Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent - Cold vapor atomic absorption spectrometry

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (11) was then eluted with 10% HNO3 and subsequently reduced by NaBH4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min(-1) sample loading rate. The detection limit was 0.2 ng L-1 and much lower than that of conventional method (around 15.8 ng L-1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L-1 of Hg and the linear working curve is from 20 to 2000 ng L-1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.

Sensitive and Selective Sensor for Biothiols in the Cell Based on the Recovered Fluorescence of the CdTe Quantum Dots-Hg(II) System

Herein, a sensitive and selective sensor for biothiols based on the recovered fluorescence of the CdTe quantum dots (QDs)-Hg(II) system is reported. Fluorescence of QDs could be quenched greatly by Hg(II). In the presence of biothiols, such as glutathione (GSH), homocysteine (Hcy), and cysteine (Cys), however, Hg(H) preferred to react with them to form the Hg(II)-S bond because of the strong affinity with the thiols of biothiols rather than quenching the fluorescence of the QDs. Thus, the fluorescence of CdTe QDs was recovered. The restoration ability followed the order GSH > Hcy > Cys due to the decreased steric hindrance effect. A good linear relationship was obtained from 0.6 to 20.0 mu mol L-1 for GSH and from 2.0 to 20.0 mu mol L-1 for Cys, respectively. The detection limits of GSH and Cys were 0.1 and 0.6 mu mol L-1, respectively. In addition, the method showed a high selectivity for Cys among the other 19 amino acids. Furthermore, it succeeded in detecting biothiols in the Hela cell.

Syntheses and structures of Na-2[Zn-II(ida)(2)].7H(2)O and Na-4[Hg-II(nta)(2)].7H(2)O

The title complexes were synthesized and the crystal structures of their salts were determined by single-crystal X-ray structure analyses. Na-2[Zn-I(ida)(2)]. 7H(2)O: Triclinic, P1, a=0.523 4(2) nm, b=0.897 10(10) nm, c=1.069 10(10) nm, alpha=85.910(10)degrees, beta= 76.380(10)degrees, gamma=83.52(2)degrees, V=0.484 2(2) nm(3), Z=1. The complex anion [Zn-I (ida)(2)](2-) has a pseudo-octahedral structure in which the two N atoms: are in a trans configuration. Na-4[Hg-I(nta)(2)]. 7H(2)O: Monoclinic, C-c, a = 1.795 0(4) nm, b = 0.892 9(2)nm, c = 1.575 4(2) nm, beta = 92.78 (3)degrees, V = 2.526 2(9) nm(3), Z = 4. The complex anion [Hg-I (nta)(2)](4-) has a pseudo-bicapped-octahedral structure in which the two N atoms are in a trans configuration.

Synthesis and evaluation of a thiourea-modified chitosan derivative applied for adsorption of Hg(II) from synthetic wastewater

In this work, a thiourea-modified chitosan derivative (TMCD) was synthesized through two steps, O-carboxymethylated first and then modified by a polymeric Schiff's base of thiourea/glutaraldehyde. The adsorption behavior of mercury (II) ions onto TMCD was investigated through batch method. The maximum adsorption capacity for Hg(II) was found to be 6.29 mmol/g at pH 5.0 and both kinetic and thermodynamic parameters of the adsorption process were obtained. The results indicated that adsorption process was spontaneous exothermic reaction and kinetically followed pseudo-second-order model. The adsorption experiments also demonstrated TMCD had high adsorption selectivity towards Hg(II) ions when coexisted with Cu(II), Zn(II), Cd(II) and Ca(II) in solution and it could be easily regenerated and efficiently reused. (C) 2010 Elsevier B.V. All rights reserved.

Separation and detection of chlorpromazine hydrochloride and promethazine hydrochloride using electrochemiluminescence followed by capillary electrophoresis

Phenothiazine drugs, chlorpromazine hydrochloride (CPZ) and promethazine hydrochloride (PMZ), were determined with Ru(bpy)(3)(2+) electrochemiluminescene by the capillary electrophoresis (CE-ECL). It was found that both CPZ and PMZ could produce an intermediate that acted as coreactants to react with Ru(bpy)(3)(2+) to produce excited states which were capable of emitting light. This CE-ECL detection method had high sensitivity, good selectivity and reproducibility for CPZ and PMZ determination.

Separation and detection of narcotic drugs on a microchip using micellar electrokinetic chromatography and electrochemiluminescence

A new approach for fast and sensitive electrochemiluminescence (ECL) detection of narcotic drugs on a microchip after separation by micellar electrokinetic chromatography (MEKC) is presented, taking the cocaine and its hydrolysate ecgonine as the test analytes. The mixture of hydrophilic BMIMBF4 ionic liquid (IL) and sodium dodecyl sulfate (SDS) was used directly as the buffer of MEKC with less noisy baselines, lower electrophoretic current and satisfactory separation performance.

Investigation on moleculare and crystal structures of metal complexes with aminopolycarboxylic acids (VII) - Syntheses and structure determination of Na-3[Hg (I) (edta) C1] center dot 6H(2)O

In this paper we describe the moleculare and crystal structures of the Na-3[Hg( II )(edta)Cl] . 6H(2)O (edta=ethylenediamine-N,N,N',N'-tetraacetate). The crystal data are as follows: orthorhombic, a=8. 083 (2) Angstrom , b=13. 870(3) Angstrom , c=38. 617(5) Angstrom , v=4329. 4 (13) Angstrom(3) , Z=8, Dc= 1. 798 g . cm(-3), mu=5. 564 mm(-1), P(000)=2280, R=0. 0317 and R-w=0. 0731 for 3883 unique reflections. In complex, the complex anion [Hg ( II ) (edta)Cl](3-) has a seven-coordination structure like a mono-capped trigonal-prism (C-2v-MTP) in which the edta(4-) acts as a hexadentate ligand with four O atoms and two N atoms and a Cl- caps a quadrilateral face as a seventh ligand. It can be known that the Hg2+ which has a d(10) electronic structure can form a high-coordinate compound with a hexadentate ligand (edta) because it has a big ionic radius.

Photoreduction of mercuric salt in UV/Fe (III)-oxalate complex system

In this paper, the photochemical reduction process of Hg (II) in aqueous solution containing ferric iron and oxalate (Ox) has been studied. Under the radiation of a low-pressure mercury lamp (lambda = 253.7 nm, 8W), Fe(III)-oxalate complexes undergo photolysis to produce ferrous ions and other organic reductive species, which reduce Hg(II) subsequently. For 0.1 mg/L Hg (II), the photoreduction efficiency is comparatively higher in the solution at pH 5.0 than that over the range of 3.0 similar to 8.0. The photoreduction efficiency of Ho (II) in aqueous solution increases with increasing, initial concentration of ferric ions from 0.02 mmol/L to 0.2 mmol/L and initial concentration of oxalate from 0.96 mmol/L to 4.8 mmol/L and then gradually approaches to a steady state. CH3OH also contributes the reduction of Hg (II). We investigate the increase of the ferric, oxalate and CH3OH concentrations resulting from the increase of reduction efficiency of Hg (II). It can be seen that ferrous ions and other reactive species are reductants of Hg (II), and the reaction product with oxalate is mainly volatile metallic mercury.

冠醚修饰电极及其在分析化学中的应用

本论文较系统地研究了Naf:on聚合物薄膜冠醚修饰电极阳极溶出伏安法在分析中的应用。首次将Naf:on薄膜冠醚类化合物修饰电极应用于铊、银和铅三种离子的测定，得到了高灵敏度的分析方法亦用于实际样品测定。用涂层法制备了Naf:on聚合物薄膜冠醚（二环已基18－冠－6）化学修饰电极，用这种修饰电极测定金属离子的高灵敏度来源于将Naf:on对大阳离子的强离子交换能力、冠醚类化合物络合金属阳离子形成大阳离子的能力与溶出伏安法的高灵敏度三者的结合，冠醚化合物中性分子可与金属阳离子络合形成大络阳离子：M~(n+)＋qC=(MC_q)~(n+) Naf:on膜由于其具有的对大阳离子的强交换能力而将冠醚与和金属离子形成的大阳离子络合并吸附于电极表面，在溶出伏安法的富集过程中，电位置于是以令（MCq）~(n+)还原的位置以使（MCq）~(n+)还原：（MCq）~(n+)＋ne=M＋qC 析出的零价态的金属可在Naf:on膜内固定，同时又放出冠醚分子成为新的未被占据的络合吸附中心，继续捕获溶液中的阳离子从而起到富集作用。由于使用溶出伏安法排除电极表面络合吸附饱和的问题，从而使本方法灵敏度大大高于一般的使用化学修饰电极进行预富集的分析测定方法。提出了Naf:on薄膜冠醚修饰电极阳极溶出伏安法测定水溶液中Te(I)的方法，在电位为－1.30 Vvs.Ag/Ag ce处0.1高氯酸锂溶液中，用该修饰电极富集30分钟，检测下限可低至2×10~(-12)M（0.4 ppt）。溶液中Te(I)浓度在5×10(-12)M～1×10(-8)M范围内与溶出峰电流成良好的线性关系且通过原点，可以用标准加入法测定。常见共存元素Zn（II），Su（II），Cu（II），Fe（II），Co（II），Ni（II），In（III）等无干扰。Pb（II）与Cd（II）共存时对Te（I）有干扰，同1×10~(-3)M EDTA掩蔽可有消除干扰。测定了合成样品中的Te（I）含量，平行测定七组样品相对标准偏差4.2％。本文法是目前Te（I）的分析中最灵敏的电化学方法之一。提出了Naf:on薄膜冠醚修饰电极阳极溶出伏安法测定水溶液中Ag（I）的方法。在0.01MHNO_3 4～7×10~(-3)M Cl混合溶液中，检测电位在－0.30Vvs.SCE富集30分钟，检出下限可低至2×10~(-12)M，是迄今所见Ag（I）的分析中灵敏度最高的电分析方法。Ag（I）浓度在2×10~(-11)M～1×10~(-8)M范围内与溶出峰电流成良好的线性关系且通过原点。五到十倍量的Hg（II）和Au（II）有干扰。用本法测定了分析纯硝酸铵中的银含量为0.000048％，平行测定七组样品相对标准偏差为3.7％。提出用Naf:on薄膜冠醚修饰电极阳极溶出伏安法测定水样中铅的方法。在0.lMLiNO_3底液中，电位在－1.10Vvs.SCE富庥3分钟检测限达5×10~(-10)M，方法快速灵敏。Pb（II）浓度在1×10~(-9)～1×10~(-7)M范围内与溶出峰电流呈线性关系。1×10~(-6)以上Cu（II）存在使Pb（II）的峰电流时显增加。用本方法测定了自来水样中的铅含量，平行测定七组样品相对标准偏差8.0％。该修饰电极在K~+浓度为1×10~(-5)～1×10~(-7)M范围内对K~+有能斯特响应。本工作为铊、铅、银的痕量分析提供了高灵敏度的方法，为溶出伏安法摆脱汞污染的问题做出了贡献，为化学修饰电极用于分析化学领域提供了新的途径。

伯胺N_(1923)萃取过渡金属离子机理的研究

伯胺由于其特殊的结构（R-NH_2），使它具有和仲、数胺不相同的一些性质。有较强的和矿物酸HX结合形成RNH_3X的能力，从而以离子交换机理萃取金属离子；也可以-NH_2上的氮、氢原子同以高价存在的过渡金属含氧酸以氢键方式相结合；另外，RNH_2也可通过氮原子以配位键形式与一些属于软酸类的过度金属离子形成配合物。通过伯胺萃取金属离子行为的研究，可发现新的萃取体系，扩大我国自行设计的伯胺N_(1923)萃取剂的应用领域，为金属离子的分离提纯工艺提供基本参数。我们实验室过去曾对伯胺N_(1923)萃取稀土（III）、Fe（III）、Zn （II）、Cd（II）、Ag（I）、Sc（III）等的机理进行了比较系统的研究。本工作是在此基础上，进一步完善及扩大N_(1923)对周期表中各族元素的萃取及应用。为此，我们选择了文献尚未报道的Ti（IV）、HgCl_2、Hg(CH_3COO)_2、Cu(CH_3COO)_2为研究对象，对它们的萃取机理进行了较详细的研究。结果表明，自由的N_(1923)或其盐对上述体系具有良好的萃取性能，并初步讨论了N_(1923)在金属离子萃取分离中的应用。一、伯胺N_(1923)萃取HgCl_2的机理 微量汞的萃取及分离对环境保护具有重要的实际意义。我们的研究结果表明，在pH值为3-4.5范围内，即使Cl~-浓度很低时，伯胺N_(1923)也能几乎定量地萃取HgCl_2，其盐酸盐亦能有效地萃取Hg（II），但两者的萃取机理不同。自由伯胺RNH_2可与HgCl_2形成配合物，其萃取机理为：RHN_(2(0)) + HgCl_2 <-> Hg(RNH_2)Cl_(2(0))对伯胺盐，实验证明其机理主要为加合反应，但当Cl~-浓度较高时，则为阴离子交换反应：加合反应：2RNH_3Cl_((0)) + HgCl_2 <-> (RNH_3Cl)_2HgCl_(2(0))交换反应：2RNH_3Cl_((0)) + HgCl_4~(2-) <-> (RNH_3)_2HgCl_(4(0)) + 2Cl~-通过考察温度对配位萃取反应的影响，求得反应的热效应ΔH = -48.82 KJ/mol，并分析了萃合物的IR、NMR谱。二、伯胺N_(1923)萃取Hg(CH_3COO)_2的机理 与HgCl_2体系相似，自由伯胺或其盐均能萃取Hg(CH_3COO)_2，萃取机理分别为：RNH_(2(0)) + Hg(CH_3CCO)_2 <-> Hg(RNH_2)(CH_3COO)_(2(0)) (CH_3COONH_3R)_(2(0)) + Hg(CH_3COO)_2 <-> (CH_3COONH_3R)_2Hg(CH_3COO)_(2(0))。在不同的萃取剂浓度下，上述反应的表观平衡常数基本不随萃取剂浓度的变化而改变，其对数值分别为：11.85、8.11。三、伯胺N_(1923)萃取Cu(CH_3COO)_2的机理 水相酸度对萃取反应的影响表明，RNH_2在近中性体系中具有很好的萃取性能，而在乙酸浓度较高的条件下，Cu（II）几乎不被RNH_2所萃取。说明自由伯胺能以配位机理的形式萃取Cu(Oh_3coo)_2，经确定，萃取反应式为：2RNH_(2(0)) + Cu(CH_3COO)_2 <-> Cu(RNH_2)_2(CH_3COO)_(2(0))并对该反应的表观平衡常数及热力学函数进行了计算。通过分析萃合物的IR谱，认为Cu(RNH_2)_2(CH_3COO)_2为平面型四配位的配合物。四、(RNH_3)_2SO_4从硫酸溶液中萃取Ti（IV）的研究 在低酸度（pH：0.84）的H_2SO_4溶液中，伯胺N_(1923)对Ti（IV）具有很强的萃取能力。用化学平衡法确定其反应式为：3(RNH_3)_2SO_(4(0)) + Ti(OH)_3~+ + SO_4~(2-) <-> 2(RNH_3)_3Ti(OH_3)(SO_4)_(2(0))我们用正十二胺代替N_(1923)，合成了上述萃合物的模拟物，经元素分析确定了萃合物的分子式：(RNH_3)_3Ti(OH)_3(SO_4)_2。并较详细地分析了萃合物的NMR、IR谱。变温NMR的结果表明，萃合物中存在两种含有活泼氢的基团，用D_2O交换后的NMR的结果亦证明了这一点。从萃合物的IR谱中，可得到SO_4~(2-)是以单齿配位形式同Ti（IV）相结合的信息。这些结果为所提出的萃取机理提供了直接的证据。并求出了上述萃取反应的表观平衡常数，其对数值为10.15，该值基本不随萃取剂浓度的变化而发生改变。反应的热效应ΔH = 66.49 KJ/mol，由计算得出的ΔG值可知，上述萃取反应有很大的向右进行的趋势。五、伯胺N_(1923)在萃取分离中的应用 为了扩大N_(1923)的应用，通过上述研究，我们对其在萃取分离中的应用进行了讨论，认为在以下几方面有可能得到应用：1、从环境废水中除Hg(II)；2、Hg(II)和Zn(II)、Cd(II)在CH_3COOH体系中的分离；3、CH_3COOH体系中Cu(II)、Co(II)、Ni(II)的萃取分离；4、在较高浓度的H_2SO_4体系中，应用(RNH_3)_2SO_4进行了Ti(IV)-Fe(II)的分离。

具有生物兴趣的金属络合物的制备与结构研究

维生素B_1(V_(B_1))是一种动物体内不可缺少的生物催化剂，它的生物功能只有在某些二价金属离子存在时才能得以发挥。本工作制备了维生素B_1与Mn(II)，Co(II)，Cu(II)，Zn(II)，Cd(II)，Hg(II)等六种过渡金属的络合物，对其进行了元素分析及红外光谱，核磁共振增，紫外一可见光谱，萤光光谱，X-射线晶体结构，热重等性质的测定。研究了上述络合物的结构特性及生成机理。结果表明。V_(B_1)与上述金属离子可以生成三种类型的络合物—离子型、M-N 配位型号以及M-O配位与离子键共存型。其中最后一种类型的V_(B_1)—金属络合物是本工作中新的发现。我们首次制得了属于M-O配位与离子键共存类型的V_(B_1)-Hg络全物并测定了它的晶体结构，首次测定了Zn-V_(B_1)络合物的晶体结构。根据光谱学，波谱学性质推测了其他络合物的化学结构。本工作还制备了维生素P的主要组分芦丁和四氯四碘萤光素二个系列各十三种稀土元素 络合物并对其进行了元素分析及热重，电导，红外光谱、紫外—可见光谱等性质的测定，研究了这些络合物的化学结构及生成机理。