Metal flux through consuming interfaces in ligand mixtures: boundary conditions do not influence the lability and relative contributions of metal species

In a mixture of metal ions and complexes, it is difficult to predict ecological risk without understanding the contribution of each metal species to biouptake. For microorganisms, the rate of uptake (internalization flux) has not only a major influence on the total metal flux but also on the bioavailability of the various metal species and their relative contributions to the total flux. In this paper, the microorganism is considered as a consuming interface, which interacts with the metal ion, M, via the Michaelis-Menten boundary conditions. The contribution of each metal complex to the overall metal flux, in relation to its lability, is examined for a number of important boundary parameters (the equilibrium constant K(a) of metal with transport sites, internalization rate constant k(int) and total transport sites concentration {R}(t)). Computations were performed for Cu(II) complexes, in a multicomponent culture medium for microoganisms. For a one-ligand system, results were acquired using rigorous mathematical expressions, whereas approximate expressions, based on the reaction layer approximation (RLA) and rigorous numerical computations (computer codes MHEDYN and FLUXY), were employed for ligand mixtures. Under the condition of ligand excess, as often found in the natural environment, the relative contribution of each metal species to the total flux is shown to be independent of the boundary conditions. This finding has important implications, including an improved basis for relating the analytical signals of dynamic metal speciation sensors to metal bioavailability.     

Roles of dynamic metal speciation and membrane permeability in metal flux through lipophilic membranes: general theory and experimental validation with nonlabile complexes

The study of the role of dynamic metal speciation in lipophilic membrane permeability in aqueous solution requires accurate interpretation of experimental data. To meet this goal, a general theory is derived for describing 1:1 metal complex flux, under steady-state and ligand excess conditions, through a permeation liquid membrane (PLM). The theory is applicable to fluxes through any lipophilic membrane. From this theory, fluxes in the three rate-limiting conditions for metal transport are readily derived, corresponding, namely, to (i) diffusion in the source solution, (ii) diffusion in the membrane, and (iii) the chemical kinetics of formation/dissociation of the metal complex in the interfacial reaction layer. The theory enables discussion of the reaction layer concept in a more general frame and also provides unambiguous criteria for the definition of an inert metal complex. The theoretical flux equations for fully labile complexes were validated in a previous paper. The general theory for semi- or nonlabile complexes is validated here by studying the flux of Pb(II) through PLMs in contact with solutions of Pb(II)-NTA and Pb(II)-TMDTA at different pHs and flow rates.     

Ligand mixture effects in metal complex lability

The degree of lability of a given metal complex species is modified in the presence of a mixture of ligands. This modification is a consequence of the coupling of the association and dissociation processes of all of the complexes according to the competitive complexation reaction scheme. We show that, because of the mixture effect, the lability of a given complex usually increases when another more labile complex is added into the system, while it decreases upon addition of a less labile one. Typically, complexes tend to adapt to the global lability of the mixture. A quantitative evaluation of these effects for diffusion-limited conditions in a finite domain by rigorous numerical simulation in a system with two complexes indicates that the lability degree of a complex can change by more than 100% with respect to that in the single ligand system. The impact of the mixture effect on the metal flux depends at least on two main factors: the respective abundance of the metal species and the particular values of their lability degrees. Dominant complexes (i.e., those most abundant when these complexes have equal diffusion coefficients) undergo smaller changes in their own lability degree, but these changes have the greater impact on the overall metal flux. Partially labile complexes are more easily influenced by the mixture than labile or inert ones. Some mixture effects can be qualitatively predicted by an analytical expression for the lability index derived using the reaction layer approximation. For a mixture of many complexes, the change in the lability degree of a complex due to the mixture effect can be understood as a combination of the changes due to all of the complexes present.     

Lability of a mixture of metal complexes under steady-state planar diffusion in a finite domain

The rigorous analytical solution for the fluxes from a mixture of 1:1 metal complexes toward an active surface under steady-state planar diffusion in a finite domain and excess ligand conditions allows for the computation of the global degree of lability of the system as well as particular degrees of lability of each complex in the mixture. This kind of system is found in a variety of fields ranging from electrochemical techniques (such as stripping chronopotentiometry at scanned deposition potential, SSCP) to analytical devices (such as diffusion gradients in thin-film gels, DGT). Among the specific effects arising from the presence of a mixture of ligands competing for the metal we highlight the following: (i) The degree of lability of a complex in the mixture differs from its degree of lability in an unmixed system with the same ligand concentration, and (ii) the degree of lability of one complex depends on (i.e., can be modified with) the concentrations of the ligands in the mixture. The impact of these characteristics on the metal flux crossing the active surface reaches the highest value when both complexes are partially labile. The complex contribution to the metal flux goes through a maximum when the thickness of the diffusion domain is varied. Thus, the thickness of the diffusion domain can be chosen to enhance the contribution of one particular complex. Lability criteria for each complex of the mixture within the reaction layer approximation are also reported. In particular, the reaction layer formulation for a complex is discussed in detail for two limiting cases: the rest of complexes are all nonlabile or the rest of complexes are all labile.     

Permeation of complexed metal ions through a hydrophobic membrane

Selective concentration of a heavy metal complex with acetylacetone (acac) through a hydrophobic polystyrene membrane was carried out under a pressure gradient. A chelate forming heavy metal was selectively concentrated about 2 fold by this method. When using a coating membrane with a high water flux, the permeabilities increased with increasing complex fraction in the aqueous solution, while using a membrane with a low water flux, a bulky complex was not highly concentrated because of steric hindrance. The complex partitioned on the membrane surface was transported and concentrated under a pressure gradient and a linear relationship was found to exist between permeabilities and partition coefficients. It will be possible to concentrate hydrophobic organic solutes by this method, for acac was concentrated when the Cu—acac complex was formed. As the permeabilities increased with decreasing pressure and membrane compaction was strong for a coating membrane, it seems effective to permeate at a low pressure.     

The metal flux: a preparative tool for the exploration of intermetallic compounds

This review highlights the use and great potential of liquid metals as exotic and powerful solvents (i.e. fluxes) for the synthesis of intermetallic phases. The results presented demonstrate that considerable advances in the discovery of novel and complex phases are achievable utilizing molten metals as solvents. A wide cross-section of examples of flux-grown intermetallic phases and related solids are discussed and a brief history of the origins of flux chemistry is given. The most commonly used metal fluxes are surveyed and where possible, the underlying principal reasons that make the flux reaction work are discussed.     

Lability criteria for successive metal complexes in steady-state planar diffusion

The lability of sequential metal complexes, ML, ML2, ML3, ... , up to a general 1:n metal/ligand stoichiometric ratio is considered for the case of metal ions (M) being accumulated at a surface (analytical sensor or organism). The analytical solution for the steady-state diffusion of M within a sequential complexation scheme allows quantification of the contribution from the dissociation of all of the complex species to the metal flux through the so-called lability degree, xi. A lability degree for each sequential complexation step is also defined which, due to the sequential character of the complexation scheme, depends not only on the proper kinetic constants of the given complexation step but also on the kinetics of the previous ones. When all contributions from the complexes are diffusion limited, the system is fully labile and xi=1. To provide simple lability criteria, the reaction layer approximation is extended to specifically deal with this sequential complexation scheme, so that a reaction layer thickness is defined when the existence of one particular rate-limiting step is assumed. Expressions for the classical lability parameter, L, are formulated using the reaction layer approximation. The change of the lability of the system as the diffusion layer thickness is modified is analyzed in detail. The contribution of the complex flux reflects the evolution of the system from labile to inert as the thickness of the sensor is appropriately decreased.     

Efficiency of various chemical cleanings for nanofiltration membrane fouled by conventionally-treated surface water

Nanofiltration systems are generally cleaned chemically. The optimal choice of the cleaning agent is a function of membrane material and foulant in a complex manner. This study evaluated the cleaning efficiency and effects of several cleaning agents on NF255 nanofiltration membrane. The nanofiltration pilot plant was fed with conventionally-treated surface water from a water treatment plant in southern Finland. Fouled membranes were cleaned weekly with different chemicals and procedures, and the cleaning efficiencies were compared in terms of flux recoveries and foulant removals. On the basis of the cleaning chemical analysis, the fouling material consisted of biofouling, organic deposits and metal complexes. In these circumstances, alkaline cleaners with chelatants resulted in the most efficient cleaning both in terms of flux recovery and foulant removal. Alkaline cleaning modified the membrane and improved the flux substantially in comparison to the virgin state. The results demonstrate that the choice of chemical cleaning agent is critical to cleaning efficiency, both technically and economically. The same flux recovery could be reached either by a single cleaning phase or by three sequential cleaning phases.     

Optimization of the preparation of153Sm-EDTMP using natural samarium targets for clinical use

¹⁵³Sm (specific activity 3.7 to 5.55 GBq/mg) was produced by irradiating natural Sm₂O₃ at a flux of 2.2·10¹³ n·cm⁻²·s⁻¹. Ethylenediaminetetramethylenephosphonate (EDTMP) was synthesised according to a reported method. Complexation was carried out by varying experimental parameters such as mole ratios of metal to ligand, pH, time and temperature of reaction to obtain quantitative yields. The radiochemical purity of the complex was assessed by various analytical techniques including HPLC. In vitro ligand exchange studies were undertaken to ensure suitability of the product for therapy. Biodistribution studies were carried out in Wistar rats and adequate bone uptake, retention and rapid clearance from blood stream were observed.     

Swelling Behavior and Metal-Ion Uptake Capacity of pH-Responsive Hydrogels of Poly(N-acryloyl-N′-ethylpiperazine)

New hydrogels based on N-acryloyl-N′-ethylpiperazine (AcrNEP) and N,N-methylene bisacrylamide (MBA) were prepared by thermal initiated solution polymerization. The hydrogels swelled extensively in buffer solutions of low pH due to protonation of the amine functions of the monomers, while the swelling was less significant in buffer solutions of high pH. The increased swelling of the gel in low pH is due to the development and interaction of fixed charges within the gel network. As a result of the electrostatic repulsion between the charges the elastic constraint of the gel is modified which leads to pronounced swelling and hence to high water uptake. Water transport in the hydrogel both in buffer solutions of pH 2.6 and pH 8.4 was non-Fickian due to polymer relaxation (anomalous process). The gels demonstrated good uptake of divalent metal ions such as Ni²⁺, Co²⁺, and Zn²⁺, with high selectivity for Ni²⁺ ions due to the formation of a more stable ligand-metal complex. The metal uptake capacity increased with increase in pH of the solution, while an increase in the crosslinker amount of the hydrogel reduced its metal uptake capacity. In the presence of metal ions the swelling of the hydrogel reduced considerably due to the formation of additional physical crosslinks within the hydrogel network. The metal ion loaded hydrogels could be stripped and regenerated with 1 M sulfuric acid without any loss in swelling or metal uptake capacities.     

Impact of ligand protonation on higher-order metal complexation kinetics in aqueous systems

The impact of ligand protonation on the complexation kinetics of higher-order complexes is quantitatively described. The theory is formulated on the basis of the usual situation for metal complex formation in aqueous systems in which the exchange of water for the ligand in the inner coordination sphere is rate-determining (Eigen mechanism). We derive expressions for the general case of lability of ML(n) species that account for the contributions from all outer-sphere complexes to the rate of complex formation. For dynamic complexes, dissociation of ML is usually the rate-determining step in the overall process ML(n) --> M. Under such conditions, it is the role of ligand protonation in the step ML --> M that is relevant for the kinetic flux. 1:2 complexes of Cd(II) with pyridine-2,6-dicarboxylic acid fall into this category, and their lability at a microelectrode is reasonably well predicted by the differentiated approach. For non-dynamic systems, the kinetic flux arising from dissociation of higher-order complexes contributes to the rate-determining step. In this case, the weighted contribution of protonated and unprotonated outer-sphere complexes in all contributing dissociation reactions must be taken into account. The kinetic flux arising from the dissociation of 1:2 complexes of Ni(II) with bicine at a conventional electrode was quite well described by this combined approach. The results establish the generic role of ligand protonation within the overall framework of metal complexation kinetics in which complexes may be dynamic to an extent that depends on the operational time scale of the measurement technique.     

Asymmetric self-assembly with atmospheric CO2 fixation of a pentanuclear carbonate NiI) complex based on dissimilar building blocks

Formation in basic solution of an asymmetric pentanuclear carbonate Ni(II) complex with a compartmental ligand involves atmospheric CO(2) uptake, either by reaction of two slightly different dinuclear precursors that yield its di- and trinuclear "building blocks", or directly, by spontaneous self-organization of metal and ligand starting reactants.     

Ternary complex formation dramatically enhances metal-sorbing vesicle selectivity

Conventional wisdom derived from experimental and theoretical studies of metal ion transport in liquid membrane systems suggests that the selective behavior of closely-related metal-sorbing vesicles (MSVs) should depend on independent interaction of ions with the membrane-bound carrier and with the encapsulated water soluble chelator. From a theoretical perspective, however, interdependent interactions between carrier, chelator and metal ion in a ternary complex can be designed into MSVs to augment significantly their metal ion selectivity. In this paper, we compare and contrast two transport models so as to elucidate MSV selectivity based on initial metal ion uptake rates from single and multi-component metal ion solutions. Our findings show that metal ion transport mechanisms that allow for interdependent interactions between the carrier and chelator, namely formation of a ternary metal ion–carrier–chelator complex at the inner vesicle wall, can enhance the overall selectivity of MSVs in accordance with a multiplicative, rather than additive, function of equilibrium metal–ligand binding constants. Therefore, design of MSVs that rely on metal ion transport mechanisms involving ternary complex formation may provide for a more economic route to extremely selective systems that employ less extensively tailored and less expensive metal-binding ligands.     

Mechanism of indium(III) exchange between NTA and transferrin: a kinetic approach

The equilibria and kinetics for the process of In(3+) exchange between nitrilotriacetic acid (NTA) and bovine serum transferrin (T) have been investigated in aqueous solution containing sodium bicarbonate. The metal exchange equilibria have been measured by difference ultraviolet spectroscopy at 25 degrees C, pH=7.4, and I=0.2 M (NaClO4). The acid dissociation constants of NTA and the binding constants of In(III) to NTA have also been measured. Kinetic experiments revealed that the process of In(3+) uptake by transferrin from [In(NTA)2](3-) is biphasic, the fast phase being completed in a few seconds, the slow phase lasting for hours. The fast phase has been investigated by the stopped-flow method and results in monoexponential kinetics. It involves rapid interaction of the 1:1 complex ML (M=In, L=NTA) with TB (T=transferrin, B=CO3(2-)) to give a quaternary intermediate MLTB which then evolves to an "open" MTB* ternary complex complex with expulsion of L. In turn, this complex interconverts to a "closed", more stable, form MTB. Neither the prevailing complex M2L nor the TB2 form of transferrin are directly involved in the exchange process but act as metal and protein reservoirs. The pH dependence of the reaction has been also investigated. The slow phase has not been investigated in detail; it takes several hours to go to the completeness, its slowness being ascribed to metal redistribution between the C-site and N-site of the protein, and/or metal release from polynuclear In(III) species.     

Mechanisms controlling the cellular accumulation of copper bis(thiosemicarbazonato) complexes

Copper (Cu) bis(thiosemicarbazonato) metal complexes [Cu(II)(btsc)s] have unique tumor-imaging and treatment properties and more recently have revealed potent neuroprotective actions in animal and cell models of neurodegeneration. However, despite the continued development of Cu(II)(btsc)s as potential therapeutics or diagnostic agents, little is known of the mechanisms involved in cell uptake, subcellular trafficking, and efflux of this family of compounds. Because of their high lipophilicity, it has been assumed that cellular accumulation is through passive diffusion, although this has not been analyzed in detail. The role of efflux pathways in cell homeostasis of the complexes is also largely unknown. In the present study, we investigated the cellular accumulation of the Cu(II)(btsc) complexes Cu(II)(gtsm) and Cu(II)(atsm) in human neuronal (M17) and glial (U87MG) cell lines under a range of conditions. Collectively, the data strongly suggested that Cu(II)(gtsm) and Cu(II)(atsm) may be taken into these cells by combined passive and facilitated (protein-carrier-mediated) mechanisms. This was supported by strong temperature-dependent changes to the uptake of the complexes and the influence of the cell surface protein on Cu accumulation. We found no evidence to support a role for copper-transporter 1 in accumulation of the compounds. Importantly, our findings also demonstrated that Cu from both Cu(II)(gtsm) and Cu(II)(atsm) was rapidly effluxed from the cells through active mechanisms. Whether this was in the form of released ionic Cu or as an intact metal complex is not known. However, this finding highlighted the difficulty of trying to determine the uptake mechanism of metal complexes when efflux is occurring concomitantly. These findings are the first detailed exploration of the cellular accumulation mechanisms of Cu(II)(btsc)s. The study delineates strategies to investigate the uptake and efflux mechanisms of metal complexes in cells, while highlighting specific difficulties and challenges that need to be considered before drawing definitive conclusions.     

Nitrogenous synergists induced potentiometric response to metal ions with polymeric liquid membranes containing thenoyltrifluoroacetone as an ionophore.

The effects of nitrogenous synergists on the potentiometric responses to divalent transition metal ions were investigated concerning polymeric liquid membranes containing thenoyltrifluoroacetone (Htta) as an ionophore. The tested synergists were pyridine (py) and 4,4'-dioctyl-2,2'-bipyridyl (C8bpy). The potentiometric responses to metal ions, such as Cd2+, Co2+, Ni2+ and Zn2+, were induced by adding the synergists into the liquid membrane systems. The coexistence of Htta and a synergist was necessary for generating the membrane potential. The tta- anion adsorbed at the liquid membrane/solution interface and the complex formation between the synergist and a given metal ion appeared to participate in preferential uptake of metal ions.     

Numerical Simulation of Metal Vapour Behavior in Double Electrodes TIG Welding

Metal vapour from the weld pool in double electrodes tungsten inert gas welding is taken into account by a unified numerical model including the arc plasma and the weld pool. The thermodynamic properties and transport coefficients of the arc plasma are dependent on both the local temperature and the mass fraction of the metal vapour. A second viscosity approximation is used to describe the diffusion coefficient of the metal vapour in the arc plasma. The temperature and the flow fields of both the arc plasma and the weld pool are calculated together with the metal vapour concentration. The simulated results are presented for the cases of 3 and 9 mm electrode separation, respectively. It is shown that the metal vapour behavior is much different in these two cases. In the case of 3 mm electrode separation, the metal vapour above the mass fraction of 0.2% is concentrated just above the weld pool surface, while in the case of 9 mm electrode separation, the metal vapour is diffused to the most region of the arc plasma for the same range of mass fraction. In addition, the arc plasma temperature as well as the heat flux at the weld pool is constricted by the presence of the metal vapour. The constricted heat flux at the weld pool results in an increase in the temperature of the weld pool about 100 K or less but a slight shrinkage of the weld pool shape.     

Study of a heavy metal biosorption onto raw and chemically modified Sargassum sp. via spectroscopic and modeling analysis

In this study, raw and formaldehyde-modified Sargassum sp. are used for heavy metal removal. A series of experiments shows that the chemical modification by formaldehyde improves biosorption capacity by approximately 20%. Solution pH plays an important role in the metal uptake. According to X-ray photoelectron spectroscopic and Fourier transform infrared spectroscopic analysis, the possible organic functional groups in the metal binding include carboxyl, ether, alcoholic, hydroxyl, and amino functional groups. A new model that includes a series of coordination reactions among a generalized functional group, alkaline earth metal ions and heavy metal ions, is developed for simulation of biosorption process. The model well describes the single- and multiple-species metal biosorption process under different conditions such as pH. The biosorption of heavy metals is due to the ion exchange between the heavy metals and alkaline earth metals and their adsorption onto the free sites of the seaweeds. Slightly more than half of the metal uptake is due to ion exchange. The metal affinity for the functional groups follows a descending order of lead > copper > alkaline earth metal.     

Kinetics of partition between aqueous solutions of salts and bulk liquid membranes containing neutral carriers

The relationship between the rates of transport of alkali metal cations through a bulk chloroform liquid membrane containing polynactin or dibenzo-18-crown-6 as neutral carrier and the rates of uptake and release of cation at the interfaces between aqueous phase and membrane phase were investigated. The fluxes of cations through the membranes and cation-distribution ratios between aqueous solution and membrane were strongly dependent on the anions present. The distribution ratio increased in the following order: Cl^? < NO₃^? < SCN^? < ClO₄^?, and the flux increased in the same order as the distribution ratio, except for the fluxes of KSCN and KClO₄ with polynactin. In the case of polynactin, the flux of KSCN was comparable to that of KClO₄ in spite of the fact that KSCN was less soluble in the membrane than was KClO₄. In order to clarify the cause of this apparently contradictory behavior, the apparent rate constants of uptake and release of potassium were determined independently using an equation derived from Fick's first law of diffusion. From the rates of uptake and release, it was suggested that the overall rate of cation transport through the membrane was dependent on the rate of release rather than that of uptake.     

Studies on Fe complexes produced by yeast. IV. Mechanism of Fe transport from an Fe(II)-oligosaccharide complex across the mucosal membrane of the rat intestine

The mechanism of Fe transport across the rat duodenal membrane from an Fe(II)-oligosaccharide complex (designated B1-c) produced in wine by yeast and showing high hematopoietic activity in rats was examined. The Fe uptake from B1-c by brush border membrane (BBM) vesicles isolated from the rat intestine was based mainly on the Fe binding to membrane components which were suggested to be inside the vesicles. Evidence that Fe was transported into the vesicles by a special transport system other than simple diffusion was obtained by observing saturation kinetics under conditions of isotope exchange, and temperature and pH dependence. This Fe uptake was not inhibited by any metal ions tested, including inorganic Fe(II), and the BBM vesicles from the duodenum had a higher Fe uptake than those from the other parts of the small intestine. Furthermore, the BBM vesicles isolated from rats with Fe deficiency showed a significantly increased Fe uptake. The Km value for B1-c uptake was 0.16 mM, lower than the values for FeSO4 and ferrous ascorbate. These results suggest that a special transport system selective for B1-c may be present on the mucosal membrane. B1-c was taken up by the BBM vesicles in the form of Fe-oligosaccharide complex. From the preloaded vesicles, B1-c was released temperature- and pH-dependently.(ABSTRACT TRUNCATED AT 250 WORDS)