Amidopyrroles: from anion receptors to membrane transport agents

Amidopyrroles have been employed in a variety of anion receptors and sensors. 2,5-Bisamidopyrroles show selective oxo-anion complexation properties in organic solution whilst bis-amides containing dipyrrolylmethane groups form strong complexes with dihydrogen phosphate anions in mixtures of DMSO-d6 and water. Deprotonation of the 2,5-bisamidopyrrole unit can lead to interesting solid-state structures including the formation of orthogonal hydrogen bonded dimers. Amidopyrrole groups have also been employed in receptors for ion-pairs and in membrane transport agents for HCl.     

Sorption of methanal by a weak basic anion exchanger

Peculiarities of the sorption of methanal on a polyfunctional anion exchanger are investigated. Based on the sorption isotherm, it is established that the distribution coefficient of the aldehyde in the ion exchanger-solution system depends exponentially on the concentration of the external solution. From breakthrough curves of sorption, the rate-determining stage of the absorption of the aldehyde in dynamic conditions is estimated. Structural changes in the sorbent phase saturated with methanal are supported by IR spectroscopy.     

Dialytic transport of carboxylic acids through an anion exchange membrane

The transport behavior of five carboxylic acids of relevance in biotechnology (acetic, propionic, lactic, oxalic, citric) in diffusion dialysis and neutralization dialysis through an anion exchange membrane is investigated. The dependence of acid anion flux on base concentration in neutralization dialysis is analyzed in terms of two limiting situations (boundary layer control and membrane control) by an empirical two-parameter flux equation in formal analogy to a Langmuir function. When coupled to a life fermenter, neutralization dialysis is a means to control the pH of the fermentation medium. By removing biotoxic acids, it improves microbial productivity, as exemplified with the Propioni system producing vitamin B₁₂ and propionic acid.     

Effect of the concentrations of triphenyltin chloride and anion exchanger on the anion selectivity of a plasticized PVC membrane electrode

 Potentiometric selectivities of a plasticized poly(vinyl chloride) (PVC) membrane containing a hydrophobic quaternary ammonium salt and triphenyltin chloride (TPTCl) for several inorganic anions were evaluated by measurements of the membrane potential of a bi-ionic system (the so-called bi-ionic membrane potential). The addition of TPTCl to the plasticized PVC membrane containing a quaternary ammonium salt gave rise to selectivity patterns different from the Hofmeister anion series, which is observed for a membrane containing only the quaternary ammonium salt. The change in the selectivity pattern from the Hofmeister to the non-Hofmeister was observed under conditions where the TPTCl concentration was higher than the quaternary ammonium salt in the membrane. Response mechanisms and the selectivity of the TPTCl-based electrode are discussed with respect to the concentration dependence of TPTCl and quaternary ammonium salt in the membrane. Received: 6 July 1995/Revised: 2 February 1996/Accepted: 6 February 1996     

Transmembrane anion transport by synthetic systems

This highlight examines recent advances in the development of synthetic membrane transporters for anions, highlighting the underlying principles of transporter design and the promising applications of such transporters to biological systems including potential future treatments for diseases like cystic fibrosis which is caused by dysregulation of chloride transport across epithelial cell membranes.     

Special features of VP-1Ap anion exchanger behavior under deep silicification

Special features of the VP-1Ap anion exchanger behavior in the presence of various forms of silicon compounds were studied. Regularities observed in the experiments were explained, and a basis for predicting the effect of exterior perturbations on the evolution of silicification processes was developed. Precautions were offered to reduce a harmful effect on sorption processes.     

Enhanced membrane transport of pharmaceutically active protic ionic liquids

We show that pharmaceutically active protic ionic liquids can be designed to rapidly transport through model membranes as neutral hydrogen bonded clusters.     

The C-terminal ester of membrane anchored peptide ion channels affects anion transport

Five heptapeptide derivatives, [CH3(CH2)17]2NCOCH2OCH2CO-Gly-Gly-Gly-Pro-Gly-Gly-Gly-OR, in which R = ethyl, 2-propyl, heptyl, benzyl, and cyclohexylmethyl, were found to transport chloride anion through a phospholipid bilayer to varying extents dependent on the identity of R. It was concluded that the R group is a membrane anchor for the synthetic chloride channels.     

Heats of exchange of chloride with pyridinecarboxylate ions in Dowex-1 anion exchanger

Journal of Thermal Analysis and Calorimetry - The heats of exchange of chloride with pyridinecarboxylic acids anions in Dowex-1 strongly basic anion exchanger was obtained by the microcalorimetric...     

New block-grafted anion exchanger for environmental water analysis by ion chromatography

The IonPac AS14A is a recently developed stationary phase that was produced using a new block-grafting technique, which enables the preparation of high-water-content anion exchangers with excellent peak shape and good chromatographic efficiency. The performance of this column for the analysis of inorganic anions was compared to that obtained using an IonPac AS4A column, which is specified in US Environmental Protection Agency Method 300.0, in addition to another commonly used alternative; the AS14 column. The AS14A column is available in two different formats; 250×4 mm I.D. (7.0 μm diameter particle) and 150×3 mm I.D. (5.5 μm diameter particle). The IonPac AS14A (in 4 mm I.D. format) was found to provide similar performance to the AS14 column with increased peak efficiency and better pH stability and is a suitable alternative for the analysis of anions in moderate- to high-ionic-strength samples. The IonPac AS14A (in 3 mm I.D. format) provides comparable run times to the AS4A column with better overall peak selectivity and improved fluoride resolution, hence this column would be a suitable column to substitute in place of either the AS4A or AS14 columns for the analysis of inorganic anions in low- to moderate-ionic-strength environmental waters. The AS14A column used with an Atlas electrolytic suppressor provides equivalent method detection limits to those obtained when using a micromembrane suppressor but with the operational convenience of a self-regenerating suppressor.     

A polar-copolymerized method to prepare silica-based anion exchanger for ion chromatography

A novel silica-based strong anion exchanger was developed for ion chromatography by copolymerizing methyltrichlorosilane and 3-chloropropyltrichlorosilane. The method allows the column capacity to be easy control simply by adjusting the ratio of silanes. The unwanted residual silanol groups onto the surface of silica gel could also be greatly reduced by this strategy. The effective column capacity of the column used was measured to be 50.8 μequiv/column (2.03 μequiv/cm). The exchanger was characterized by solid state CP/MAS ¹³C NMR and elemental analysis and its separation performance was evaluated for the separation of common inorganic anions. The results showed that the column had good separation efficiency (e.g. the plate number of nitrite is 80,000/m) and the separation mechanism was observed to be dominantly governed by ion exchange mechanism. The utility of the column was demonstrated for the determination of nitrite and nitrate in saliva sample.     

Facilitated transport of salts by neutral anion carriers

Partitioning of ions from water to the membrane solvent (NPOE) can be quantified by Gibbs free energies of transfer, deltaG(tr,NPOE)(ion). These were derived from transport studies of lipophilic salts through supported liquid membranes (SLMs) in the absence of the carrier. Partition coefficients Kp for various salts can now be calculated. The neutral anion receptors uranyl sal(oph)enes 1-5 transport Cl- and H2PO4- as tetrapropylammonium salts. The transport is diffusion-limited and can be described by two transport parameters Dm and K(ex). From the extraction constants K(ex) and the partition coefficients Kp of the transported salts, the association constants Ka of the anion receptors for Cl- and H2PO4- in NPOE were determined. Competitive transport with carriers 3 and 4 of NPr4H2PO4 and NPr4Cl demonstrated highly selective transport of H2PO4- even in the presence of excess of Cl-.     

Chromium(VI) transport through the Raipore 1030 anion exchange membrane

The flat sheet Raipore R1030 anion exchange membrane has been evaluated as a sample interface in an optical sensor for Cr(VI) monitoring. The R1030 is an anion exchange membrane containing quaternary ammonium groups. The Donnan dialysis (DD) that takes place has been enhanced with facilitated transport of Cr(VI) anions by using a 1,5-diphenylcarbazide (DPC) solution as stripping phase. The DPC acts as a reducing reagent for Cr(VI), and as a complexing reagent for the generated Cr(III). The Cr(III) complex is a strongly absorbing species, and this is the basis of the optical detection. The effect of chemical parameters on Cr(VI) transport has been evaluated. Experiments with UV-VIS detection have shown that the membrane R1030-DPC system exhibits features suitable for Cr(VI) optical sensing. A simplified model based on a kinetic approach is reported describing the transport mechanism of the chemically facilitated DD process.     

Synthesis of temperature-responsive anion exchanger via click reaction

The temperature-responsive anion exchanger was synthesized by immobilizing the poly(N-isopropylacrylamide) (PNIPAM), a kind of the temperature-responsive polymer, on the external surface of mesoporous silica via click reaction. The structure of this synthesized composite was characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), elemental analysis, and nitrogen adsorption experiment. The amount of PNIPAM immobilized on the external surface of mesoporous silica, which was calculated from the weight loss measured by thermogravimetry, increased from 5.3 wt.% to 12.9 wt.% (dry) depending on the amount of PNIPAM added in the click reaction. The adsorption-desorption behavior of methyl orange (MO) ions in this synthesized anion exchanger was affected by the temperature of aqueous solution: the MO ions were adsorbed and desorbed reversibly and repeatedly with changing the pH of the solution at 25 °C, while the amount of adsorbed MO ions remained nearly constant at about 0.05 mmol/g independent of the pH of the solution at 40 °C. Also, the amount of PNIPAM immobilized on the mesoporous silica influenced the adsorption rate of MO ions, suggesting that the adsorption rate in this composite is controlled by the diffusion of MO ions through the PNIPAM layer.     

Curvature-regulated transmembrane anion transport by a trifluoromethylated bisbenzimidazole

In this paper,we demonstrate that modification of anion-transport active 1,3-bis(benzimidazol-2-yl)benzene with strongly electron-withdrawing trifluoromethyl and nitro groups leads to a dramatic increase in the anionophoric activity,and the activity may be greatly regulated by the curvatures of the liposomes used.     

Transmembrane anion transport mediated by adamantyl-functionalised imidazolium salts

We present the design, synthesis and transmembrane anion transport properties of a new class of mobile organic transporters, possessing a central imidazolium cation and two external adamantyl units. We demonstrate herein that the imidazolium cation can be incorporated in the structure of active mobile anion transporters. Depending on the nature of the counter-anion of the salt, as well as the extravesicular anions, different anion selectivities were obtained. We show the importance of the H2 proton of the imidazolium cation in order to obtain a higher binding constant of the chloride anion. Furthermore, we demonstrate the importance of the flexibility of the spacers between the adamantyl groups and the imidazolium cation in the transport process.     

A novel silica based click lysine anion exchanger for ion exchange chromatography

Ion chromatography (IC) is one of the most powerful analysis technologies for the determination of charged compounds. A novel click lysine stationary phase was prepared via Cu(I) catalyzed alkyne-azide 1,3-dipolar cycloaddition (CuAAC) and applied to the analysis of inorganic ions. The chromatographic evaluation demonstrated good performance (e.g. the plate number of thiocyanate is ～50,000 plates m(-1)) and effective separation ability for the common inorganic anions with aqueous Na(2)SO(4) eluent. The separation mechanism was observed to be mainly dominated by ion exchange interaction. The retention of these analytes is highly dependent on the pH value of eluent. Compared with the lysine stationary phase prepared via the conventional manner, the click lysine exchanger demonstrated shorter retention time and better ion separation characteristics under the same chromatographic conditions, which is a great advantage for rapid separation and analysis of inorganic ions.     

Aggregation and supramolecular membrane interactions that influence anion transport in tryptophan-containing synthetic peptides

Self-assembly is a desired property in supramolecular chemistry, but extensive aggregation may be counterproductive. Rigid systems typically have better organization, but are inherently less dynamic. This work shows that ion transport by amphiphilic heptapeptides (synthetic anion transporters or SATs) is affected by aggregation of the monomers in the bulk aqueous phase to which they are added and within the bilayer. Ion transport was assessed for all compounds by assay of Cl(-) release from liposomes. The mechanism of ion transport was confirmed by planar bilayer conductance studies for two compounds at opposite ends of the efficacy scale. Dynamic light scattering, the Langmuir trough, transmission electron microscopy, ion release from liposomes, and planar bilayer conductance studies were used to assess the importance of self-assembly versus aggregation in ion transport. Generally, greater aggregation was has an adverse effect on the transport, although at least dimerization is required for amphiphilic heptapeptides to readily transport Cl(-). Anion transport in these systems was found to be sensitive to changes in the C-terminal portion of the (Gly)(3)Pro(Gly)(3) sequence. Moreover, a significant difference in transport efficacy was apparent when L-Trp was replaced by D-Trp in the same position.     

ATP-dependent active transport simulations based on a phosphatase-channel-kinase membrane structure

Simulations of coupled interactions involving enzymatic reaction diffusion and electrostatic interactions were conducted under a fixed phosphatase-channel-kinase (PCK) topology oriented from the outside to the inside of a charged membrane structure. Depending on the phosphatase and kinase locations, we recently demonstrated that active transport of a phosphorylated substrate may occur via this PCK topology. The present analysis demonstrates that, if in addition to this topology, a phosphatase activity (P(1)) is also present on the inner side of the membrane, but outside the unstirred layer surrounding the inner membrane surface, then active transport of the corresponding unphosphorylated substrate may also occur. Therefore, this PCK membrane topology, which behaves as a specific ATP-dependent transporter, appears as a general topology permitting; first, on its own the active transport of a phosphorylated substrate; second, when associated with a phosphatase acting in the bulk of the receiver compartment, the active transport of the corresponding unphosphorylated substrate, that is, in most cases, the transport of an uncharged substrate. The general mathematical model given permits the active transport of a phosphorylated substrate to be analyzed (in the absence of P(1)), the active transport of an unphosphorylated substrate (in the presence of P(1)), whatever the charge distributions on both sides of the membrane surface and whatever the positions of the membrane-bound phosphatase and the membrane-bound kinase. This general model also takes into account the consumption of ATP occurring into the receiver compartment during the time course of these transport phenomena. A broad analysis of the role played by the main parameters taken into account in the model was conducted to precisely define the physicochemical conditions and the membrane topology needed for the highest active transports within the shortest time.