腺嘌呤和质子化腺嘌呤的结构和振动光谱

用密度泛函方法B3LYP/aug-cc-pVTZ分析了腺嘌呤和质子化腺嘌呤的低能稳定异构体的结构和振动光谱. 结果发现, 对于中性腺嘌呤分子, 腺嘌呤的异构体N9H比N7H的能量低32.76 kJ·mol-1(在极化连续模型下为6.28 kJ·mol-1). 基于标度量子力场方法所得到的势能分布, 对异构体N9H的部分振动基频重新进行了归属. 在极化连续模型下, 质子化腺嘌呤分子有5种低能稳定构型, 其中N1位质子化的9-位氢腺嘌呤最为稳定. 基于振动模式分析, 对这种最稳定构型的振动基频进行了归属, 并对腺嘌呤在pH=1的高氯酸溶液中的实验拉曼光谱进行了指认.     

轨道和波函数

分子（或原子）轨道是化学的基本概念之一。本文从Bohr原子轨道入手,介绍轨道概念的演化,以及轨道与波函数之间的关系,分子轨道与原子轨道之间的关系,并结合量化计算介绍基组与分子轨道的关系。     

准确度和精密度

20世纪40～50年代,分析化学大师Kolthoff建立了分析化学学科.从那时起,分析测试工作的实际质量水平就用误差(error)来表述准确度(accuracy),用偏差(deviation)来表述精密度(precision).     

珍珠粉和贝壳粉的化学成分和结构特征分析

<正>珍珠粉是将珍珠贝壳动物马氏珠母贝、蚌科动物三角帆蚌或褶纹冠蚌等双壳动物受刺激形成的珍珠用物理的方法粉碎磨细而成的粉状物,自古以来就是名贵中药,具有安神定惊、明目消翳、解毒生肌之功效[1]。但是,市场上常出现以将蚌壳用碱去除其表面的角质层研细而成的贝壳粉,混充珍珠粉。查阅文献发现,由于珍珠粉和贝壳     

物质的量和摩尔

叙述了两种物质的量的比率的测量方法。介绍了物质的量的SI单位——摩尔。定义了涉及物质的量的一些量,其中包括摩尔质量、一般的摩尔量、阿伏伽德罗常数、摩尔气体常数及法拉第常数等。对物质的量及其单位摩尔的概念作了有关历史的叙述。     

Kr和Kr2的实验和理论研究

利用超声分子束技术、同步辐射和反射式飞行时间质谱仪得到了Kr和Kr2的光电离质谱和光电离效率谱,确定了Kr和Kr2的电离能,利用Gaussian-03程序中的MP2(Full)/6-31G*,QCISD/cc-pVTZ以及B3LYP/6-31G方法优化了Kr2的结构,计算了它们的振动频率和电离能,计算结果显示:当采用相同的理论水平和皋组时,随着Kr同位素质荷比(m/z)的增大,它们结构和电离能保持不变,而振动频率逐渐变小.与此同时,用G2方法计算了Kr(84)和Kr2(168)的电离能,它们的电离能的理论值与实验结果符合得比较好.     

稀土和氮对灰铸铁耐腐蚀性和抗氧化性的影响

采用包内孕育法研究了稀土和氮对高碳当量灰铸铁耐腐蚀性和抗氧化性的影响。灰铸铁采用中频感应电炉熔炼，化学成分为Ｃ３４％～３５％，Ｓｉ２３％～２４％，Ｍｎ０７０％～０７５％。稀土和氮采用稀土硅铁合金和锰氮铁合金以孕育剂形式加入。研究结果表明，...     

拉丁语alchemia和chemia的词源考据和意义分析

在古埃及、希腊和阿拉伯语文献中没有“炼金术”和“化学”的区别。文艺复兴以后的拉丁语文献中逐渐出现了alchemia和chemia两个词。其中alchemia直接来源于阿拉伯语(al-kīmiya),而chemia更多地来源于希腊语文献中的χημεíα。尽管这2个词的来源不同,但它们基本上是同义词,很难从字面上把它们区分为现代意义上的神秘“炼金术”和实验“化学”。所以,这2个词的出现不能作为“炼金术”与“化学”两个学科独立的依据,在拉丁语文献中炼金术与化学没有明显区别,这也是近代科学发展中神秘法术与经验知识混合的一个典型例证。     

阿达玛变换光谱和成像技术的应用和研究进展

阿达玛变换(HT)作为一种多通道光谱调制技术，具有多通道同时检测能力、多通道成像能力以及适用于数据处理等优点。综述了近十年来HT光谱和成像技术在分析科学中的应用和研究进展。主要从HT模板编码技术和HT激发序列应用技术等方面讨论了其最新发展和存在的问题，并展望了其发展前景。     

Investigation of Copper(II) Interference on the Anodic Stripping Voltammetry of Lead(II) and Cadmium(II) at Bismuth Film Electrode

The bismuth‐coated electrode is known to be prone to errors caused by copper(II). This study investigates copper(II) interference at bismuth film electrode for the detection of lead(II) and cadmium(II). It was conducted using glassy carbon electrode, while the bismuth film was plated in situ simultaneously with the target metal ions at ? 1200 mV. Copper(II) presented in solution significantly reduced the sensitivity of the electrode, for example there was an approximately 70 % and 90 % decrease in peak signals for lead(II) and cadmium(II), respectively, at a 10‐fold molar excess of copper(II). The decrease in sensitivity was ascribed to the competition between copper and bismuth or the metal ions for surface active sites. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) analysis suggested a large decrease in the amount of bismuth nanoparticles formed on the electrode surface in the presence of copper(II) occurred, validating the competition between copper and bismuth ions for surface active sites. Recovery of the stripping signal of lead(II) and cadmium(II) was obtained by adding ferrocyanide ion to the solution. Finally, the proposed method was successfully applied to determine lead(II) and cadmium(II) in water samples and the method was validated by ICP‐MS technique.     

Determination of cadmium(II) at a gold electrode in the presence of selenium(IV) by anodic-stripping voltammetry with enhancement by iodide ion

Anodic-stripping voltammetry (ASV) has been used in the derivative mode for the determination of cadmium, with a gold electrode in sulphuric add medium containing seleniurn(IV). The peak height for cadmium is enhanced by the presence of iodide. The sensitivity for cadmium is very high, with a peak in the stripping voltamperogram at -0.27V (vs. Ag/AgCl). The peak height for cadmium is not affected by over a 100-fold level of lead in the presence of selenium(IV). The dependence of peak height on the cadmium concentration is linear in the range 0.05-10ng ml .     

Voltammetric determination of mercury(II) at a carbon paste electrode in aqueous solutions containing tetraphenylborate ion

The determination of mercury(II) ions can be achieved by monitoring the decrease in the oxidation peak of the tetraphenylborate ion in the presence of this metal ion at a carbon paste electrode. The reaction between mercury(II) and the tetraphenylborate ion results in the formation of diphenylmercury, thus providing the method with good selectivity over other metal ions. Using anodic stripping voltammetry in a neutral electrolyte, a linear dependence of the decrease of peak height was observed on increasing the mercury(II) concentration in the range 1 x 10(-6)-8 x 10(-9)M mercury(II). Zinc(II), cadmium(II), lead(II), nickel(II), cobalt(II), tin(II), potassium(I) and ammonium(I) ions did not interfere at a 1000-fold concentration excess. Iron(III) and chromium(III) did not interfere at a 250-fold and 50-fold concentration excess, respectively. Following masking procedures, copper(II), bismuth(III) and silver(I) did not interfere at a 100-fold concentration excess. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal.     

The differential pulse anodic stripping voltammetry of copper and lead and their determination in EDTA extracts of soils with the mercury film glassy carbon electrode

The differential pulse anodic stripping voltammetry of copper and lead at the mercury film glassy carbon electrode is discussed. The mercury film prevents the occurrence of a monolayer stripping peak for copper. The influence of antimony and bismuth on the anodic stripping voltammetric behaviour of copper and lead is discussed. An interaction between copper and antimony distorts the copper stripping peak and gives rise to an intermediate peak. The method described is suitable for determining copper and lead simultaneously in EDTA extracts of soils.     

Resolving the copper interference effect on the stripping chronopotentiometric response of lead(II) obtained at bismuth film screen-printed electrode

As copper(II) is a common ion in a variety of analytical samples, its effect on the stripping response of lead(II) at bismuth film screen-printed carbon electrode (BFSPCE) was investigated. The study was conducted using a screen-printed three-electrode system (working, counter and reference electrodes), with the carbon-working electrode plated in situ with bismuth film. Copper present at significant concentration level in samples was found to affect the sensitivity of the electrode by reducing the constant current stripping chronopotentiometric (CCSCP) response of lead(II). Recovery of the lead stripping response at the BFSPCE in the presence of copper was obtained when 0.1 mM ferricyanide was added to the test solution. The ferricyanide added circumvents the detrimental effect of copper(II) by selectively masking the copper ions by forming a complex. The analytical utility of the procedure is illustrated by the stripping chronopotentiometric determinations of lead(II) in soil extracts.     

Use of binary metal deposits on a cylindrical carbon-fiber microelectrode in the voltammetric determination of metal ions

The effect of binary metal deposits on a cylindrical carbon-fiber microelectrode on the determination of metals by direct and stripping voltammetry was studied. The electrolytic deposition of a binary system of copper and thallium, cadmium, lead, or mercury on the electrode in an alkaline solution resulted in the disappearance of the electroreduction peak of dissolved oxygen in the potential range from -0.8 to -1.4 V and in a decrease in the background current. Under the conditions of limited diffusion, the peak currents of Ni(II), Co(II), and Zn(II) in differential pulse voltammograms were 3–7 times higher than those calculated for a reversible electrode process under the conditions of semi-infinite diffusion. Because of this, the determination limit for metal ions in direct voltammetry was lowered to 1 X 10^-6 M. With a binary copper-thallium system, the peak current of zinc(II) reduction can be be detected in the presence of 5000-fold molar amounts of copper(II). The deposition of binary copper-lead and copper-thallium systems under the conditions of limited diffusion reduced the effect of negative interaction between the components of these systems and made possible the determination of lead(II) and thallium(I) by stripping voltammetry using additional peaks.     

Determination of Gold by Stripping Voltammetry in Platinum Gold Ore Mineral Raw Materials on Grafite Electrode Modified by Bismuth

The paper considers the possibility of determining the gold (III) by stripping voltammetry on graphite electrode modified by bismuth. It is shown the modification of the graphite electrode by bismuth increases the sensitivity of detection of gold in 2 times. The comparison of the results of gold determination by stripping voltammetry and by atomic absorption is presented. The advantages of stripping voltammetry on a graphite electrode modified with bismuth for gold determination are given.     

Determination of trace metals by anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode

A bismuth-modified carbon nanotube electrode (Bi-CNT electrode) was employed for the determination of trace lead, cadmium and zinc. Bismuth film was prepared by in situ plating of bismuth onto the screen-printed CNT electrode. Operational parameters such as preconcentration potential, bismuth concentration, preconcentration time and rotation speed during preconcentration were optimized for the purpose of determining trace metals in 0.1M acetate buffer solution (pH 4.5). The simultaneous determination of lead, cadmium and zinc was performed by square wave anodic stripping voltammetry. The Bi-CNT electrode presented well-defined, reproducible and sharp stripping signals. The peak current response increased linearly with the metal concentration in a range of 2-100 microg/L. The limit of detection was 1.3 microg/L for lead, 0.7 microg/L for cadmium and 12 microg/L for zinc (S/N=3). The Bi-CNT electrode was successfully applicable to analysis of trace metals in real environments.     

Anodic stripping voltammetry and chronopotentiometry of copper at a rotating carbosital disk electrode

The use of a new carbon material — carbosital — for electrodes is reviewed. The behaviour of copper deposited on the carbosital electrode surface in anodic stripping voltammetry and chronopotentiometry is discussed. In anodic stripping voltammetry with a rotating carbosital disk electrode, the peak current and the number of coulombs involved in stripping copper are directly proportional to the square root of the electrode rotation rate during preelectroiysis; the peak current is directly proportional to the potential scan rate during stripping. For anodic stripping voltammetry and anodic stripping chronopotentiometry, linear calibration graphs are obtained in the range 1 X 10^-3–1 x 10^-6 M copper(II). The method is applicable to analysis of high-purity cadmium for copper.     

Electroanalytical determination of cadmium(II) and lead(II) using an in-situ bismuth film modified edge plane pyrolytic graphite electrode.

A highly sensitive and simple electroanalytical methodology is presented using an in-situ bismuth film modified edge plane pyrolytic graphite electrode (BiF-EPPGE) which is exemplified with the simultaneous determination of cadmium(II) and lead(II). Square-wave anodic stripping voltammetry is utilised with the effects of several experimental variables studied. Simultaneous additions of cadmium(II) and lead(II) were investigated where two linear ranges between 0.1-100 and 0.1-300 microg/L and also detection limits of 0.062 and 0.084 microg/L were obtained, respectively. The method was then successfully applied to the simultaneous determination of cadmium(II) and lead(II) in spiked river water, where recoveries of 100.5 and 98% were obtained, respectively. This electroanalytical protocol using edge plane pyrolytic graphite electrodes is one of the simplest methodologies to date using non-mercury based electrodes and is simpler and cheaper than alternatives such as carbon nanotube electrode arrays, suggesting the use of edge plane pyrolytic graphite electrode for routine sensing.