterisation of a novel motor neuron like cell line for its ability to produce O 2 - and NO in response to extracellular glutamate and AMPA, the interaction of O 2 - with NO in an animal models of migraine headache and the modulatory effect of α-melanocyte stimulating hormone (α-MSH) on NO production by human epidermal melanocytes.
直接的实时电化学测量为自由基相互作用在许多细胞模型中的重要性提供了新的见解。首先研究了星形细胞、神经元和混合星形细胞/神经元细胞群体中O -和NO生成之间的相互关系。结果表明,星形胶质细胞一氧化氮合酶(cNOS)在调节大鼠星形胶质细胞胞外o2生成中的新功能。研究结果表明,细胞外生成的一氧化氮激活了神经胶质细胞产生一氧化氮。电化学测量促进的其他发现包括一种新的运动神经元样细胞系的特征,它能够响应细胞外谷氨酸和AMPA产生O -和NO,偏头痛动物模型中O -与NO的相互作用,α-促黑素细胞激素(α-MSH)对人类表皮黑素细胞产生NO的调节作用。
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引用次数: 10
Influence of secondary interactions on high performance size exclusion chromatography. Application to the fractionation of landfill leachates 二次相互作用对高效粒径排阻色谱的影响。垃圾渗滤液分馏的应用
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000169
F. L. Coupannec, D. Morin, O. Sire, J. Peron
The leachates from municipal landfills are characterised by the complex chemical distribution and wide molecular weights range of their constituents. We have designed a high performance size exclusion chromatography method to take into account these two aspects. By using eluents of low ionic strength, electrostatic interactions between the eluted molecules and the negative sites of the stationary phase are enhanced. Thus, the compounds are eluted mostly according to their physico-chemical properties. Contrarily, using eluents of high ionic strength allows eliminating most of these electrostatic interactions which, in turn, permits to estimate the molecular weights, since steric exclusion is then the dominating mechanism of separation. A spec- troscopic fingerprint may also be determined through multidetection (UV absorption, fluorescence and evaporative light scatter- ing detection) coupled on line which allows to sort out the compounds into a few number of families.
城市垃圾填埋场的渗滤液具有化学分布复杂、成分分子量范围广的特点。考虑到这两个方面,我们设计了一种高效的粒径排阻色谱法。通过使用低离子强度的洗脱液,洗脱分子与固定相负电荷之间的静电相互作用增强。因此,这些化合物主要是根据它们的物理化学性质来洗脱的。相反,使用高离子强度的洗液可以消除大多数这些静电相互作用,这反过来又允许估计分子量,因为空间排斥是分离的主要机制。光谱指纹图谱也可以通过多重检测(紫外吸收、荧光和蒸发光散射检测)在线耦合来确定,从而可以将化合物分类为几个科。
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引用次数: 2
■ Design of electrochemical microsensors to monitor nitric oxide production in biological systems: a global compilation ■设计电化学微传感器以监测生物系统中一氧化氮的产生:全球汇编
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000280465
M. Pontie, F. Bedioui
We report in this paper a global and exhaustive overview of the various attempts reported in the literature to develop electrochemical microsensors for the direct determination of nitric oxide (NO) in biological systems. In this compilation, we address the physico-chemical characteristics and the performances (in term of sensitivity) of the numerous chemically modified microelectrodes that were specially designed for the determination of NO, without judging what the biological applications might be.
我们在本文中报告了文献中报道的开发用于直接测定生物系统中一氧化氮(NO)的电化学微传感器的各种尝试的全球和详尽概述。在本汇编中,我们讨论了专门用于测定NO的许多化学修饰微电极的物理化学特性和性能(在灵敏度方面),而不判断生物学应用可能是什么。
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引用次数: 8
■ Advantages and limits of the electrochemical method using Nafion and Ni-porphyrin-coated microelectrode to monitor NO release from cultured vascular cells ■利用Nafion和ni -卟啉包被微电极监测培养血管细胞NO释放的电化学方法的优点和局限性
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000280469
A. Brunet, C. Privat, O. Stepien, M. David‐Dufilho, J. Devynck, M. Devynck
Electrochemical monitoring with a porphyrinic microsensor of in situ nitric oxide production from cultured cells offers numerous advantages but requires cautious analysis, repeated calibration and accurate localisation of the electrode. It also had some limitations. We describe here some characteristics of this method, the stability of the electrode response during experiments and its application to nitric oxide production by constitutive and inducible nitric oxide synthases. Real-time measurements of NO concentration allow the study of the kinetics of NO production. This is illustrated by the time-course of NO release from cultured human endothelial cells. How NO production by inducible nitric oxide synthase in cultured smooth muscle cells obtained from human internal mammary artery can be evaluated by Nafion- and Ni-porphyrin-coated electrode is also described. The results thus obtained are compared to the cumulated NO 2 - production evaluated by the Griess method.
用卟啉微传感器对培养细胞的原位一氧化氮生产进行电化学监测具有许多优点,但需要谨慎分析,反复校准和准确定位电极。它也有一些局限性。我们在这里描述了这种方法的一些特点,实验中电极响应的稳定性以及它在本构型和诱导型一氧化氮合酶生产一氧化氮中的应用。实时测量一氧化氮浓度可以研究一氧化氮产生的动力学。这是通过培养的人内皮细胞释放NO的时间过程来说明的。本文还描述了如何利用Nafion和ni -卟啉包被电极来评价诱导型一氧化氮合酶在培养的人乳腺内动脉平滑肌细胞中产生NO。所得结果与用Griess法计算的累积二氧化氮产量进行了比较。
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引用次数: 9
■ Mathematical treatment of chemiluminescence data allowing an optimised kinetic analysis of vascular NAD(P)H-dependent superoxide anion production ■化学发光数据的数学处理,可以优化血管NAD(P) h依赖性超氧阴离子产生的动力学分析
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000280479
J. Iliou, N. Villeneuve, M. Fournet-Bourguignon, F. Robin, C. Jacquemin, V. Lestriez, C. Petit, A. Pillon, J. Vilaine
Regulation of vascular redox homeostasis plays a central role in the control of vascular tone (e.g.: redox modulation of endothelial NO synthase and soluble guanylate cyclase activities). Superoxide anion is one of the main reactive oxygen species involved in the modulation of the redox status of the vessel. It is crucial to know if pathological situations or drug treatments are able to modify NAD(P)H oxidase-dependent production of O 2 - . As a steady-state approach is the only way for a valid assessment of these parameters, a mathematical treatment allowing visualisation of the linear portion of the initial velocity of O 2 - production was developed. Using two vascular preparations (rat aortic rings and mouse thoracic aortae), the chemiluminescence (CL) in the presence of lucigenin was recorded every second in the 15-30 minute period after successive injections of NADPH and superoxide dismutase (SOD). Because, both O 2 - and photons are labile and evanescent products, visualisation of the steady-state requires calculation of their cumulative production by integral calculus using a first order integral equation. The cumulative production of CL and/or O 2 - was plotted as a function of the NADPH concentrations, were determined from the linear portion of these plots. For a precise molar quantification of O 2 - production, a calibration curve of initial velocities using xanthine oxidase + xanthine as a source of O 2 - was plotted by comparing CL and cytochrome C reduction. The NADPH-dependent CL production exihibited Michaelian behavior and SOD acted as a noncompetitive inhibitor. For example, the values for NADPH oxidase in rat aorta were: Km = 237 ± 2μM; Vmax = 500-600 pmol O 2 - /min/ring.
血管氧化还原稳态的调节在血管张力的控制中起着核心作用(例如:内皮NO合成酶和可溶性鸟苷酸环化酶活性的氧化还原调节)。超氧阴离子是参与调节血管氧化还原状态的主要活性氧之一。了解病理情况或药物治疗是否能够改变NAD(P)H氧化酶依赖性o2 -的产生是至关重要的。由于稳态方法是有效评估这些参数的唯一方法,因此开发了一种数学处理方法,可以将o2生产初速度的线性部分可视化。采用两种血管制剂(大鼠主动脉环和小鼠胸主动脉),连续注射NADPH和超氧化物歧化酶(SOD)后,在15 ~ 30分钟内每秒钟记录lucigenin存在下的化学发光(CL)。因为o2和光子都是不稳定的、易逝的产物,所以要想可视化稳态,就需要用一阶积分方程通过积分计算它们的累积产量。CL和/或o2 -的累积产量被绘制为NADPH浓度的函数,由这些图的线性部分确定。通过比较CL和细胞色素C还原量,绘制了以黄嘌呤氧化酶+黄嘌呤为o2 -源的初始速度标定曲线。nadph依赖性CL的产生表现出Michaelian行为,SOD作为非竞争性抑制剂。例如,大鼠主动脉内NADPH氧化酶值为:Km = 237±2μM;Vmax = 500-600 pmol o2 - /min/环。
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引用次数: 3
Use of a chloride ion selective electrode as a tool for monitoring relatively fast kinetic processes. Application to the hydrolysis of yperite analogues in presence of oximate nucleophiles 使用氯离子选择电极作为监测相对快速动力学过程的工具。在邻氧亲核试剂存在下亚闪石类似物水解的应用
Pub Date : 2000-07-01 DOI: 10.1051/ANALUSIS:2000168
S. P. Rodrigues, L. Coppée, J. Toullec, G. Moutiers
Experimental conditions have been designed which allowed the use of a chloride ion selective electrode for the mon- itoring of reactions that proceed with a moderately fast departure of Cl - ion, i.e. t1/2 ∪ 40 seconds, in aqueous solution. The pro- cedure has been applied in particular to the hydrolysis of yperite (HD) analogues (CEES, CEMS, CEPS) in aqueous solution in presence of HEPES buffer and oximate nucleophiles. Kinetic parameters were obtained in these conditions and the S N1 mecha- nism for the hydrolysis was confirmed.
实验条件已被设计,允许使用氯离子选择电极监测的反应,以适度快速的离开Cl -离子,即t1/2∪40秒,在水溶液中进行。该方法特别适用于在HEPES缓冲液和邻苯二甲酸酯亲核试剂存在下的水溶液中亚辉石(HD)类似物(CEES, CEMS, cceps)的水解。在此条件下获得了动力学参数,并确定了sn1的水解机理。
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引用次数: 1
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