Differential pulse adsorptive stripping voltammetric determination of nickel and cobalt in high purity aluminium

A sensitive method for the simultaneous determination of trace amounts of nickel and cobalt in pure aluminium has been described using differential pulse adsorptive stripping voltammetry (DPASV) by adsorptive accumulation of the dimethyl glyoxime (DMG) complex on the hanging mercury drop electrode (HMDE). As supporting electrolyte 0.1 mol/l ammonia buffer, pH 9.0, containing ammonium citrate and 5×10^–4 mol/l DMG has been used. The determination limit obtained has been as low as 0.5 g/g for Ni and 0.2 g/g for Co (using about 100 mg sample) with a relative standard deviation of 13% and 22%, respectively.     

Element Fractionation in Suspended Matter in Landfill Leachate Using Single Extractions

This study presents the determination of the pseudo-total and available element contents in suspended matter in leachate using stripping voltammetry (DPASV) on a hanging mercury drop electrode and an inductively coupled plasma mass spectrometer (ICP-MS). The following elements were studied: Zn, Pb, As, Sb, Co, Cu, Ni, Cr, Sn, Mo and Cd. To determine the pseudo-total metal contents, we applied microwave digestion using a mixture of HNO₃ and HClO₄ with a small quantity of HF. To assess the metal availability from suspended matter in leachate, the single extraction procedure with 0.1mol·L^–1 acetic acid and 0.01mol·L^–1 ammonium acetate was applied. Metal bioavailability based on single extraction with 15% H₂O₂ was determined. We also estimated the association with particular phases of suspended matter in leachate.     

Determination of subnanomolar concentrations of cobalt by adsorptive stripping voltammetry at a bismuth film electrode

Procedures for trace cobalt determinations by adsorptive stripping voltammetry at in situ and ex situ plated bismuth film electrodes are presented. These exploit the enhancement of the cobalt peak obtained by using the Co(II)–dimethylglyoxime–cetyltrimethylammonium bromide–piperazine-N,N-bis(2-ethanesulfonic acid) system. The calibration graph for an accumulation time of 120 s was linear from 2 × 10^–10 to 2 × 10^–8 mol L^–1. The relative standard deviation from five determinations of cobalt at a concentration of 5 × 10^–9 mol L^–1 was 5.2%. The detection limit for an accumulation time of 300 s was 1.8 × 10^–11 mol L^–1. The proposed procedure was applied to cobalt determination in certified reference materials and in tap and river water samples.     

Adsorptive stripping voltammetric determination of cobalt in the presence of dimethylglyoxime and cetyltrimethylammonium bromide

A sensitive procedure for determination of micro-traces of Co(II) by adsorptive stripping voltammetry is proposed. The procedure exploits the enhancement of the cobalt peak obtained by use of the system Co(II)–dimethylglyoxime–piperazine-1,4-bis(2-ethanesulfonic acid)–cetyltrimethylammonium bromide. Using the optimized conditions, a detection limit (based on the 3 criterion) for Co(II) of 1.2×10^–11 mol L^–1 (0.7 ng L^–1) was achieved. The calibration plot for an accumulation time of 30 s was linear from 5×10^–11 to 4×10^–9 mol L^–1. The procedure was validated by analysis of certified reference materials and natural water samples.     

Voltammetric Quantification of Zn and Cu,Together with Hg and Pb,Based on a Gold Microwire Electrode,in a Wider Spectrum of Surface Waters

The simultaneous determination of Zn and Cu by anodic stripping voltammetry (ASV) is prone to errors due to the formation of Cu‐Zn intermetallic compounds. The main aim of this work was to study the possibility of simultaneous determination of Zn and Cu, together with Hg and Pb, using a mercury‐free solid gold microwire electrode. The multi‐element detection was carried out by differential pulse anodic stripping voltammetry (DPASV), in a chloride medium (0.5 M NaCl) under moderate acid conditions (HCl 1.0 mM) in the presence of oxygen, where the gold microwire electrode was used as stationary or vibrating working electrode during the deposition step. Under these conditions, no formation of Cu‐Zn intermetallic compounds were found for concentrations usually determined in surface waters. In addition, quantification of Zn and Cu, together with Hg and Pb, can be performed in a wide range of concentrations (about two orders of magnitude) using the same sample, in a very short period of time. The detection limits for Cu, Hg, Pb and Zn, using a vibrating electrode and 30 s of deposition time, were 0.2 µg L^?1 for Hg, 0.3 µg L^?1 for Pb and 0.4 µg L^?1 for Zn and Cu, respectively. The proposed DPASV methods were successfully applied to the determination of Cu, Hg, Pb, and Zn in a certified reference fresh water, river, tap and coastal sea waters. These results proved the applicability and versatility of the proposed methods for the analysis of different water matrices and showed that a gold microwire electrode is a suitable choice to determine simultaneously Zn and Cu.     

Electrochemical Properties and Analytical Applications of Keggin-type Phosphomolybdic Anions in Electrostatically Linked 2-Aminoethanethiol Self-Assembled Monolayers

A composite film containing a heteropolyanion was prepared on a 2-aminoethanethiol (AT) self-assembled monolayer film-modified gold electrode by attaching the Keggin-type phosphomolybdic anion. The surface structures and electrochemical properties of the composite films were characterized by using ATR-FTIR, AC impedance, cyclic voltammetry and chronocoulometry. FTIR studies indicated that there was some electrostatic interaction between Pmo₁₂O₄₂^7– and surface NH₃⁺. Three reversible redox couples were observed in 1.0molL^–1 H₂SO₄ in the potential range of 0–0.7V for the composite film modified electrode, which were attributed to two-electron and two-proton electrochemical processes of PMo₁₂O₄₂^7–. The diffusion coefficient is determined to be 2.04×10^–7cm²s^–1. The composite film shows good catalytic activities for the reduction of nitrite (NO₂^–) in acidic solution and the catalytic mechanisms are described. The modified electrode provides a linear response for NO₂^– in the concentration range of 1.0×10^–4 to 1.0×10^–7molL^–1 by differential pulse adsorptive stripping voltammetry with a correlation coefficient of 0.9965. The detection limit (three times the signal blank/slope) was 2.0×10^–8molL^–1. The modified electrode was used for the determination of NO₂^– in wastewater.     

New voltammetric procedure for the simultaneous determination of copper and mercury in environmental samples

Summary A new voltammetric procedure for the simultaneous determination of Cu and Hg down to the ng/l-range in environmental samples is described. Differential pulse anodic stripping voltammetry (DPASV) at a gold electrode is applied. There are two versions. For Hg-levels typically below 100 ng/l in presence of substantially higher Cu-concentrations (300 ng/l or more), e.g. in sea water, Hg has to be determined by the subtractive mode of DPASV at a twin gold electrode and programmed polarisation has to be applied during the cathodic deposition stage, while the usually higher Cu-levels can be determined by common DPASV at a normal gold electrode. For Hglevels above 100 ng/l the determination of Hg and Cu can be performed in the same run by common DPASV at a normal gold electrode. The application of the gold electrode always requires medium exchange to 0.1 M HClO₄ plus 2.5×10^–3 M HCl subsequent to the cathodic accumulation stage before stripping. The method has been successfully applied to natural waters and wine. The necessary sample pretreatment remains simple and consists just in UV-irradiation to release the trace metal amount bound to dissolved organic matter, which is performed with samples from natural waters after prior 0.45 -filtration to separate from suspended particulate material.

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Neues voltammetrisches Verfahren zur simultanen Bestimmung von Kupfer und Quecksilber in Umweltmaterial

Zusammenfassung Als Bestimmungsverfahren werden zwei Versionen der differentiellen Pulsinversvoltammetrie (DPASV) an der Goldelektrode eingesetzt. Bei Quecksilbergehalten typisch unter 100 ng/l und gleichzeitiger Anwesenheit höherer Kupferkonzentrationen (300 ng/l), wie z.B. im Meerwasser, muß Hg mit der subtraktiven DPASV an einer Zwillingselektrode aus Gold bestimmt werden und während des kathodischen Anreicherungsschrittes erfolgt programmierte Polarisation der Goldelektrode. Hingegen können die gewöhnlich höheren Cu-Gehalte mit der üblichen konventionellen DPASV an einer normalen Goldelektrode bestimmt werden. Bei Hg-Gehalten oberhalb 100 ng/l kann die Bestimmung von Hg und Cu in einem voltammetrischen Arbeitsgang mit der konventionellen üblichen DPASV an einer normalen Goldelektrode erfolgen. Die Verwendung der Goldelektrode verlangt immer Wechsel des Mediums zu 0,1 M HClO₄ plus 2,5 ×10^–3 M HCl nach der kathodischen Anreicherung vor der stripping-Phase. Die Methode hat erfolgreiche Anwendung bei der Untersuchung natürlicher Gewässer und von Wein gefunden. Die erforderliche Probenvorbereitung bleibt einfach und besteht in einer UVBestrahlung, um den durch gelöste organische Materie gebundenen Spurenmetallanteil zu mobilisieren. Bei Proben aus natürlichen Gewässern erfolgt vorher eine 0,45 -Filtration zur Abtrennung von Schwebstoffen.

     

Determination of dinoseb by adsorptive stripping voltammetry using a mercury film electrode

An adsorptive stripping voltammetric method for the determination of the pesticide dinoseb (2-sec.-butyl-4,6-dinitrophenol) at the mercury film electrode is described. The deposition of the mercury film on a glassy carbon disk electrode was optimized. The temperature, at which the mercury film was deposited, was demonstrated to have a strong influence on the stripping peaks, the first one being much more intense than the second. A systematic study of the variables affecting the stripping response was carried out by differential pulse voltammetry. The results obtained have been compared with those at the HMDE; a significant improvement in the sensitivity of the method developed with the MFE was observed. Using a 300 s accumulation time, the limits of determination and detection were 3.6 × 10^–10 and 1.1 × 10^–10 mol L^–1, respectively. The effect of the presence of several herbicides on the dinoseb response was also tested. The method has been applied to the determination of the pesticide in spiked apple juice at two concentration levels: 12.0 and 1.2 g L^–1 of juice.     

Determination of dopamine in synthetic cerebrospinal fluid by SWV with a graphite–polyurethane composite electrode

This work describes an electroanalytical investigation of dopamine using cyclic voltammetry (CV) and the graphite–polyurethane composite electrode (GPU). In CV studies, well-defined redox peaks characterize the oxidation process at the GPU electrode, which is indicative of electrocatalytic effects associated with active sites on the GPU electrode surface. A new analytical methodology was developed using the GPU electrode and square wave voltammetry (SWV) in BR buffer solution (0.1 mol L^–1; pH 7.4). Analytical curves were constructed under optimized conditions (f=60s^–1, E_a=50 mV, E_I=2 mV) and detection and quantification limits of 6.4×10^–8 mol L^–1 (12.1 g L^–1) and 5.2×10^–6 mol L^–1 (0.9 mg L^–1), respectively, were achieved. The precision of the method was checked by performing ten successive measurements for a 9.9×10^–6 mol L^–1 dopamine solution. For intra-assay and inter-assay precisions, the relative standard deviations were 1.9 and 2.3%, respectively. In order to evaluate the developed methodology, the determination of dopamine was performed with good sensitivity and selectivity, without the interference of ascorbic acid in synthetic cerebrospinal fluid, which indicates that the new methodology enables reliable analysis of dopamine.     

Determination of medecamycin by adsorptive stripping voltammetry with an activated electrode

The adsorptive and electrochemical behaviors of medecamycin were investigated on a glassy carbon electrode (GCE) pretreated by anodic oxidation at +1.8 V for 5 min in 0.025 mol l^–1 NH₃-NH₄Cl (pH 8.6) solution. An adsorptive stripping voltammetric method for the determination of medecamycin at the pretreated glassy carbon electrode has been developed. Medecamycin was accumulated in NH₃-NH₄Cl buffer (pH 9.0) at a potential of –0.7 V (vs. saturated calomel electrode (SCE)) for a certain time, and then determined by second-order differential anodic stripping voltammetry. The second-order differential anodic stripping peak current at +0.72 V was proportional to the concentration of medecamycin in the range 2.0 g ml^–1 to 50.0 g ml^–1. The detection limit (three times the signal-to-noise) was 1.0 g ml^–1 and the relative standard deviation of the results was 3.28% for eight successive determinations of 10.0 g ml^–1 medecamycin. This method has been applied to the direct determination of medecamycin in commercial tablets and spiked urine samples with satisfactory results.     

Electrochemical behavior of a covalently modified glassy carbon electrode with aspartic acid and its use for voltammetric differentiation of dopamine and ascorbic acid

Aspartic acid was covalently grafted on to a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation of the amino-containing compound. X-ray photoelectron spectroscopic (XPS) measurement and cyclic voltammetric experiments proved the aspartic acid was immobilized as a monolayer on the GCE. Electron transfer to Fe(CN)₆^4– in solution of different pH was studied by cyclic voltammetry. Changes in solution pH resulted in the variation of the charge state of the terminal group; surface pK_a values were estimated on the basis of these results. Because of electrostatic interactions between the negatively charged groups on the electrode surface and dopamine (DA) and ascorbic acid (AA), the modified electrode was used for electrochemical differentiation between DA and AA. The peak current for DA at the modified electrode was greatly enhanced and that for AA was significantly reduced, which enabled determination of DA in the presence of AA. The differential pulse voltammetric (DPV) peak current was linearly dependent on DA concentration over the range 1.8×10^–6–4.6×10^–4 mol L^–1 with slope (nA mol^–1 L) and intercept (nA) of 47.6 and 49.2, respectively. The detection limit (3) was 1.2×10^–6 mol L^–1. The high selectivity and sensitivity for dopamine was attributed to charge discrimination and analyte accumulation. The modified electrode has been used for determination of DA in samples, in the presence of AA, with satisfactory results.     

Rapid Determination of Mercury in Water by Stripping Voltammetry at a Gold-Modified Carbon Electrode

A procedure was developed for determining mercury in natural water by stripping voltammetry on a gold-modified carbon electrode. The concentration dependence of the anodic stripping current of mercury is linear in the range 0.02–5 g/L Hg(II). The interference of Fe(III), Cu(II), Cl^–, Br^–, I^–, and F^– ions with the determination of mercury was studied. Ozonation was used for rapid sample preparation. The detection limit for mercury was 0.02 g/L at an electrolysis time of 5 min.     

Electrocatalytic Oxidation and Direct Determination of L-Tyrosine by Square Wave Voltammetry at Multi-wall Carbon Nanotubes Modified Glassy Carbon Electrodes

The electrochemical behavior of L-tyrosine was investigated at a multi-wall carbon nanotubes modified glassy carbon electrode. L-tyrosine itself showed a poor electrochemical response at the bare glassy carbon electrode; however, a multi-wall carbon nanotubes film fabricated on the glassy carbon electrode can directly enhance the electrochemical signal of L-tyrosine when applying cyclic voltammetry and square wave stripping voltammetry without any mediator. Cyclic voltammetry was carried out to study the electrochemical oxidation mechanism of L-tyrosine, which shows a totally irreversible process and an oxidation potential of 671 mV at the modified electrode and 728 mV at the bare electrode, ΔE_p = 57 mV. The anodic peak current linearly increases with the square root of scan rate in the low range, suggesting that the oxidation of L-tyrosine on the multi-wall carbon nanotubes modified electrode is a diffusion-controlled process. The square wave stripping voltammetry currents of L-tyrosine at the multi-wall carbon nanotubes modified electrodes increased linearly with the concentration in the range of 2.0 × 10⁻⁶–5.0 × 10⁻⁴ mol L⁻¹. The detection limit was 4.0 × 10⁻⁷ mol L⁻¹. The method is simple, quick, sensitive and accurate.     

Development of cysteine-modified screen-printed electrode for the chronopotentiometric stripping analysis of cadmium(II) in wastewater and soil extracts

Screen-printed carbon electrodes were fabricated with amino acid functionality by using in situ co-deposition of mercury and cysteine. The three-electrode configuration (graphite carbon working electrode, carbon counter electrode and silver/silver chloride reference electrode) incorporating a cysteine-modified working electrode exhibited good sensitivity towards cadmium(II). Several experimental variables affecting the sensor stripping response were characterised and optimised. These include cysteine and mercury concentrations, deposition time, deposition potential and stripping current. Surface analysis was also conducted using scanning electron microscopy (SEM) in order to characterize the electrode surface during cadmium analysis. The stripping chronopotentiometric response for cadmium(II) was linear in the concentration range 0.4–800 g L^–1 when a deposition time of 2 min was used. A detection limit of 0.4 g L^–1 was obtained using 0.025 M Tris–HCl buffer containing 0.1 M KCl (pH 7.4) as the supporting electrolyte. The analytical utility of the cysteine-modified sensor was demonstrated by applying it to cadmium analysis in various wastewater and soil samples collected from a contaminated site and extracted using acetic acid. The results obtained using the developed electrodes agreed satisfactorily with the values achieved using atomic absorption spectrometry and inductively coupled plasma mass spectrometry analysis. These results demonstrate the feasibility of using this type of sensor for cadmium analysis.     

Determination of heavy metals at the pg/g level in Antarctic snow with DPASV and IDMS

Summary Differential pulse anodic stripping voltammetry (DPASV) and isotope dilution mass spectrometry (IDMS) were used to analyse heavy metals in Antarctic snow samples. It was possible to determine Pb and Cd with DPASV at the German Antarctic station Georg-von-Neumayer whereas the analyses of Pb, Cd, Tl, Cr, Ni, Cu, Zn, and Fe with IDMS were carried out at the University of Regensburg. 80% of the elemental concentrations in surface snow samples analysed with IDMS lay in the following ranges: Pb=3–40 pg/g, Cd<0.2–3 pg/g, Tl<0.2 pg/g, Cr<0.8–15 pg/g, Ni<4.8–40 pg/g, Cu<11–30 pg/g, Zn=30–500 pg/g, and Fe=(0.5–1.5)×10³ pg/g. In most cases an acceptable agreement between the DPASV and IDMS results was obtained for Pb and Cd. More than 50% of all Pb analyses agreed within a deviation of 0–10 pg/g. The Cd results between both methods usually deviated by less than 1 pg/g. Slightly higher Pb concentrations were analysed in the average with IDMS compared with DPASV. This effect was not observed for the Cd data. A possible explanation for this fact are non-ionic Pb species in the melted snow samples, which cannot be analysed by DPASV. One particular investigation of Pb concentrations showed that the analysed data with DPASV decreased with the increasing length of sun-shine after a snowfall when samples of the same origin were determined. Blank control is the major requirement for accurate analysis results of heavy metals in this low concentration range. On the other hand, accuracy must always be tested by independent analytical methods. In this work it is shown that Pb and Cd can be analysed directly in the Antarctica with DPASV and that the result of this method is in acceptable agreement with the definitive method IDMS.

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Bestimmung von Schwermetallen im pg/g Bereich in antarktischen Schneeproben durch differentielle Pulsinversvoltammetrie und massenspektrometrische Isotopenverdünnungsanalyse

     

Binding constants of calcium and/or magnesium electrolytes and aggregation numbers in oil-in-water type microemulsions formed by an amphoteric surfactant

The effects of anti-symmetric electrolytes (CaCl₂, Ca(SCN)₂, MgCl₂, and/or Mg(SCN)₂) and pH on the phase behavior, the -potential, the hydrodynamic diameter and the surface charge density of an oil-inwater type (O/W-type) microemulsion formed in solutions of an amphoteric surfactant (N ,N -dimethyl-N -lauroyllysine, DMLL)/n-octane/1-pentanol/brine have been examined. The formation of the microemulsion in the presence of CaCl₂ and/or Ca(SCN)₂ is of Winsor-type with an increase in the concentration of 1-pentanol. Particularly, microemulsion is not formed by the addition of Ca(SCN)₂ in a pH region less than 2.6. The -potential and the surface charge density of the microemulsion in the presence of CaCl₂ decrease with an increase in pH and show slightly positive values in the isoelectric region (pH 5-7), while, in the presence of Ca(SCN)₂, the -potential and the surface charge density show negative values in the same region at which the net charge of DMLL molecules becomes almost zero. The hydrodynamic diameters in the presence of CaCl₂ show a maximum value around pH 2.5, whereas, in the presence of Ca(SCN)₂, the minimum value is around pH 5.5. Similar tendencies are recognized in results for the -potential, the hydrodynamic diameter and the surface charge density of the O/W-type microemulsion in the presence of MgCl₂ and Mg(SCN)₂. A new formula to estimate the binding constants (K) of Ca²⁺, Mg²⁺, Cl^–, and SCN^– to the hydrophilic groups in DMLL molecules and the adsorption density of DMLL molecules on the oil/water interface (N) in the presence of antisymmetric electrolytes has been derived.K for Ca²⁺, Mg²⁺, Cl^–, and SCN^– was found to beK _Ca=0.12M^–1,K _Mg=0.14 M^–1,K _Cl=0.0084±0.0016 M^–1, respectively.N for DMLL molecules in the presence of CaCl₂, Ca(SCN)₂, MgCl₂ and/or Mg(SCN)₂ was found to be 0.50 nm^–2, 0.38 nm^–2, 0.44 nm^–2, and 0.47 nm^–2, respectively; and the surfactant (DMLL) numbers per O/W-type microemulsion droplet change from a few hundreds to a few thousands with changing pH. The larger the hydrodynamic diameter of the O/W-type microemulsion, the greater the number of DMLL molecules adsorbed on the O/W-type microemulsion surfaces.     

Studies on the voltammetric behaviour of a 2-mercaptoimidazole containing carbon paste electrode: determination of traces of silver

The voltammetric behaviour of a 2-mercaptoimidazole (2-MI) containing carbon paste electrode was studied. When mixed to carbon paste as an electrode modifier, 2-MI can be reduced at negative potentials (–1 V vs. SCE), but it does not give a response in the potential range where Ag(0) is oxidized to Ag(I). Silver could be accumulated from 0.1 mol l^–1 acetate buffer onto a 2-MI modified carbon paste electrode without a potential applied; after medium exchange, it was reduced at –1 V vs. SCE in 0.1 mol l^–1 acetate buffer solution and determined by differential pulse anodic stripping voltammetry. With suitable preconcentration times, the detection limit was 0.1 g l^–1; a linear relation between current and concentration was found to exist within a range of 0.5 to 1000 g l^–1. In the presence of EDTA, common metal ions have no or only little effect on the voltammetric determination of silver.     

Electrochemical Sensors for the Stripping Voltammetric Determination of Antimony(III)

The conditions of the modification of a glassy-carbon electrode with various polyphenols were studied by multicyclic voltammetry over a wide range of pH. The state of the electrode surface was additionally monitored by measuring cyclic voltammograms of ferrocyanide ions in the presence of a phosphate buffer solution (pH 7.0). It was found that the electrooxidation of all the studied polyphenols at the electrode surface resulted in the formation of a water-insoluble film which is capable of accumulating antimony(III) from aqueous solutions. The surface concentration of chemically active cites was of the order n × 10^–9 M/cm². The electrochemical sensors thus prepared were found to be suitable for the selective determination of antimony(III) by adsorption stripping voltammetry. The maximum signals of antimony(III) were obtained at electrodes modified with pyrocatechol and pyrogallol upon metal deposition from acetate buffer solutions (pH 4.5). The detected peak areas S (A · s) were directly proportional to the deposition time t _d (min) and the concentration of antimony(III). The analytical range was 10–250 g/L at t _d = 5.0 min, and the detection limit was 6 g/L. It was found that a sensor based on a pyrogallol film can selectively determine antimony(III) in the presence of Sb(V), Cu(II), and Pb(II), and can be used for the analysis of natural water.     

Thick-film electrodes for measurement of superoxide and hydrogen peroxide based on direct protein–electrode contacts

Cytochrome c was immobilized on screen-printed thick-film gold electrodes by a self-assembly approach using mixed monolayers of mercaptoundecanoic acid and mercaptoundecanol. Cyclic voltammetry revealed quasi-reversible electrochemical behavior of the covalently fixed protein with a formal potential of +10 mV vs. Ag/AgCl. Polarized at +150 mV vs. Ag/AgCl the electrode was found to be sensitive to superoxide radicals in the range 300–1200 nmol L^–1. Compared with metal needle electrodes sensitivity and reproducibility could be improved and combined with the easiness of preparation. This allows the fabrication of disposable sensors for nanomolar superoxide concentrations. By changing the electrode potential the sensor can be switched from response to superoxide radicals to hydrogen peroxide—another reactive oxygen species. H₂O₂ sensitivity can be provided in the range 10–1000 mol L^–1 which makes the electrode suitable for oxidative stress studies.     

Preparation,spectroscopic and structural analysis of uranium-arabinose complexes

The reaction betweenL-arabinose and hydrated uranyl salts has been investigated in aqueous solution and the solid complexes of the type UO₂(L-arabinose)X ₂ · 2 H₂O, whereX=Cl^–, Br^–, and NO ₃ ^– , have been isolated and characterized. Due to the marked similarities with those of the structurally known Ca(L-arabinose)X ₂ · 4 H₂O and Mg(L-arabinose)X ₂ · 4 H₂O (X=Cl^– or Br^–) compounds, the UO ₂ ²⁺ ion binds obviously to twoL-arabinose moieties, through O1, O5 of the first and O3, O4 of the second molecule resulting into a six-coordinated geometry around the uranium ion with no direct U-X (X=Cl^–, Br^– or NO ₃ ^– ) interaction. The intermolecular hydrogen bonding network of the freeL-arabinose is rearranged upon uranium interaction. The -anomer configuration is predominant in the freeL-arabinose, whereas the -anomer conformation is preferred in the uranium complexes.

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Darstellung, spektroskopische und Strukturanalyse von Uran-Arabinose Komplexen

Zusammenfassung Es wurde die Reaktion zwischenL-Arabinose und hydratisierten Uranylsalzen in wäßriger Lösung untersucht und kristalline Komplexe des Typs UO₂(L-Arabinose)X ₂ · 2 H₂O mitX=Cl^–, Br^– und NO ₃ ^– isoliert und charakterisiert. Wie aus markanten Ähnlichkeiten der Komplexe mit den bekannten Verbindungen Ca(L-Arabinose)X ₂ · 4 H₂O und Mg(L-Arabinose)X ₂ · 4 H₂O (X=Cl^– oder Br^–) abzuleiten ist, bindet das UO ₂ ²⁺ -Ion mit zweiL-Arabinose Einheiten, wobei sich durch die O1,O5-Koordination des ersten und die O3,O4-Koordination des zweiten Moleküls eine sechs-koordinierte Geometrie um das Uranylion [ohne direkte U-X (X=Cl^–, Br^– oder NO ₃ ^– ) Wechselwirkung] ausbildet. Die intermolekularen Wasserstoffbrücken zeigen nach der Wechselwirkung mit dem Uranylion eine Umgruppierung. In der freienL-Arabinose ist das -Anomere vorherrschend, in den Urankomplexen hingegen das -Anomere.