一种裸眼识别Cu~(2+)和Hg~(2+)传感器的合成与性质研究

设计合成了一种香豆素修饰的罗丹明类衍生物L,用作程序型Cu2+与Hg2+检测传感器。采用核磁共振谱、高分辨质谱、红外光谱对其结构进行了表征。利用紫外光谱考察L对不同金属离子的识别作用,研究发现L可以高选择性和高灵敏度识别Cu2+。向L溶液中加入不同的金属离子时(Zn2+,Hg2+,Cu2+,Fe3+,Cd2+,Co2+,Ni 2+,Mg2+,Ca2+,Al 3+,La3+,K+,Na+,Mn2+,Pb2+和Ag+),只有Cu2+的加入会使溶液由无色变为粉色,并且在534nm出现一个新的吸收峰,说明传感器L可以裸眼识别Cu2+。通过紫外滴定得到L可以识别Cu2+的最低检测限为1.9×10-8 mol·L-1。制备了基于L的Cu2+检测试纸,该试纸可以方便快捷的检测水中的Cu2+。通过Job’s曲线和高分辨质谱确定了配合物L-Cu2+之间的结合比为1∶1。另外,若向L-Cu2+的DMSO溶液中加入1equiv.EDTA,溶液瞬间由粉色变为无色,说明EDTA可以取代L并与Cu2+结合,因此传感器L识别Cu2+是可逆的。另外,向L-Cu2+的配合物中加入Hg2+,溶液会由粉色变为无色(而加入其他阳离子没有明显变化),这可顺序实现对Hg2+的裸眼识别。通过紫外滴定计算出L-Cu2+识别Hg2+的最低检测限为2.9×10-7 mol·L-1。因此该程序型传感器L可以有序的裸眼识别Cu2+和Hg2+。     

Direct determination of total mercury in phosphate rock using alkaline fusion digestion

The aim of this work was to develop a new method to determine the mercury (Hg) concentrations in phosphate rock using a dedicated analytical instrument (the DMA80 Tricell by Milestone) that employs an integrated sequence of thermal decomposition followed by catalyst conversion, amalgamation and atomic absorption spectrophotometry. However, this instrument underestimates Hg concentrations when phosphorite and apatite rocks are investigated with a classic thermal decomposition treatment that complies with US EPA method 7473.     

Direct determination of mercury in cosmetic samples by isotope dilution inductively coupled plasma mass spectrometry after dissolution with formic acid

A new method was proposed for the accurate determination of mercury in cosmetic samples based on isotopic dilution (ID)-photochemical vapor generation (PVG)-inductively coupled plasma mass spectrometry (ICP MS) measurement. Cosmetic samples were directly dissolved in formic acid solution and subsequently subjected to PVG for the reduction of mercury into vapor species following by ICP MS detection. Therefore, the risks of analyte contamination and loss were avoided. Highly enriched ²⁰¹Hg isotopic spike is added to cosmetics and the isotope ratios of ²⁰¹Hg/²⁰²Hg were measured for the quantitation of mercury. With ID calibration, the influences originating from sample matrixes for the determination of mercury in cosmetic samples have been efficiently eliminated. The effects of several experimental parameters, such as the concentration of the formic acid, and the flow rates of carrier gas and sample were investigated. The method provided good reproducibility and the detection limits were found to be 0.6 pg mL⁻¹. Finally, the developed method was successfully applied for the determination of mercury in six cosmetic samples and a spike test was performed to verify the accuracy of the method.     

A specific and ratiometric chemosensor for Hg based on triazole coupled ortho-methoxyphenylazocalix[4]arene

Calix[4]arene 3, which contains two distal triazole groups on the lower rim and two distal o-methoxyphenylazo groups on the upper rim, was synthesized and found to be a specific and ratiometric sensor for Hg²⁺ in a polar protic solvent. A series of o-methoxyphenylazo derivatives (3, 4, 5, 7, and 9) were synthesized, which proved that the lower-rim triazoles and the hydroxyl azophenol(s) were the major ligands for metal ion binding. Though analogues 4 and 10 showed some sensitivity for Hg²⁺, compound 3 was the only ratiometric chemosensor for Hg²⁺ among the series of azocalix[4]arenes synthesized in this work. The formation of 3·Hg²⁺ complex was supported by UV/vis and NMR titration studies and Mass spectrometry. Based on the symmetrical features of NMR spectra of 3·Hg²⁺, the complex is believed to be symmetrical with respect to the calix[4]arene cavity. Furthermore, the complex was determined to be 1:1 binding stoichiometry by Job’s plot, and the association constant was determined to be 4.02×10³ M⁻¹ using Benesi-Hildebrand plot.     

Synthesis, electrochemistry and metal binding properties of monosubstituted ferrocenoyl peptides with thioether-containing sidechains

Ferrocenoyl peptides incorporating thioether functionality respond more strongly to mercury(II) than to other heavy metal ions in solution. Compounds reported previously in this context are all 1,1′-disubstituted, and all include two or more sulfur-containing amino acids. To test whether two thioether groups are required for effective mercury binding by these systems, we have prepared a series of singly-substituted ferrocenoyl peptides from ferrocenecarboxylic acid and l-methionine, S-methyl-l-cysteine or S-trityl-l-cysteine, and tested them as electrochemical probes for mercury(II). Nine ferrocenoyl peptides have been synthesised using a Boc-protecting group strategy and HBTU-mediated peptide coupling. The electrochemical properties of these compounds have been determined using cyclic voltammetry, and all show fully reversible one electron oxidation steps. Forward sweep half wave peaks (E_F), reverse sweep half wave peaks (E_R), peak separations (ΔE_P) and half wave potentials (E_1/2) are reported. Changes in the potential of the iron(II)/iron(III) redox couple of the ferrocene core have been used to quantify heavy metal-peptide interactions, revealing that these monotopic systems also respond more strongly to mercury(II) than to zinc(II), cadmium(II), silver(I) and lead(II). NMR experiments to characterise the peptide-mercury interaction implicate the thioether sulfur as the site of mercury binding and indicate 1:1 stoichiometry. The crystal structure of ferrocenoyl-S-methyl-l-cysteine methyl ester is also reported. The greater responsiveness of these systems to mercury(II) makes them interesting leads for the development of biologically inspired sensors for this toxic heavy metal.     

Stripping voltammetric determination of mercury(II) at antimony-coated carbon paste electrode

A new procedure was elaborated to determine mercury(II) using an anodic stripping square-wave voltammetry at the antimony film carbon paste electrode (SbF-CPE). In highly acidic medium of 1 M hydrochloric acid, voltammetric measurements can be realized in a wide potential window. Presence of cadmium(II) allows to separate peaks of Hg(II) and Sb(III) and apparently catalyses reoxidation of electrolytically accumulated mercury, thus allowing its determination at ppb levels. Calibration dependence was linear up to 100 ppb Hg with a detection limit of 1.3 ppb. Applicability of the method was tested on the real river water sample.     

Structural, theoretical and multinuclear NMR study of mercury(II) complexes with a new ambidentate phosphorus ylide

The reaction of the new ambidentate ylide, Ph₃PCHCOCH₂COOC₂H₅ (EAPPY), with HgX₂ (X = Cl, Br and I) in equimolar ratios using methanol as the solvent leads to binuclear complexes of the type [EAPPY·HgX₂]₂ (X = Cl (1), Br (2) and I (3)). Single crystal X-ray analysis reveals the presence of a centrosymmetric dimeric structure containing the ylide and HgX₂ (X = Br or I)_. The IR and NMR data of the product [(EAPPY)·HgCl₂]₂ (1), formed by the reaction of mercury(II) chloride with the same ylide, are similar to those of 2 and 3. Analytical data indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in each of the three products. Theoretical studies indicate that the nature of the R group in ylides of the type Ph₃PCHCOR has a weak effect on the Hg-C(ylide) bond length in binuclear Hg₂L₂I₄ complexes.     

Alkynyl Ti-M complexes with M = Cd and Hg: Synthesis, characterization, and reaction chemistry

The synthesis and properties of heterobimetallic Ti-Cd complexes of type {[Ti](μ-η¹:η²-CCR)₂}CdX₂ ([Ti] = Ti(η⁵-C₅H₄SiMe₃)₂; R = SiMe₃: 3a, X = Cl; 3b, X = Br; 3c, X = I; R = Fc: 3d, X = Br; Fc = Fe(η⁵-C₅H₄)(η⁵-C₅H₅) is reported. These compounds were accessible by treatment of [Ti](CCR)₂ (1a, R = SiMe₃; 1b, R = Fc) with the cadmium salts CdX₂ (2a, X = Cl; 2b, X = Br; 2c, X = I) in a 1:1 M ratio in diethyl ether. Dissolving, for example, 3b in tetrahydrofuran afforded coordination polymer [Cd(μ-Br)₂(thf)₂]_n (4) along with the tweezer molecule 1a. Treatment of 3b with two equiv of LiCCFc (5) gave {[Ti](μ-η¹:η²-CCSiMe₃)₂}Cd(CCFc)₂ (6) which eliminated at ambient temperature the all-carbon buta-1,3-diyne FcCC-CCFc (7) producing 1a and elemental Cd. The same reaction behavior was observed, when 2b was reacted with 5. The thus obtained bis(alkynyl) cadmium complex Cd(CCFc)₂ (8) is redox-active at low temperature producing 7 and Cd(0). When mercury halides HgX₂ (9a, X = Cl; 9b, X = Br) are used, then the titanocene dihalides [Ti]X₂ (10a, X = Cl; 10b, X = Br) together with Me₃SiCC-CCSiMe₃ (11) and Hg(0) were formed. Nevertheless, mercury acetylides were available by treatment of Hg(OAc)₂ (12) with HCCFc (13) in a 1:2 M ratio. Thus obtained Hg(CCFc)₂ (14) gave with [CuBr] (15) coordination polymer [{Hg(η²-CCFc)₂}(Cu₂(μ-Br)₂]_n (16), while with [AgPF₆] oxidation of the ferrocenyl moieties took place affording dicationic [Hg(CCFc)₂]²⁺ (18).The structures of 3b and 4 in the solid state are reported. Compound 3b shows the typical characteristics for heterobimetallic organometallic π-tweezer complexes with cadmium in a tetrahedral environment, while 4 corresponds to a one-dimensional coordination polymer in which the Cd(II) ions are linked in a edge-sharing fashion by bromide bridges in the pseudo-equatorial plane. The appropriate tetrahydrofuran molecules are completing the pseudo-octahedral coordination sphere at cadmium.The cyclic voltammogram of 14 is reported showing a single reversible redox event at E⁰ = 0.108 V with ΔE_p = 76 mV indicating that there is no communication between the Fc termini along the mercury acetylide unit.     

氢化物发生-原子荧光光谱法测定水中汞的测量不确定度分析

对氢化物发生-原子荧光光谱法测定水中汞的分析方法的测量不确定度进行了估计。认为在分析的全过程中,标准溶液的配制、校准曲线的绘制以及试样的分析是测量不确定度的三项主要来源。基于这一认识,建立了相应的数学模型,对关系式中的各个变量作了分析并对其不确定度进行量化。最后,按统计学的计算方法给出了合成不确定度和扩展不确定度。     

Synthesis and Characterization of [Hg(sulfamethoxazolato)2]·2DMSO and[Cu2(μ‐CH3CO2)4(sulfamethoxazole)2]

[Hg(sulfamethoxazolato)₂]·2DMSO ( 1 ) and [Cu₂(CH₃COO)₄(sulfa‐methoxazole)₂] ( 2 ) can be obtained by the reaction of sulfamethoxazole with mercury acetate or copper acetate in methanol. The structures of the two complexes were characterized by single crystal X—ray diffractometry. Compound 1 consists of sulfamethoxazolato ligands bridging the metal ions building an unidimensional chain. Two solvent dimethylsulfoxide molecules are involved via N‐H···O hydrogen bridges. The mercury atom shows a linear primary coordination arrangement formed by two trans deprotonated sulfonamidic nitrogen atoms. The overall coordination around the metal atom may be regarded as a strongly distorted octahedron when the interactions of mercury with four sulfonamidic oxygen atoms [bond distances of 2.761(4) Å—2.971(4) Å] are also considered to build an equatorial plane and the N1 and N1′ atoms [bond distance of 2.037(5) Å] occupy the apical positions. Compound 2 is a dinuclear complex in which the copper ions are bridged by four syn‐syn acetate ligands which are related by a symmetry centre located in the centre of the complex. Each copper atom presents a nearly octahedral coordination where the equatorial plane is formed by four oxygen atoms and an isoxazolic nitrogen atom and the second copper atom occupy the apical positions.