膦系阻垢剂阻碳酸钙垢机理的研究

在模拟循环水中, 通过静态阻垢实验研究了HEDP, PBTCA, ATMP和EDTMP对碳酸钙的阻垢性能, 在相同的加药浓度下(按物质的量浓度计)阻垢性能的强弱顺序为HEDP＞PBTCA＞ATMP＞EDTMP; 同时采用分子动力学方法, 模拟计算了阻垢剂负二价离子与方解石(104), (102), (202)和(113)面的相互作用. 结果表明: 阻垢剂分子中的膦酸基团和羧酸基团与碳酸钙中的Ca^2＋形成的离子键对吸附起到了主要作用, 同时阻垢剂与晶面间存在较弱的范德华力相互作用. 阻垢剂与各晶面的结合能强弱顺序为(113)≥(102)≥(202)＞(104); 分子中的羟基易与垢晶面形成氢键而加强阻垢效果; 羧基的位置不同对阻垢作用的影响不同. 将静态阻垢的实验结果与分子动力学模拟结果进行了相关性分析, 发现阻垢剂在(104)面和(102)面上的吸附对阻垢作用的贡献较大.     

Copper-complexation index as a polarographic summation parameter for the determination of chelating agents in water

Polarography of the copper(II)-complexes of chelating agents is shown to be a suitable basis for a summation parameter for the total concentration of these chemicals in water (expressed as the copper-complexation index). Using 12 chelating agents (ATMP, BAED, CDTA, DTPA, DTPMP, EDTA, EDTMP, EDTP, EGTA, HEDP, NTA, PBTC) all listed in DIN 38409-H26 and DIN 38413-P5 a satisfactory reproducibility of the method used was obtained. In addition several commercial tensides, detergents in washing and deliming products were investigated.     

Remote in situ analytical spectroscopy and its applications in the nuclear industry

Heavy metals exist in natural waters in different species. Mobility and bioavailability of bound metals can be influenced by some complex factors in the aquatic environment. Therefore, it is useful to determine the complexation properties of various ligands influenced by different metals. The copper and zinc complexation capacity was determined for a natural ligand (fulvic acid) and anthropogenic pollutants (e.g. nitrilotriacetic acid and ethylenediaminetetraacetic acid). The interactions between several ligands and metal ions and their effects on the complexation capacity were analyzed in particular. Applying methods of experimental design, such as multifactorial plans, it is possible to determine influence and interaction of various parameters (e.g. concentration of zinc or copper) by a minimum number of experiments. Differential pulse polarography was used for the determination of the complexation capacity. Methods of parametric and robust multiple linear regressions were applied for the interpretation of the measured values.     

Polymer supported catalysts for oxidation of phenol and cyclohexene using hydrogen peroxide as oxidant

Polymer supported transition metal complexes of N,N′-bis (o-hydroxy acetophenone) hydrazine (HPHZ) Schiff base were prepared by anchoring its amino derivative Schiff base (AHPHZ) on cross-linked (6 wt%) polymer beads and then loading iron(III), copper(II) and zinc(II) ions in methanol. The loading of HPHZ Schiff base on polymer beads was 3.436 mmol g⁻¹ and efficiency of complexation of polymer anchored HPHZ Schiff base for iron(III), copper(II) and zinc(II) ions was 83.21, 83.40 and 83.17%, respectively. The efficiency of complexation of unsupported HPHZ Schiff base for these metal ions was lower than polymer supported HPHZ Schiff base. The structural information obtained by spectral, magnetic and elemental analysis has suggested octahedral and square planar geometry for iron(III) and copper(II) ions complexes, respectively, with paramagnetic behavior, but zinc(II) ions complexes were tetrahedral in shape with diamagnetic behavior. The complexation with metal ions has increased thermal stability of polymer anchored HPHZ Schiff base. The catalytic activity of unsupported and polymer supported HPHZ Schiff base complexes of metal ions was evaluated by studying the oxidation of phenol (Ph) and epoxidation of cyclohexene (CH). The polymer supported metal complexes showed better catalytic activity than unsupported metal complexes. The catalytic activity of metal complexes was optimum at a molar ratio of 1:1:1 of substrate to oxidant and catalyst. The selectivity for catechol (CTL) and epoxy cyclohexane (ECH) in oxidation of phenol and epoxidation of cyclohexene was better with polymer supported metal complexes in comparison to unsupported metal complexes. The energy of activation for oxidation of phenol (22.8 kJ mol⁻¹) and epoxidation of cyclohexene (8.9 kJ mol⁻¹) was lowest with polymer supported complexes of iron(III) ions than polymer supported Schiff base complexes of copper(II) and zinc(II) ions.     

Catalytic activities of polymer‐supported metal complexes in oxidation of phenol and epoxidation of cyclohexene

The metal complexes of N, N′‐bis (o‐hydroxy acetophenone) propylene diamine (HPPn) Schiff base were supported on cross‐linked polystyrene beads. The complexation of iron(III), copper(II), and zinc(II) ions on polymer‐anchored HPPn Schiff base was 83.4, 85.7, and 84.5 wt%, respectively, whereas the complexation of these metal ions on unsupported HPPn Schiff base was 82.3, 84.5, and 83.9 wt%. The iron(III) complexes of HPPn Schiff base were octahedral in geometry, whereas copper(II) and zinc(II) ions complexes were square planar and tetrahedral. Complexation of metal ions increased the thermal stability of HPPn Schiff base. Catalytic activity of metal complexes was tested by studying the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The polymer‐supported HPPn Schiff base complexes of iron(III) ions showed 73.0 wt% conversion of phenol and 90.6 wt% conversion of cyclohexene at a molar ratio of 1:1:1 of substrate to catalyst and hydrogen peroxide, but unsupported complexes of iron(III) ions showed 63.8 wt% conversion for phenol and 83.2 wt% conversion for cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 and 98.3 wt%, respectively with supported HPPn Schiff base complexes of iron(III) ions but was lower with HPPn Schiff base complexes of copper(II) and zinc(II) ions. Activation energy for the epoxidation of cyclohexene and phenol conversion with unsupported HPPn Schiff base complexes of iron(III) ions was 16.6 kJ mol^?1 and 21.2 kJ mol^?1, respectively, but was lower with supported complexes of iron(III) ions. Copyright © 2007 John Wiley & Sons, Ltd.     

Polymer Supported Schiff Base Complexes of Iron(III), Cobalt(II) and Nickel(II) Ions and their Catalytic Activity in Oxidation of Phenol and Cyclohexene

The polymer supported transition metal complexes of N,N′‐bis (o‐hydroxy acetophenone) hydrazine (HPHZ) Schiff base were prepared by immobilization of N,N′‐bis(4‐amino‐o‐hydroxyacetophenone)hydrazine (AHPHZ) Schiff base on chloromethylated polystyrene beads of a constant degree of crosslinking and then loading iron(III), cobalt(II) and nickel(II) ions in methanol. The complexation of polymer anchored HPHZ Schiff base with iron(III), cobalt(II) and nickel(II) ions was 83.30%, 84.20% and 87.80%, respectively, whereas with unsupported HPHZ Schiff base, the complexation of these metal ions was 80.3%, 79.90% and 85.63%. The unsupported and polymer supported metal complexes were characterized for their structures using I.R, UV and elemental analysis. The iron(III) complexes of HPHZ Schiff base were octahedral in geometry, whereas cobalt(II) and nickel(II) complexes showed square planar structures as supported by UV and magnetic measurements. The thermogravimetric analysis (TGA) of HPHZ Schiff base and its metal complexes was used to analyze the variation in thermal stability of HPHZ Schiff base on complexation with metal ions. The HPHZ Schiff base showed a weight loss of 58% at 500°C, but its iron(III), cobalt(II) and nickel(II) ions complexes have shown a weight loss of 30%, 52% and 45% at same temperature. The catalytic activity of metal complexes was tested by studying the oxidation of phenol and epoxidation of cyclohexene in presence of hydrogen peroxide as an oxidant. The supported HPHZ Schiff base complexes of iron(III) ions showed 64.0% conversion for phenol and 81.3% conversion for cyclohexene at a molar ratio of 1∶1∶1 of substrate to catalyst and hydrogen peroxide, but unsupported complexes of iron(III) ions showed 55.5% conversion for phenol and 66.4% conversion for cyclohexene at 1∶1∶1 molar ratio of substrate to catalyst and hydrogen peroxide. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 90.5% and 96.5% with supported HPHZ Schiff base complexes of iron(III) ions, but was found to be low with cobalt(II) and nickel(II) ions complexes of Schiff base. The selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was different with studied metal ions and varied with molar ratio of metal ions in the reaction mixture. The selectivity was constant on varying the molar ratio of hydrogen peroxide and substrate. The energy of activation for epoxidation of cyclohexene and phenol conversion in presence of polymer supported HPHZ Schiff base complexes of iron(III) ions was 8.9 kJ mol^?1 and 22.8 kJ mol^?1, respectively, but was high with Schiff base complexes of cobalt(II) and nickel(II) ions and with unsupported Schiff base complexes.     

Reexamination of the ORAC assay: effect of metal ions

The oxygen radical absorbance capacity (ORAC) assay method has been employed extensively in the field of antioxidant and oxidative stress. It uses fluorescein as probe for oxidation by peroxyl radical. Hundreds of reports have been published on the use of this method to determine antioxidant capacity in food and biological samples. The question is whether the results of all these reports are influenced by antioxidant autoxidation, which occurs during the ORAC test. Indeed, the presence of metal ions in the studied matrix will influence antioxidant stability, thereby leading to the underestimation of their antioxidant properties. Ethylenediaminetetraacetic acid hydrate (EDTA) can be used as a metal complexation agent. This paper examines the effect of the addition of EDTA on the ORAC values of pure compounds (quercetin, ascorbic, and dehydroascorbic acid) and five food juices (kiwi, orange, tomato, red grape, and apple). Metal complexation by EDTA (80 μM) clearly increased the ORAC values, given that the antioxidant was protected against rapid autoxidation incited by trace metal ions within samples and then by free radicals. Our finding also undoubtedly demonstrated that the number of literature values is potentially underestimated.     

Calorimetric investigation of complex formation of some humic compounds

In the present paper we studied the complexation capacity towards copper ion of fulvic acids extracted from Arno River and Lake Como sediments, as well as Antarctic Sea water at different pHs in order to evaluate the interaction of different complexing groups of fulvic acids with copper ions. The binding capacity studies were carried out by means of titration with a copper-selective electrode and calorimetric measurements. For the same purpose, the heat of reaction in the complexation of copper ions with small molecules containing functional groups similar to fulvic acid was also determined. Titration results indicated that the fraction of bound metal increases with increasing pH (from 5 to 7). This may be accounted for by the increase in the ionisation of the fulvic acid molecule. Results obtained from calorimetric measurements show that the quantity of total heat involved in the metal ion-fulvate interactions determines a decreasing exothermic response with increasing pH values. This revised version was published online in July 2006 with corrections to the Cover Date.     

Spectral and thermal studies on new hydrazinium metal sulfite dihydrates

Some new hydrazinium transition metal sulfite dihydrate complexes of the formula (N₂H₅)₂M(SO₃)₂(H₂O)₂ where M=Fe, Co, Ni, Cu and Zn have been prepared and characterized by hydrazine and metal analyses, magnetic studies, electronic and infrared spectra and thermal analysis. The magnetic studies coupled with electronic spectra of iron, cobalt, nickel and copper complexes indicate their high spin octahedral nature. However the zinc complex is diamagnetic and show only the charge transfer transition. The infrared spectra shows that both the hydrazinium ions are coordinated to the metal ions, the sulfite ions are present as bidentate ligand. The simultaneous TG-DTA of these complexes were investigated in air and nitrogen atmospheres. In air, cobalt, nickel and zinc complexes give respective metal sulfate as the final residue while iron and copper complexes give the mixture of respective metal oxide and sulfate as the decomposition product. In nitrogen atmosphere respective metal sulfites are formed as the end residue.     

Silica-immobilized formylsalicylic acid as a selective phase for the extraction of iron(III)

The immobilization of formylsalicylic acid compounds on the surface of amino group-containing silica gel phases is described. The resulting phases were tested for the extraction of iron(III) and showed an exchange capacity of 0.95-0.96 mmol g(-1). The other metal ions tested showed lower metal capacity values than iron(III). The selectivity of the phases tested for the extraction of iron(III) from a mixture containing several other metal ions was evaluated using atomic absorption spectrometry. A method for the recycling of immobilized silica gel after metal extraction is described for practical applications.     

Studies on the liquid-liquid extraction of iron(III) and titanium(IV) with 3-phenyl-4-benzoyl-5-isoxazolone

The extraction behaviour of iron(III) and titanium(IV) from acidic chloride solutions has been investigated using 3-phenyl-4-benzoyl-5-isoxazolone (HPBI) in xylene as an extractant. The results demonstrate that these metal ions are extracted into xylene as Fe(PBI)(3) and TiO(PBI)(2). The equilibrium constants of the extracted complexes have been deduced by non-linear regression analysis by taking into account complexation of metal ion with inorganic ligands in the aqueous phase and all plausible complexes extracted into the organic phase. IR and proton NMR ((1)H NMR) spectra were used to further clarify the nature of complexes extracted into organic phase. The effect of the nature of the diluent on the extraction of iron(III) and titanium(IV) has been studied and correlated with dielectric constants. The extraction behaviour of titanium(IV) has also been compared with that of other metal ions, viz. magnesium(II), vanadium(V), chromium(VI), iron(III), manganese(II), zinc(II) and zirconium(IV), which are associated with the titanium in waste chloride liquors of the titanium-mineral-processing industry.     

Characterisation of human metallothioneins from foetal liver and adult kidney using differential pulse polarography

The electrochemical behaviour of four human metallothioneins (MT) from foetal liver and adult kidney with respect to solution pH as well as the influence of the addition of cadmium and/or zinc were studied using differential pulse polarography. The complexation equilibrium of dissociation and the formation from their metal depleted form was investigated, going from basic to acid solution and vice versa. The stability of these human MTs with respect to changes in the pH of the solution is low. In fact, the complexation equilibrium is not reversible and consequently, the protein, at acid pH, is denatured and the metal binding capacity to complex the cations through the thiol groups is lost. In the case of some of these MTs two different electrochemical responses due to the reduction of complexed Cd(II), as well as to the Zn(II) complexes were distinguished. The predominance of each of these two species for both cations seems to depend on the total concentration, on the ratio between zinc and cadmium concentrations and on the solution pH. In each of the molecules studied, the addition of zinc provokes the transformation of the peak attributed to the Cd-Thionein complex CdT, initially found in the native MT, into another form, CdT′, having different characteristics to the initial one. The MTs are able to incorporate the added metal ions into their molecule. This implies a new reorganisation of the initial molecule in which both cadmium and zinc complexes are involved. The apparent stability constants of the Cd-MT, Zn-MT and Hg-MT complexes were estimated at different pH values.     

Nuclear magnetic resonance relaxometry as a spectroscopic probe of the coordination sphere of a paramagnetic metal bound to a humic acid mixture

Protons on water molecules are strongly affected by paramagnetic ions. Since the acid-base properties of water facilitate rapid proton exchange, a single proton nuclear magnetic resonance (NMR) signal is seen in aqueous solutions of paramagnetic ions. Proton relaxation times are significantly affected by paramagnetic species and the readily detectable single signal serves as a powerful amplifier of the information contained concerning the protons in the paramagnetic environment. Where water molecules coordinated to free paramagnetic ions and to metal complexes of ligands that form non-labile (on the NMR time scale) complexes, the effects on water in the two environments can be distinguished. This can provide information on the nature of the ligand binding sites. The example of Cu²⁺ bound to the Laurentian humic acid mixture reported here using convenient low field NMR relaxometers shows that the information can enrich our understanding of complexation and speciation in the presence of complex mixture ligands characteristic of natural water systems. In this case, the data underline the role of aggregation and conformation in defining the complexation sites.     

Preferential recognition of zinc ions through a new anthraquinonoidal calix[4]arene

A novel anthraquinonoidal calix[4]arene derivative was designed and synthesized for the preferential recognition of biologically important zinc in preference to prominently similar cadmium ions and other metal ions via quenching of fluorescence intensity. The stoichiometry of host guest complexation has been determined to be 1:1. The fluorescence changes associated with the recognition event may be attributed to the interaction of zinc ions with the nitrogenous functionality attached at the lower rim of calix[4]arene cavity which allows spatial disposition of the anthraquinonoid segments.     

A new bis(3-hydroxy-4-pyridinone)-IDA derivative as a potential therapeutic chelating agent. Synthesis, metal-complexation and biological assays

A new bis(3-hydroxy-4-pyridinone) derivative of iminodiacetic acid, imino-bis(acetyl(1-(3'-aminopropyl)-3-hydroxy-2-methyl-4-pyridinone)), IDAPr(3,4-HP)(2), has been prepared and studied in its interaction with a set of hard metal ions. This tetradentate ligand presents a much higher chelating efficiency for trivalent hard metal ions (Fe, Ga, Al) than the monodentate derivative Deferriprone, namely at the diluted conditions prevailing in physiological conditions and at low clinical doses. A similar behaviour was also observed for the complexation with Zn(II) but at a significantly lower extent. This compound presents a moderate hydrophilic character at physiological pH (logD=-1.72). In vivo assays showed much more rapid clearance of (67)Ga from most tissues of metal-loaded mice than the drug Deferriprone and the radioactivity excretion occurs mostly through the kidneys. Therefore, results from in vitro and in vivo studies indicated good perspectives for this compound to be a potential decorporating agent for hard metal ions in overload situations without depletion of essential metal ions such as zinc.     

Alkali cation attachment to derivatized fullerenes studied by matrix-assisted laser desorption/ionization

The complexation of alkali metal ions with amphiphilic fullerene derivatives has been investigated by matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry. The formation of analyte ions occurs via two competing mechanisms including electron transfer from matrix-derived ions and metal ion attachment. The interplay of these processes has been examined by laser fluence dependent sample activation and by variation of the target composition. The attachment of metal ions has been established as the gentler and thus more efficient route towards the formation of intact analyte ions. Investigations into the metal ion complexation have been conducted to reveal the reactivity order of the alkali metals in these reactions and to elucidate the influence of structural differences of the analytes, as well as to unravel effects caused by the anionic counter ion of the metal. The experimental data have been derived by two complementary approaches. Competing reactants were either studied simultaneously, so that the product distribution would provide direct insight into the reactivity pattern, and/or product distributions were obtained in a large variety of separate experiments and normalized for reliable comparison. It has been found that the extent to which complexation is observed follows the charge density order of the alkali metal ions. The structural features of the fullerene-attached ligands were of profound influence on the attachment of the metal ion, inducing enhanced selectivity for the complexation with less reactive metals. The metal ion attachment is reduced with the use of smaller anionic counter ions. Rationalization of these findings is provided within the framework of the mechanisms of ion formation in MALDI.     

Interaction of nickel(II) and cobalt(II) salts with chitosan hydrochloride and acetate in aqueous solutions

Fundamental aspects of the complexation of cobalt(II) and nickel(II) ions with chitosan hydrochloride in water and chitosan in an aqueous solution of acetic acid were studied. The relation between the numbers of chitosan moles and metal ions involved in the interaction was found. The optimal conditions for synthesis of complexes were determined and their chemical composition and spectral properties were analyzed. The possible reaction mechanisms were discussed.     

Retention Behavior of Proteins on Glutamic Acid-Boned Silica Stationary Phase

A glutamic acid-bonded silica (Glu-silica) stationary phase with cation-exchange properties was synthesized using l-glutamic acid as ligand and silica gel as matrix. The effects of solution pH value, salt concentration and metal ion on the retention of proteins were examined. The standard protein mixture was separated with a prepared chromatographic column and an iminodiacetic acid column, and compared. The influence of the binding capacity of an immobilized metal ion on the complexation of metal chelate column was studied. The results indicate that the obtained column displays cation-exchange characteristic and better separation ability for proteins. As fixing metal ion on the Glu-silica column, retention of proteins on the column is a cooperative interaction of metal chelate and cation-exchange. The stationary phase shows the typical metal chelate properties with the increase of the sorption capacity of immobilized metal ion.     

高速离子交换色谱法分离重金属离子及铜和锌的测定

本文使用国产SY-202高速离子交换色谱仪(库仑检测器)以及国产YSG-SO₃Na型阳离子交换树脂研究了铜、锌、镍、钴、镉、铅和锰等七种二价离子在酒石酸盐、乳酸盐及柠檬酸盐体系洗脱液中的分离情况,考察了洗脱液及其流速对保留时间和柱效的影响以及不同离子和不同进样量对电解效率的影响。测定了黄铜和废水样品中的铜和锌。     

Selective solid phase extraction and preconcentration of iron(III) based on silica gel-chemically immobilized purpurogallin

The immobilization of purpurogallin on the surface of amino group containing silica gel phase for the formation of a newly synthesized silica gel-bound purpurogallin (SGBP) is described. The surface modification was studied and evaluated by determination of the surface coverage value by both the elemental analysis and metal probe testing method, which was found to be 0.485 and 0.460 mmol g⁻¹, respectively. The metal sorption properties of SGBP were examined by a series of di- and tri-valent metal ions. The metal capacity values (mmol g⁻¹) for this series of metal ions were also determined under different buffer solutions (pH 1.0–6.0) as well as shaking times by the batch equilibrium technique. The results of this study confirmed the strong affinity and selectivity as well as the fast equilibration and interaction processes of SGBP and Fe(III) compared to the other tested metal ions. The reduction–oxidation process of iron(II)/iron(III) by SGBP was also studied and the results indicated only 2.1% reduction of iron(III) into iron(II). The selectivity incorporated into silica gel phase via the immobilization of purpurogallin was intensively studied for a several binary mixtures containing iron(III)—another interfering metal ion. The determined percentage extraction values of iron(III) from these mixtures were found to be in the range of 94–100%. The potential applications of SGBP as a selective solid extractor for iron(III) from natural tap water samples and real matrices were also studied and the results revealed good percentage extraction values of iron(III) (93.5−94.9±4.6−5.3%) of the spiked iron(III) in the acidified tap water samples as well as a high preconcentration factor of 500 was also established when SGBP was used as a selective solid phase extractor and preconcentration of iron(III) from acidified soft drink samples with percentage recovery values of (98.0−97.4±4.7−5.3%) of the spiked iron(III).