稀土铽离子对辣根过氧化物酶活力指数的影响(英)

0IntroductionHorseradishperoxidase(HRP)isaplanthemeenzymecatalyzingoxidationofawidevarietyofaro鄄maticmoleculesbyhydrogenperoxideanditisthemostwidelystudiedmemberoftheperoxidasefamily[1~3].ThecrystalstructureofHRPhasbeensolved[2].ThestructuralfeaturesofHR…     

Gravimetric Determination of Mercury(II) and Vanadium(IV) with Benzoylacetanilide

Abstract

Gravimetric methods for the determinations of mercury(II) and vanadium(IV) with benzoylacetanilide have been described. These metals have been separated from commonly associated ions and a procedure for the determination of vanadium content of steel has been developed. By these methods, 14 to 50 mg. of mercury and 5 to 20 mg. of vanadium have been estimated with relative standard deviations of 0.18% and 0.10%, respectively.     

Selective Detection of Mercury（Ⅱ） and Copper（Ⅱ） Based on the Opposite Size-dependent Fluorescence Quenching of CdTe Quantum Dots

Three different size CdTe quantum dots （QDs） capped by 3-mercaptopropionic acid （MPA） have been prepared in aqueous solutions, and their interactions with Cu^2＋ and Hg^2＋ have been investigated. The opposite size-dependent fluorescence quenching of CdTe QDs by Hg^2＋ and Cu^2＋ was observed： Hg^2＋ quenched smaller particles more efficiently than larger ones while larger particles were more markedly quenched by Cu^2＋. Based on the different size responses, Hg^2＋ and Cu^2＋ were respectively detected with high sensitivity and selectivity, for the first time, using the QDs with different sizes but the same components and capping ligands.     

Improvement of an Enzyme Immunoassay for the Determination of Mercury(II)

Three systems were tested for the optimization of a heterogenous non-competitive enzyme immunoassay (EIA) for the determination of Hg (II). The sensitivity of the non optimized Hg-EIA with a detection limit of 2.1 μg/L Hg (II) was improved by an avidin-biotin-complex (ABC) amplification system to a 2-fold lower detection limit (1.1 μg/L Hg (II)). A conventional competitive ElA with the competition reaction between bound and free Hg (II) for antibody (ab) binding sites yielded a detection limit of 1.0 μg/L Hg (II). Further improvement of sensitivity could be achieved by a competitive displacement EIA. In this case ab molecules bound to immobilized haptens are displaced in the next step by free Hg (II). The detection limit of the displacement approach is 0.4 μg/L Hg (II).     

The Solvent Effect on Composition and Dimensionality of Mercury(II) Complexes with Picolinic Acid

Three new mercury(II) coordination compounds, {[HgCl(pic)]}_n (1), [HgCl(pic)(picH)] (2), and [HgBr(pic)(picH)] (3) (picH = pyridine-2-carboxylic acid, picolinic acid) were prepared by reactions of the corresponding mercury(II) halides and picolinic acid in an aqueous (1) or alcohol–methanol or ethanol (2 and 3) solutions. Two different types of coordination compounds were obtained depending on the solvent used. The crystal structures were determined by the single-crystal X-ray structural analysis. Compound 1 is a one-dimensional (1-D) coordination polymer with mercury(II) ions bridged by chelating and bridging N,O,O′-picolinate ions. Each mercury(II) ion is four-coordinated with a bidentate picolinate ion, a carboxylate O atom from the symmetry-related picolinate ion and with a chloride ion; the resulting coordination environment can be described as a highly distorted tetrahedron. Compounds 2 and 3 are isostructural mononuclear coordination compounds, each mercury(II) ion being coordinated with the respective halide ion, N,O-bidentate picolinate ion, and N,O-bidentate picolinic acid in a highly distorted square-pyramidal coordination environment. Compounds 1–3 were characterized by IR spectroscopy, PXRD, and thermal methods (TGA/DSC) in the solid state and by ¹H and ¹³C NMR spectroscopy in the DMSO solution.     

Synthesis, Spectral and Thermal Studies of o-vanillin Oxime Complexes of Zinc(II), Cadmium(II) and Mercury(II)

Zinc(II), cadmium(II) and mercury(II) complexes of o-vanillin oxime have been synthesized and characterized by different physicochemical techniques. All the complexes have been subjected to non-isothermal decomposition studies in nitrogen atmosphere using thermogravimetry. The kinetic parameters for the decomposition of these complexes were evaluated using different methods and comparatively better results were obtained by these different methods. It has also been found that the decomposition processes of all these complexes follow first order kinetics. This revised version was published online in July 2006 with corrections to the Cover Date.     

外源镧(III)对辣根过氧化物酶的结构的影响

运用荧光光谱、傅立叶变换红外光谱以及曲线拟合等技术研究了镧离子对辣根过氧化物酶的结构的影响 .结果表明荧光增强的原因是由于镧离子的加入使镧离子和酶结合 ,酶的二级结构发生变化 ,导致荧光发色基团所处的微环境也相应变化 ;并运用它推测了镧离子对该酶的激活作用机制 .     

Indirect Complexometric Determination of Mercury(II) Using Potassium Bromide as Selective Masking Agent

 A complexometric method for the determination of mercury in presence of other metal ions based on the selective masking ability of potassium bromide towards mercury is described. Mercury(II) present in a given sample solution is first complexed with a known excess of EDTA and the surplus EDTA is titrated against zinc sulfate solution at pH 5–6 using xylenol orange as the indicator. A known excess of 10% solution of potassium bromide is then added and the EDTA released from Hg-EDTA complex is titrated against standard zinc sulfate solution. Reproducible and accurate results are obtained for 8 mg to 250 mg of mercury(II) with a relative error ± 0.28% and standard deviations ≤0.5 mg. The interference of various ions is studied. This method was applied to the determination of mercury(II) in its alloys. Received April 18, 2001 Revision October 10, 2001     

Investigation of 3-amino-1,2,4-triazole azodye derivatives as reagents for determination of mercury(II)

The reaction of mercury(II) with 3-(2,4-dihydroxyphen-1-ylazo)-1,2,4-triazole (HL¹), 3-(2-hydroxy-5-methylphen-1-ylazo)-1,2,4-triazole (HL²), 3-(2-hydroxy-5-ethoxycarbonylphen-1-ylazo)-1,2,4-triazole (HL³), 3-(2-hydroxy-5-acetylphen-1-ylazo)-1,2,4-triazole (HL⁴), 3-(2-hydroxy-5-formylphen-1-ylazo)-1,2,4-triazole (HL⁵), and 3-(2-hydroxy-5-bromophen-1-ylazo)-1,2,4-triazole (HL⁶) was studied. A new, direct, and simple procedure was suggested for the spectrophotometric determination of mercury(II) based on its complexation reaction with HL¹-HL⁶. The best reagent was found to be HL³ due to its high sensitivity and selectivity. In aqueous media of pH 9.0 containing 40 vol. % of methanol, Hg(II) reacts with HL³ to form a 1:2 (Hg(II) · HL³) complex having a sensitive absorption peak at 490 nm with the molar extinction coefficient of 3.31 × 10⁴ L mol⁻¹ cm⁻¹ using 4 × 10⁻⁴ M of the reagent. Beer’s law is obeyed over the range from 0.00 μg mL⁻¹ to 12.04 μg mL⁻¹ of mercury(II). The proposed method was applied in the determination of mercury(II) in tap water, seawater and synthetic seawater samples, without the need of prior treatment, with satisfactory results.     

Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity

In this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF₆ and [Ru(LLL)(dpp)OH₂](PF₆)₂ (LLL=tpy =2,2’ : 6’,2’’-terpyridine; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazine and dpp=2,3-bis(2-pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF₆, the complete structure was determined by X-ray diffraction. Catalytic studies of aqua-complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD-DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV-Visible bands and redox states.     

Synthesis and Multinuclear NMR Study of Benzoyl Methylene Triparatolylphosphorane Ylide and the Reaction of this Ylide with Mercury(II) Halides

The reaction of the title ylide {PhCOCHP(p-tolyl)₃} with Pd(II), Pt(II). Hg(II), and Ag(I) in equimolar ratios using CH₃CN, CH₃OH, and CH₂Cl₂ as solvents have yielded [{(p-tolyl)₃PCHCOC₆H₅} PdCl₂]₂ (I), [{(p-tolyl)₃ PCHCOC₆H₅} PtCl₂]₂(2), [Hg(NO₃)₂ {(p-tolyl)₃ PCHCOC₆H₅}](3), and [Ag{(p-tolyl)₃ PCHCOC₆H₅ < eqid1 > ₂]⁺ (4). The IR, ¹H ¹³C, and ³¹P NMR together with micro analysis data of the products were obtained.     

Syntheses and spectroscopic studies on zinc(II) and mercury(II) complexes of isatin-3-thiosemicarbazone

Zinc(II) and mercury(II) complexes were prepared by reacting isatin-3-thiosemicarbazone (ISTSCH) with zinc(II) acetate or mercury(II) bromide. The complexes were characterized by IR, Raman, diffuse reflectance, ¹H and ¹³C NMR spectra and elemental analysis. Tetrahedral structures for Zn(ISTSC)₂ and Hg(ISTSCH)Br₂ are suggested.     

Determination of Fluoride,Cyanide, and Thiocyanate Using Horseradish Peroxidase Immobilized on Modified Silica Gel

Abstract

Silica gels modified with different functional groups (amino, epoxy, cycloepoxy, isocyanate, and thiocyanate) were used for the covalent immobilization of horseradish peroxidase (HRP). The catalytic activity and stability of the obtained enzyme preparations were studied using the reaction of o‐dianisidine oxidation with hydrogen peroxide as an indicator. The covalent immobilization of horseradish peroxidase using silica gel modified with thiocyanate groups provided not only the improvement of the enzyme stability, but also the development of the sensitive, rapid, and simple procedures for the determination of fluoride, cyanide, and thiocyanate. Enzymatic determination of inorganic anions is based on their inhibitory effect on the enzyme as the ligands capable to form stable complexes with Fe(III)‐HRP cofactor. The proposed procedures were applied for the determination of F^? in mineral and drinking waters; CN^? and SCN^?—in biological fluids (blood and saliva).     

Sulfur-Bonded Coordination Compounds of Palladium(II) and Platinum(II) and Their Antimicrobial Activity

The synthetic, spectroscopic, and biological studies of some new palladium(II) and platinum(II) complexes derived from biologically active sulfur donor ligands 1H-indol-2,3-dione benzothiazoline (Bzt ₁ H) and 5-nitro-1H-indol-2,3-dione benzothiazoline (Bzt ₂ H) have been described. The reactions were carried out in 1:2 molar ratios. The authenticity of the benzothiazolines and their complexes has been established on the basis of elemental analyses; molecular weight determinations; and IR, ¹ H NMR, ¹³ C NMR, and UV spectral studies. Based on IR and ¹ H NMR spectral studies, a square-planar structure has been assigned to these complexes. Studies were conducted to assess the comparative growth inhibiting potential of the synthesized complexes against the benzothiazolines for a variety of fungal and bacterial strains. The studies demonstrate that the ligands and complexes possess antimicrobial properties. Further, it was noted that the growth-inhibiting potential of the complexes is greater than the parent benzothiazolines.     

Bis(2-mercaptobenzoxazolato)mercury(II) and bis(2-pyridinethiolato)mercury(II) complexes as carriers for thiocyanate selective electrodes

Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on bis(2-mercaptobenzoxazolato)mercury(II) [Hg(MBO)₂] and bis(2-pyridinethiolato)mercury(II) [Hg(PT)₂] complexes as new carriers for thiocyanate-selective electrodes are reported. The electrodes were prepared by coating the membrane solution containing PVC, plasticizer, carriers and additives on the surface of graphite electrodes. Influence of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses towards thiocyanate over a wide concentration range of 1×10⁻⁶ to 0.1 M, with slopes of 60.6±0.8 and 57.5±1.2 mV per decade of thiocyanate concentration for Hg(MBO)₂ and Hg(PT)₂ carriers, respectively, over a wide pH range of 3-11. The limit of detection for both electrodes was ∼6×10⁻⁷ M. The sensors have response times of ≤5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show fairly good discrimination of thiocyanate over several inorganic and organic anions. The electrodes were successfully applied to direct determination of thiocyanate in saliva and as indicator electrodes in precipitation titrations.     

Simultaneous Determination of Copper (II) and Mercury (II) by Using a Zero-Crossing Method

Abstract

The application of a zero-crossing method to the simultaneous determination of copper (II) and mercury (II) with methylethylenediaminetetraacetic acid (MEDTA) is described. The procedure does not require equations to be solved, and it is suitable for concentrations of 0.008–0.036 mg ml^?1 of copper and 0.025–0.300 mg ml^?1 of mercury. The main interferences, both anionic and cationic, were easily eliminated. The method was applied to different aqueous matrices. It was compared with an atomic absorption spectrophotometry method (AA) and good results were obtained.     

Simple flow injection method for simultaneous spectrophotometric determination of Fe(II) and Fe(III)

The method is based on spectrophotometric determination of Fe(II) and Fe(III) at a single wavelength (530 nm) with the use of a dedicated reversed-flow injection system. In the system, EDTA solution is injected into a carrier stream (HNO₃) and then merged with a sample stream containing a mixture of sulfosalicylic acid and 1,10-phenanthroline as indicators. In an acid environment (pH ≅ 3) the indicators form complexes with both Fe(III) and Fe(II), but EDTA replaces sulfosalicylic acid, forming a more stable colourless complex with Fe(III), whereas Fe(II) remains in a complex with 1,10-phenenthroline. As a result, the area and minimum of the characteristic peak can be exploited as measures corresponding to the Fe(III) and Fe(II) concentrations, respectively. The analytes were not found to affect each other's signals, hence two analytical curves were constructed with the use of a set of standard solutions, each containing Fe(II) and Fe(III). Both analytes were determined in synthetic samples within the concentration ranges of 0.05–4.0 and 0.09–6.0 mg L⁻¹, respectively, with precision less than 1.5 and 2.6% (RSD) and with accuracy less than 4.3 and 5.6% (RE). The method was applied to determination of the analytes in water samples collected from artesian wells and the results of the determination were consistent with those obtained using the ICP-OES technique.     

Adsorption of Mercury(II) on Amidoxime Chelating Resins with Magnetic Properties

Two amidoxime chelating resins were prepared. The preparation process was carried out through copolymerization of acrylonitrile with N,N′-methylene-bis-acrylamide (MBA) as a crosslinker in the presence and absence of magnetite (Fe₃O₄) particles. The resins obtained were subsequently treated with hydroxylamine to give the corresponding amidoxime chelating resins. The uptake behavior of the resins toward Hg(II) in aqueous solutions using batch and column techniques was studied. The oxide containing resin gave higher uptake capacities relative to oxide free resin confirming the advantage of embedded particles on the uptake capacity. Thermodynamic and kinetic parameters of the uptake process were calculated. Regeneration of the resins was carried out using 0.5 M KI and the desorption ratio was found to be more than 97%.     

Kinetic Determination of Trace Amounts of Cu(II) in Water Based on its Catalytic Effect on the Reaction of Mercaptosuccinic Acid and Cr(VI)

 A kinetic method is presented for the determination of Cu(II) in water. It is based on the catalytic effect of Cu(II) on the oxidation of mercaptosuccinic acid by chromate in acidic media. The extent of the reaction is followed spectrophotometrically at 345 nm and pseudo-first order rate coefficients are determined as a function of catalyst concentration. The optimum operating conditions regarding ionic strength, temperature and concentration of reagents were established. Interference by several ionic species was studied and the effects of Fe(III) and Pb(II) were suppressed by complexation with pyrophosphate. Calibration lines were obtained for both low (30–640 μg · l⁻¹) and high (640–1500 μg · l⁻¹) catalyst concentrations. The relative standard deviation for 625 μg · l⁻¹ Cu(II) is 6.1% (n = 5). The detection limit is 22 μg · l⁻¹. The method was applied to real samples of river water of the mining region of Baia-Mare, Northern Romania. The results were compared to those obtained by an officially standardized AAS method. Good agreement was attained. The method is inexpensive, fairly rapid and sensitive. Moreover, its working range covers the exact range of concentrations usually encountered in the mentioned geographic area. Received July 28, 2000; accepted December 10, 2001; published online June 24, 2002     

Some neutral three-coordinate complexes of mercury(II) halides and pseudohalides with N-methylnicotinamide

Coordination compounds of mercury(II) chloride, bromide, cyanide and thiocyanate with N-methylnicotinamide, a potentially bidentate ligand, have been prepared. The complexesisolated have 1∶1 (metal:ligand)stoichiometry. Molecular weight measurements in molten camphor indicate that the mercury (II) chloride and bromide complexes are monomeric. Based on conductance values, molecular weight determinations and infrared spectral data, it is inferred that in the solid state in all these complexes the metal ion has a coordination number three and is bonded to the N-methylnicotinamide via its pyridine ring nitrogen, and is terminally bonded to the halogen/pseudohalogens.