Complexation studies with lanthanides and humic acid analyzed by ultrafiltration and capillary electrophoresis-inductively coupled plasma mass spectrometry

For the long-term storage of radioactive waste, detailed information about geo-chemical behavior of radioactive and toxic metal ions under environmental conditions is necessary. Humic acid (HA) can play an important role in the immobilisation or mobilisation of metal ions due to complexation and colloid formation. Therefore, we investigate the complexation behavior of HA and its influence on the migration or retardation of selected lanthanides (europium and gadolinium as homologues of the actinides americium and curium). Two independent speciation techniques, ultrafiltration and capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICP-MS) have been compared for the study of Eu and Gd interaction with (purified Aldrich) HA. The degree of complexation of Eu and Gd in 25 mg l(-1) Aldrich HA solutions was determined with a broad range of metal loading (Eu and Gd total concentration between 10(-6) and 10(-4) mol l(-1)), ionic strength of 10 mM (NaClO4) and different pH-values. From the CE-ICP-MS electropherograms, additional information on the charge of the Eu species was obtained by the use of 1-bromopropane as neutral marker. To detect HA in the ICP-MS and separate between HA complexed and non complexed metal ions in the CE-ICP-MS, we have halogenated the HA with iodine as ICP-MS marker.     

Synthesis and anion sensing of water-soluble metallomacrocycles

The self-assembly of (TMEDA)Pd(NO(3))(2) or (TMEDA)Pt(NO(3))(2) (where TMEDA = N(1),N(1),N(2),N(2)-tetramethylethane-1,2-diamine) and anthracene- or ferrocene-based diimidazole ligands (L(1-3)) in aqueous solution affords a series of positively charged [M(2)L(2)](4+) dimetallomacrocycles. Their structures were characterized by (1)H NMR and electrospray ionization mass spectrometry and in the cases of {[(TMEDA)Pd](2)L(1)(2)}(NO(3))(4) (1), {[(TMEDA)Pd](2)L(1)(2)}(PF(6))(4) (1a), and {[(TMEDA)Pd](2)L(3)(2)}(NO(3))(4) (4) by single-crystal X-ray diffraction analysis. Interestingly, the NMR spectra of 1 and 1a revealed that the difference of their structures, as confirmed by X-ray diffraction analysis, was that a NO(3)(-) of 1 was encapsulated inside the cavity of the basket-shaped metallomacrocycle by C-H···O hydrogen bonds, while PF(6)(-) of 1a was bound outside by C-H···F hydrogen bonds. The fluorescence titration experiment exhibited the formation of 1:1 host-guest complexation for anthracene-based positively charged [M(2)L(2)](4+)-type metallomacrocycles with NO(3)(-). The interactions between metallomacrocycles and various anions were investigated via fluorescence titration and cyclic voltammetry studies, respectively.     

Protein release behavior from porous microparticle with lysozyme/hyaluronate ionic complex

Porous microparticles (PMs) with a low density (<0.4 g/cm3) for pulmonary protein delivery were prepared by the water-in-oil-in-water (W1/O/W2) multi-emulsion method using a cyclodextrin derivative as a porogen. The complexation of positively charged lysozyme (Lys) and negative-charged hyaluronate (HA) was investigated for long-term protein release from PMs. The interaction of Lys and HA not only increased protein encapsulation efficiency but also stabilized Lys against a denaturing organic solvent (dichloromethane). Furthermore, PMs with Lys/HA complexes increased the Lys release period up to 7 days, as opposed to a 4h Lys release time from PMs without Lys/HA complexes. In particular, PMs containing 10mg of HA and 50mg of Lys showed almost zero-order Lys release kinetic for 7 days and preserved the bioactivity of Lys more than 98% during its entire release period. This result suggests that PMs with Lys/HA complexes may be applied in long-term pulmonary administration of protein or peptide drugs, including those that require particles to arrive at a deep lung epithelium with the help of low density (high porosity) of PMs.     

Silver binding by humic acid as determined by equilibrium ion-exchange and dialysis

One of the major challenges in environmental analytical chemistry is to develop methods for determining metal speciation in natural waters that contain low metal concentrations and dissolved organic matter (DOM). Because of its complex heterogeneous nature, metal binding to DOM cannot be predicted accurately using equilibrium models. Two independent speciation methods, the equilibrium ion-exchange technique (IET) and equilibrium dialysis (EqD), were used to determine silver binding by standard Suwannee River humic acid. Both approaches gave very similar results, although for a given silver loading, the concentration of free silver obtained by IET was somewhat higher than that determined by EqD. Our results suggest that any high-affinity binding sites present within the humic acid are likely saturated at [Ag(T)] > 10(-9) M. This comparison of free metal ion concentrations with two independent methods provides useful speciation information in the absence of reliable complexation constants for the reaction of silver with humic acid.     

Study of interactions of concentrated marine dissolved organic matter with copper and zinc by pseudopolarography

The interaction of dissolved organic matter (DOM) with copper and zinc in a concentrated seawater sample was characterised by pseudopolarography. Measurements performed at increased concentrations of copper(II) ions showed successive saturation of active DOM sites which indicate possible partition of copper between (i) free or labile complexes, (ii) reduced and released within the potential window of the method, and (iii) electroinactive copper complexes. Pseudopolarograms measured at pH 4 indicate a release of copper which was bound to the active sites of DOM that formed non-labile complexes. Variation of the peak position and half-peak width along the scanned deposition potentials and with the increasing concentration of copper bear the information about the complex electrochemical processes at the electrode surface and in the bulk of the solution. Pseudopolarograms of zinc showed a strong dependence of the peak current and the peak position along the scanned deposition potentials on pH values, indicating preferentially complexation of zinc with carboxylic-like active sites of DOM in the measured sample. Pseudopolarography is a valuable method in the trace metal complexation and speciation studies, serving as a fingerprint of the analysed sample.     

Effect of ionic liquid on the determination of aromatic amines as contaminants in hair dyes by liquid chromatography coupled to electrochemical detection

The room temperature ionic liquid (IL) 1-butyl-3-methylimidazolium bis-(trifluorometanesulfonyl)imide BMIm[NTf?] was used as a novel medium for improvement of separation and quantization of 16 aromatic amines typically present as contaminants in consumer products and detected by HPLC coupled to an electrochemical detector. The aromatic amines, namely 4,4'-diaminodiphenylmethane, 4-chloroaniline, 2-methoxy-5-methyl-aniline, 3,3'-dimethylbenzidine, 2,4-diaminotoluidine, 2-chloro-4-nitroaniline, 4,4'-oxydianiline, aniline, 3,3'-ichlorobenzidine, benzidine, 4-aminobiphenyl, o-dianisidine, o-anisidine, o-toluidine, 4,4'-methylene-bis-2-chloroaniline and 2-naphthylamine are oxidized in methanol/BMIm[NTf?] at a potential around +0.68V to +0.93V vs. Ag/AgCl at a glassy carbon electrode, which is the base for their determination by HPLC/ED. Using the optimized conditions of methanol/BMIm[NTf?] 70:30 (v/v) as mobile phase, flow-rate of 0.8 mL·min?1, column CLC-ODS, Eap = +1.0 V and T = 40 °C analytical curves were constructed for each of the tested amines. Good linearity was obtained in the concentration range of 1.09 mg·L?1 to 217 mg·L?1, with excellent correlation coefficients. The limits of detection reached 0.021 mg·L?1 to 0.246 mg·L?1 and good relative standard deviations (RSD, n = 3) were obtained from the measurements. Satisfactory recovery for each aromatic amine was achieved, ranging from 95 to 103%. The developed method was successfully applied to determine six aromatic amines present as contaminants in commercial hair dye samples.     

Europium (III) and Uranium (VI) complexation by natural organic matter (NOM): Effect of source

For the safe long‐term storage of high‐level radioactive waste (HLW), detailed information about geo‐chemical behavior of radioactive and toxic metal ions under environmental conditions is important. Natural organic matter (NOM) can play a crucial role in the immobilization or mobilization of these metal ions due to its complexation and colloid formation tendency. In this study, the complexation of europium (as chemical homologue of trivalent actinides such as americium) and uranium (as main component of HLW) by ten humic acids (HA) from different sources and Suwannee NOM river extract has been analyzed. Capillary electrophoresis in combination with inductively coupled plasma mass spectrometry has been used for the evaluation of complex stability constants log β. In order to determine the complex stability constants a conservative single site model was used in this study. In dependence of their source and thus of NOM structure the log β values for the analyzed humic acids are in the range of 6.1–7.0 for Eu(III) and 5.2–6.4 for U(VI) (UO₂²⁺), respectively. In contrast to the results for HA the used Suwannee river NOM reveals log β values in the range of nearly two orders of magnitude lower (4.6 for Eu³⁺ and 4.5 for UO₂²⁺) under the geochemical conditions applied in this study.     

Measuring the pollutant transport capacity of dissolved organic matter in complex matrixes

Dissolved organic matter (DOM) facilitated transport in contaminated groundwater was investigated through the measurement of the binding capacity of landfill leachate DOM (Vejen, Denmark) towards two model pollutants (pyrene and phenanthrene). Three different methods for measuring binding capacity were used and evaluated, head-space solid-phase micro-extraction (HS-SPME), enhanced solubility (ES) and fluorescence quenching (FQ). It was concluded that for samples with complex matrixes it was possible to measure the net effect of the DOM binding capacity and the salting out effect of the matrix. It was further concluded that DOM facilitated transport should be taken into account for non-ionic PAHs with lg?K?_OW above 5, at DOM concentrations above 250?mg?C/L. The total DOM concentration was found to be more important for the potential of facilitated transport than differences in the DOM binding capacity.     

Dissolved Cu(II) Speciation in Unpolluted Soil Solutions of a Planosolic Horizon

Dissolved Cu(II) speciation in unpolluted soil solutions from different horizons was studied using differential pulse anodic stripping voltammetry (DPASV). Three sites were selected according to topography and monitored for three years. Experiments evidence Cu(II) can be bound by DOM (Dissolved Organic Matter) through complexation and/or adsorption reactions. The complexation capacity and the corresponding conditional stability constant were determined for complexation reactions. The adsorbing sites were titrated. A potential binding coefficient was calculated to compare both types of reactions. Results show adsorption is less frequent than complexation but exhibits higher binding coefficient.     

Enzyme-responsive polysaccharide supramolecular nanoassembly for enhanced DNA encapsulation and controlled release

An enzyme-responsive polysaccharide supramolecular targeted nanoassembly was successfully constructed by the host-guest complexation of positively charged mono-(6-(tetraethylenepentamine)-6-deoxy)-β-cyclodextrin(TEPA-CD) with adamantane-grafted hyaluronic acid(HA-ADA).Possessing a series of positively charged polyamine chains, the obtained polysaccharide nanoassembly could serve as a biocompatible plasmid DNA(p DNA) container. More interestingly, the p DNA could be released from the nanoassembly through the enzymatic degradation of HA skeleton, which realized the controlled p DNA binding and release. Besides, the polysaccharide nanoassembly exhibited lower cytotoxicity than the commercial transfection reagents 25 k Da b PEI(PEI25 k), accompanied by similar gene delivery effect. We believe that this work might present a convenient method for targeted,controlled gene delivery.     

Competition between humic acid and carbonates for rare earth elements complexation

The competitive binding of rare earth elements (REE) to humic acid (HA) and carbonates was studied experimentally at various pH and alkalinity values by combining ultrafiltration and inductively coupled plasma mass spectrometry techniques. The results show that the REE species occur as binary humate or carbonate complexes but not as ternary REE-carbonate-humate as previously proposed. The results also reveal the strong pH and alkalinity dependence of the competition as well as the existence of a systematic fractionation across the REE series. Specifically, carbonate complexation is at a maximum at pH 10 and increase with increasing alkalinity and with the atomic number of the REE (LuCO(3)>LaCO(3)). Modeling of the data using Model VI and recently published stability constants for complexation of REE by humic acid well reproduced the experimental data, confirming the ability of Model VI to accurately determine REE speciation in natural waters. This modeling also confirms the reliability of recently published stability constants. This work shed more light not only on the competition between carbonates and HA for REE complexation but also on the reliability of WHAM 6 and Model VI for calculating the speciation of REE with organic matter in alkaline organic-rich water.     

Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime

Glutarimidedioxime (H(2)A), a cyclic imide dioxime ligand that has implications in sequestering uranium from seawater, forms strong tridentate complexes with UO(2)(2+). The stability constants and the enthalpies of complexation for five U(vi) complexes were measured by potentiometry and microcalorimetry. The crystal structure of the 1?:?2 metal-ligand complex, UO(2)(HA)(2)·H(2)O, was determined. The re-arrangement of the protons of the oxime groups (-CH[double bond, length as m-dash]N-OH) and the deprotonation of the imide group (-CH-NH-CH-) results in a conjugated system with delocalized electron density on the ligand (-O-N-C-N-C-N-O-) that coordinates to UO(2)(2+)via its equatorial plane.     

Sensing of biologically relevant d-metal ions using a Eu(III)-cyclen based luminescent displacement assay in aqueous pH 7.4 buffered solution

1·Eu·BPS was developed as a luminescent lanthanide sensor for use in displacement assays for detection of d-metal ions by monitoring the changes in the europium emission, which was quenched for iron(II), with a detection limit of ～10 pM (0.002 μg L(-1)) for Fe(II) in buffered pH 7.4 solution.     

Positively charged covalent organic framework and its application in the dispersive solid-phase extraction of ultraviolet-filters from food packaging material migrants

Abstract

Covalent organic frameworks (COFs) show excellent property, such as high porosity and excellent structure stability and were well applied in fields such as catalysis and adsorption, but most of the COFs showed similar structure and thus similar adsorption performance. Modification of simple COFs to enhance its adsorption performance in separation technique is an important issue. In this study, quaternary ammonium groups with long hydrophobic chain were introduced into a simple COF (TpPa-1) for the first time. The positively charged COF (PC-TpPa-1) can form electrostatic interaction and hydrophobic effect with negatively charged analytes, and showed good adsorption performance for ultraviolet-filters (UV filters). Under the optimum conditions, i.e. adsorbent amount 20?mg, pH?=?7, 1.0?mL acetonitrile as eluent, the obtained recoveries for all UV filters were in the range of 86.4–96.7%.The developed method was successfully applied to the determination of UV filters from food packaging material migrants with the aid of HPLC as a detector.     

Concurrently Increasing Specific Energy and Suppressing Self-Discharge of Electrochemical Capacitors by Complexing Carbon Nanotubes with Redox Active Units-Containing Charged Copolymers

Specific energy and self-discharge are two important performances of electrochemical capacitors. In this work, we have fabricated the composite electrodes by complexing the negatively charged carboxylated multi-walled carbon nanotubes (cMWCNT) with the redox active units-containing positively charged random copolymers. 2, 2, 6, 6-Tetramethylpiperidinyl-N-oxyl and viologen are employed as model redox active units to exemplify the strategy of the concurrent increase of specific energy and suppression of self-discharge of a two-electrode device. The slower hydrogen and oxygen evolution reactions compared with the reactions of the redox active units lead to an increased electrolyte decomposition window, thereby giving rise to an increase in specific energy. On the other hand, the complexation between the cMWCNT and the copolymers suppresses both the redox shuttling and the cross-diffusion of the redox active units-containing polymer chains, leading to an improved performance of self-discharge. Based on the complexation between carbon nanotubes and redox active units-containing charged copolymers, this work provides a convenient and universal strategy to concurrently increase specific energy and suppress self-discharge of electrochemical capacitors.     

Anionic gallium-based metal-organic framework and its sorption and ion-exchange properties

A gallium-based metal-organic framework Ga(6)(C(9)H(3)O(6))(8)·(C(2)H(8)N)(6)(C(3)H(7)NO)(3)(H(2)O)(26) [1, Ga(6)(1,3,5-BTC)(8)·6DMA·3DMF·26H(2)O], GaMOF-1; BTC = benzenetricarboxylate/trimesic acid and DMA = dimethylamine], with space group I43d, a = 19.611(1) ?, and V = 7953.4(6) ?(3), was synthesized using solvothermal techniques and characterized by synchrotron-based X-ray microcrystal diffraction. Compound 1 contains isolated gallium tetrahedra connected by the organic linker (BTC) forming a 3,4-connected anionic porous network. Disordered positively charged ions and solvent molecules are present in the pore, compensating for the negative charge of the framework. These positively charged molecules could be exchanged with alkali-metal ions, as is evident by an ICP-MS study. The H(2) storage capacity of the parent framework is moderate with a H(2) storage capacity of ~0.5 wt % at 77 K and 1 atm.     

Complexation as the most important factor in the fate and transport of heavy metals in the Dnieper water bodies

The results of long-term investigations of the concentrations of dissolved forms of some heavy metals (Mn, Cu, Zn, Pb, Cr, Cd) and their species in the water of the Dnieper reservoirs and the Dnieper-Bug estuary are considered. Chemiluminescent methods, anodic stripping voltammetry, membrane filtration, ion-exchange, and gel-permeation chromatography were used for study of the speciation of the metals. It has been found that binding of heavy metals into complexes with dissolved organic matter (DOM) is the dominant factor of their stabilization in solution. The molecular weight distribution of organic metal complexes and their chemical nature, as well as the potential complexing ability of DOM were investigated. Humic substances, particularly fulvic acids, play a major role in the complexation. These ligands bind from 45 to 80% of metals in the form of organic complexes. Metal complex compounds of relatively low molecular weight (<5 kDa) predominated in the organic complexes.     

腐植酸作用下γ-六氯环己烷在冰相中的光转化

研究了腐植酸(HA)存在下冰相体系中γ-六氯环己烷(γ-HCH)的光转化规律.结果表明,HA浓度对γ-HCH的光转化率呈现低浓度促进而高浓度抑制的现象;盐离子浓度、NO_2~-及NO_3~-对γ-HCH的光转化率均有促进作用;低浓度Fe~(3+)对γ-HCH的光转化率有促进作用,当Fe~(3+)的浓度增大到50μmol/L时,呈现抑制效应;γ-HCH在不同p H值条件下光转化速率的大小顺序为碱性中性酸性.冰相中HA通过产生单线态氧(~1O_2)、羟基自由基(·OH)及三重激发态(HA*)加速γ-HCH的光转化.HA存在下γ-HCH的光转化产物主要是五氯环己烯、邻二氯苯和对二氯苯、一氯苯,光转化过程中~1O_2通过消耗中间产物间接加速了γ-HCH的光转化过程.     

Humic Acid Improves Zn Fertilization in Oxisols Successively Cultivated with Maize–Brachiaria

Zinc (Zn) is an essential micronutrient for plant growth, and Zn deficiency is a global issue, especially in tropical soils. This study aimed to investigate the effects of humic acid (HA) and the Zn addition (Zn sulfate + HA) on the growth of maize and brachiaria in two contrasting Oxisols. The potential complexation of Zn sulfate by HA was evaluated by Fourier-transform infrared (FTIR) spectroscopy analysis. Zinc content and its availability in solution and the shoot and root biomass of maize and brachiaria were determined. FTIR spectroscopy revealed the complexation of Zn sulfate by HA through its S and C functional groups. In both Oxisols, solution Zn increased due to the combined use of Zn and HA. In a soil type-dependent manner, maize biomass and Zn in its shoots were affected only by the exclusive use of Zn fertilization. In the Yellow Oxisol, brachiaria growth and Zn accumulated in its shoot were positively affected by the combined use of Zn fertilization with HA. In the Oxisol with lower organic matter content, HA can assure adequate supplying of residual Zn, while increasing growth of brachiaria cultivated in sequence to maize.     

Sorption speciation of nickel(II) onto Ca-montmorillonite: batch, EXAFS techniques and modeling

The sorption speciation of Ni(II) on Ca-montmorillonite was evaluated using a combination of batch experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy and modeling. The pH and temperature at the aqueous-montmorillonite interface affects both the extent of Ni(II) sorption as well as the local atomic structure of the adsorbed Ni(II) ions. At 0.001 mol L(-1) Ca(NO(3))(2) and low pH, the study reveals that the majority of Ni(II) is adsorbed in the interlayers of Ca-montmorillonite coordinated by six water molecules in an octahedron as an outer-sphere complex. At higher pH, inner-sphere surface complexes are formed. The Ni-Si/Al distances (R(Ni-Al) = 3.00 ?, R(Ni-Si1) = 3.10 ? and R(Ni-Si2) = 3.26 ?) determined by EXAFS confirm the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5 and 8.5. At pH 10.0, the Ni-Ni/Si distances (R(Ni-Ni) = 3.07 ? and R(Ni-Si) = 3.26 ?) indicates the formation of Ni-phyllosilicate precipitates. A rise in temperature promotes inner-sphere complexation, which in turn leads to an increase in Ni(II) sorption on Ca-montmorillonite. Sorption edges are fitted excellently by surface complexation model (SCM) with the aid of surface species determined from EXAFS spectroscopy.