Regina Krachler

Ionic liquids for extraction of metals and metal containing compounds from communal and industrial waste water

In a fundamental study the potential of ionic liquids based on quaternary ammonium- and phosphonium cations and thiol-, thioether-, hydroxyl-, carboxylate- and thiocyanate-functionalized anions has been assessed for future application in advanced sewage treatment. The elimination of the metal(oid)s Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Pt, Sn, Zn and the cancerostatic platinum compounds cisplatin and carboplatin was screened using a liquid phase micro-extraction set-up. The analytical tool-set consisted of ICP-SFMS and LC-ICP-MS for quantification of metal(oid)s and cancerostatic platinum compounds, respectively. The purity of the ILs was assessed for the investigated metal(oid)s on the base of present EU environmental quality standards and was found to be sufficient for the intended use. In model solutions at environmental relevant concentrations extraction efficiencies≥95% could be obtained for Ag, Cu, Hg and Pt with both phosphonium- and ammonium-based ILs bearing sulphur functionality in the form of thiosalicylate and 2-(methylthiobenzoate) anions, as well as with tricaprylmethylammonium thiocyanate within an extraction time of 120 min. All other metals were extracted to a lower extent (7-79%). In the case of cancerostatic platinum compounds a phosphonium-based IL bearing thiosalicylate functionality showed high extraction efficiency for monoaquacisplatin. For the first time, liquid phase micro extraction with ionic liquids was applied to industrial and communal waste water samples. The concentration of all investigated metal(oid)s could be significantly reduced. The degree of elimination varied with the initial concentration of metals, pH and the amount of suspended particulate matter.

Phosphonium and Ammonium Ionic Liquids with Aromatic Anions: Synthesis, Properties, and Platinum Extraction

Several hydrophobic long-chain quaternary ammonium and phosphonium ionic liquids (ILs) with functionalized aromatic anions were prepared following a metathesis route using tricaprylmethylammonium chloride (Aliquat 336) and trihexyl(tetradecyl)phosphonium chloride (Cyphos IL101) as precursors. The incorporation of aromatic anions bearing hydroxy-, methoxy-, thiol-, and thioether functionalities as well as tetraphenylborate anions resulted in an increased chemical stability of the ILs and an alteration of their physico-chemical properties. Furthermore, aromatic anions significantly decreased the water solubility and water uptake of both ammonium and phosphonium-based ILs. Thiol- and thioether ILs were applied for the extraction of platinum from aqueous phase using liquid phase micro-extraction. Time dependent studies showed a rapid elimination of up to 95% platinum after 30 min. With a leaching of the anion <0.01 wt-% into the aqueous media, the evaluated ILs were found to be suitable as extracting agents for platinum from aqueous solutions.

Application of the grand canonical ensemble to the study of equilibrium point defect concentrations in binary intermetallic phases with the B2-structure

Abstract A statistical thermodynamic model of ordering in nonstoichiometric B2-phases is developed, based on the oldest and simplest theory of ordering, the mean-field approximation with constant pair-wise interaction energies between nearest-neighbor atoms. This approximation is limited to the description of the distribution of atoms and vacancies on the different sublattices, a possible short-range ordering tendency of point defects is neglected. The expressions for the point defect concentrations as a function of composition and temperature are derived from the grand canonical ensemble. In B2-phases the vacancy concentration depends on composition and temperature and it is therefore necessary to consider an open system, where the transfer of atoms to or from the outside is allowed. In B2-phases not only one defect equilibrium is involved, but there are four defect equilibria to be considered. It is shown that, if a series of defect equilibria is involved, it is necessary to apply the principle of microscopic reversibility to formulate the required number of independent equilibrium conditions. Expressions for the activities and partial molar enthalpies of the alloy components as a function of composition and temperature are derived, and a comparison with experimental data for β′-FeAl is given, which shows the practicability of this approach.

Uranium extraction from aqueous solutions by ionic liquids.

For determining natural levels of (236)U with its environmental abundance of 10(-16)% rather large sample volumes (approximately 30L) are necessary, therefore the conventional radiochemical uranium analysis (pre-concentration and column chromatography) is very time consuming. To speed up the procedure hydrophobic ionic liquids (ILs) were evaluated as a potential extraction agent for uranium from aqueous solutions. High selectivity and efficiency for uranium compared to calcium and magnesium in natural water was achieved with tricaprylmethylammonium thiosalicylate, [A336][TS]. Uranium was stripped successfully from the investigated ILs with 2M HNO(3).

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration.

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

L- and D-proline thiosemicarbazone conjugates: coordination behavior in solution and the effect of copper(II) coordination on their antiproliferative activity.

Two enantiomerically pure thiosemicarbazone-proline conjugates with enhanced aqueous solubility, namely, 2-hydroxy-3-methyl-(S)-pyrrolidine-2-carboxylate-5-methylbenzaldehyde thiosemicarbazone [L-Pro-STSC or (S)-H(2)L] and 2-hydroxy-3-methyl-(R)-pyrrolidine-2-carboxylate-5-methylbenzaldehyde thiosemicarbazone [D-Pro-STSC or (R)-H(2)L] have been synthesized and characterized by elemental analysis, spectroscopic methods (UV-vis and (1)H and (13)C NMR), and electrospray ionization mass spectrometry. The metal complexation behavior of L-Pro-STSC, stoichiometry, and thermodynamic stability of iron(II), iron(III), copper(II), and zinc(II) complexes in 30% (w/w) dimethyl sulfoxide/H(2)O solvent mixture have been studied by pH-potentiometric, UV-vis-spectrophotometric, circular dichroism, electron paramagnetic resonance, (1)H NMR spectroscopic, and spectrofluorimetric measurements. By the reaction of CuCl(2)·2H(2)O with (S)-H(2)L and (R)-H(2)L, respectively, the complexes [Cu[(S)-H(2)L]Cl]Cl and [Cu[(R)-H(2)L]Cl]Cl have been prepared and comprehensively characterized. An X-ray diffraction study of [Cu[(R)-H(2)L]Cl]Cl showed the formation of a square-planar copper(II) complex, which builds up stacks with interplanar separation of 3.3 Å. The antiproliferative activity of two chiral ligands and their corresponding copper(II) complexes has been tested in two human cancer cell lines, namely, SW480 (colon carcinoma) and CH1 (ovarian carcinoma). The thiosemicarbazone-proline conjugates L- and D-Pro-STSC show only moderate cytotoxic potency with IC(50) values of 62 and 75 μM, respectively, in CH1 cells and >100 μM in SW480 cells. However, the corresponding copper(II) complexes are 13 and 5 times more potent in CH1 cells, based on a comparison of IC(50) values, and in SW480 cells the increase in the antiproliferative activity is even higher. In both tested cell lines, L-Pro-STSC as well as its copper(II) complex show slightly stronger antiproliferative activity than the compounds with a D-Pro moiety, yielding IC(50) values of 4.6 and 5.5 μM for [Cu(L-Pro-STSC)Cl]Cl in CH1 and SW480 cells, respectively.

Factors Controlling Extremely Productive Heterotrophic Bacterial Communities in Shallow Soda Pools

Dilute soda lakes are among the world’s most productive environments and are usually dominated by dense blooms of cyanobacteria. Up to now, there has been little information available on heterotrophic bacterial abundance, production, and their controlling factors in these ecosystems. In the present study the main environmental factors responsible for the control of the heterotrophic bacterial community in five shallow soda pools in Eastern Austria were investigated during an annual cycle. Extremely high cyanobacterial numbers and heterotrophic bacterial numbers up to 307 × 109 L−1 and 268 × 109 L−1 were found, respectively. Bacterial secondary production rates up to 738 µg C L−1 h−1 and specific growth rates up to 1.65 h−1 were recorded in summer and represent the highest reported values for natural aquatic ecosystems. The combination of dense phytoplankton blooms, high temperature, high turbidity, and nutrient concentration due to evaporation is supposed to enable the development of such extremely productive microbial populations. By principal component analysis containing the data set of all five investigated pools, two factors were extracted which explained 62.5% of the total variation of the systems. The first factor could be interpreted as a turbidity factor; the second was assigned to as concentration factor. From this it was deduced that bacterial and cyanobacterial abundance were mainly controlled by wind-induced sediment resuspension and turbidity stabilized by the high pH and salinity and less by evaporative concentration of salinity and dissolved organic carbon. Bacterial production was clustered with temperature in factor 3, showing that bacterial growth was mainly controlled by temperature. The concept of describing the turbid water columns of the shallow soda pools as “fluid sediment” is discussed.

Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering

Quaternary ammonium salts (quats) are an economically advantageous class of industrial compounds. They have surface-active properties, possess anti-microbial activity and are known to be bioactive (Boethling & Lynch, 1992; Juergensen et al., 2000). Contrary, reports regarding low melting tetraalkylphosphonium salts were relatively rare in the literature during the last decades (Bradaric et al., 2003). Although ILs based on quaternary ammonium cations have been known and produced for years, and also numerous phosphonium based ILs have been produced even in ton-scale, these groups of ionic liquids have been more or less “neglected” in the literature comparing to their imidazolium or pyridinium based counterparts. However, during the last decade significant work has been done, pointing out the advantages and broad application spectrum of these types of ionic liquids. Their improved thermal and chemical stability in comparison to e.g. pyridinium and imidazolium based ILs, their unique miscibility behaviour and solvating properties advances their use in specific applications (Rogers et al., 2002; Plechkova & Seddon, 2007; Chowdhury et al., 2007; Wasserscheid & Welton, 2008). Several ILs based on these classes of cations are already commercially available and have been successfully applied as phase-transfer catalysts, solvents, lubricants, gas capture agents, coating materials, or chemical sensors (Bradaric et al., 2003; Weng et al., 2006; Pernak et al., 2006; Yuan et al., 2007; Fraser & MacFarlane, 2009; Werner et al., 2010). Tricaprylylmethylammonium chloride (trade name Aliquat® 336), produced in ton-scale by Henkel, is nowadays widely used as metal extraction agent, phase transfer catalyst, surfactant, or antistatic agent. In contrast, trihexyl(tetradecyl)phosphonium chloride (trade name Cyphos® IL 101) was developed by Cytec Industries as a thermally stable phase transfer catalyst (Bradaric et al., 2003). Due to the relatively simple preparation route, Cyphos® IL 101 is produced in ton-scale and therefore represents a fairly cheap IL. Hence, due to their commercial availability and low prices, both Aliquat® 336 and Cyphos® IL 101 can be used themselves or represent favorable precursors for a series of ionic liquids. The goal of this chapter is to give some insight into the fascinating and fast-growing field of

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe6(μ3-O)2(μ4-O2)L10(OAc)2(H2O)2]·2.625Et2O·2.375H2O (1) and [Fe(III)11Cl(μ4-O)3(μ3-O)5L16(dmf)(2.5)(H2O)(0.5)]·Et2O·1.25dmf·3.8H2O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mössbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe6(O2)(O)2}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe4(μ3-O)(μ4-O)3}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Preparation and characterization of immobilized [A336][MTBA] in PVA-alginate gel beads as novel solid-phase extractants for an efficient recovery of Hg (II) from aqueous solutions.

The coarse PVA-alginate matrix gel beads entrapping the micro-droplets of the ionic liquid tricaprylylmethylammonium 2-(methylthio) benzoate ([A336][MTBA]) as novel solid-phase extractants were prepared for the removal of mercury (II) from aqueous media. The ionic liquid [A336][MTBA] immobilized PVA-alginate beads (PVA/IL) have been characterized by FTIR, SEM and TGA. The influence of the uptake conditions was investigated including aqueous pH, PVA/IL dosage, the content of [A336][MTBA] and initial Hg (II) concentration; maximum Hg (II) ion adsorption capacity obtained was 49.89 (± 0.11)mgg(-1) at pH 5.8 with adsorptive removal of approximately 99.98%. The selectivity of the PVA/IL beads towards Hg (II), Pb (II) and Cu (II) ions tested was Hg>Pb>Cu. The rate kinetic study was found to follow second-order and the applicability of Langmuir, Freundlich and Tempkin adsorption isotherm model were tested as well. The results of the study showed that PVA/IL beads could be efficiently used as novel extractants for the removal of divalent mercury from aqueous solutions under comparatively easy operation conditions.