Controlling cesium cation recognition via cation metathesis within an ion pair receptor

Ion pair receptor 3 bearing an anion binding site and multiple cation binding sites has been synthesized and shown to function in a novel binding-release cycle that does not necessarily require displacement to effect release. The receptor forms stable complexes with the test cesium salts, CsCl and CsNO(3), in solution (10% methanol-d(4) in chloroform-d) as inferred from (1)H NMR spectroscopic analyses. The addition of KClO(4) to these cesium salt complexes leads to a novel type of cation metathesis in which the "exchanged" cations occupy different binding sites. Specifically, K(+) becomes bound at the expense of the Cs(+) cation initially present in the complex. Under liquid-liquid conditions, receptor 3 is able to extract CsNO(3) and CsCl from an aqueous D(2)O layer into nitrobenzene-d(5) as inferred from (1)H NMR spectroscopic analyses and radiotracer measurements. The Cs(+) cation of the CsNO(3) extracted into the nitrobenzene phase by receptor 3 may be released into the aqueous phase by contacting the loaded nitrobenzene phase with an aqueous KClO(4) solution. Additional exposure of the nitrobenzene layer to chloroform and water gives 3 in its uncomplexed, ion-free form. This allows receptor 3 to be recovered for subsequent use. Support for the underlying complexation chemistry came from single-crystal X-ray diffraction analyses and gas-phase energy-minimization studies.     

Strong surface adsorption of aqueous sodium nitrite as an ion pair

We describe the first detailed experimental characterization of surface adsorption of an aqueous ion pair and quantify the unusual surface behavior of sodium nitrite, a ubiquitous component of natural waters. The onset of unusually strong adsorption at concentrations as low as ca. 0.1 M resembles the controversial ‘Jones–Ray Effect,’ wherein 13 salts exhibited surface tension minima in the millimolar region before resuming the normal linear increase with bulk concentrations. Given the compelling analogy recently found between adsorption of ions to the air–water interface, and the Hofmeister Effects of biochemistry, these results have important implications for the mechanism underlying these phenomena.     

Dynamics for reaction of an ion pair in aqueous solution: reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse

[reaction: see text]. The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H4(13)CH(Me)18OC(O)C6F5 in 50/50 (v/v) trifluoroethanol/water, k(solv) + k(iso) = 1.22 x 10(-5) s(-1), is larger than k(solv) = 1.06 x 10(-5) s(-1) for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k(-1) = 7 x 10(9) s(-1) for internal return by unimolecular collapse of the ion pair, which is significantly larger than k(Nu) = 5 x 10(8) M(-1) x s(-1) for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+.     

Clotrimazole-triiodide ion association as an ion exchanger for a triiodide ion-selective electrode.

A novel triiodide ion-selective electrode based on a clotrimazole-triiodide ion pair as a membrane carrier was prepared. It has a linear response to triiodide from 8 x 10(-6) to 5 x 10(-3) M with a slope of -68.9 mV per decade and a detection limit of 5 x 10(-6) M. The electrode response is independent of the pH of the solution in the pH range 2-9. It has a very short response time and can be used for at least 3 months without any considerable divergence in the potentials. The proposed sensor revealed very good selectivities for I3- over a variety of other anions. It was used as an indicator electrode in the potentiometric titration of triiodide ions and in an indirect potentiometric determination of clotrimazole in pharmaceutical preparations.     

Size-dependent maximum in ion conductivity: the levitation effect provides an alternative explanation

We propose an alternative explanation of the size-dependent maximum in ion mobility in water in terms of the levitation effect, which accounts for the observed size-dependent maximum in the mobility of guest diffusion in porous media. In this explanation, the size at which the maximum occurs is related to the structure of the void space of the water; at the mobility maximum, the diffusant passes smoothly through necks connecting voids, and its potential energy shows minimum fluctuations. Molecular dynamics simulations of charged spheres of varying sizes are used to support this hypothesis. As in the levitation effect, the friction coefficient, the potential energy fluctuations, and the activation energy are found to be minima for particles with maximum self diffusivities similar to the guest diffusion in zeolites. Wavelength-dependent self diffusivities indicate a monotonic and oscillatory dependence, respectively, on wavenumber k for anomalous (AR) and linear regimes (LR). These are associated with single and biexponential decay of the incoherent intermediate scattering function.     

Langmuir monolayer behavior of an ion pair amphiphile with a double-tailed cationic surfactant

The spread or Langmuir monolayer behavior of an ion pair amphiphile (IPA), hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS), with a double-tailed cationic surfactant, dihexadecyldimethylammonium bromide (DHDAB), at the air/water interface was analyzed with surface pressure-area isotherms, area relaxation curves, and Brewster angle microscope (BAM) images. The surface pressure-area isotherms showed that with increasing the DHDAB molar ratio, X(DHDAB), spread monolayers of HTMA-DS with DHDAB became rigid. In addition, unreasonably small limiting areas per alkyl chain of the molecules in the monolayers were found, especially at X(DHDAB)=0.5, implying the molecular loss from the monolayers at the interface. For spread HTMA-DS/DHDAB monolayers at the interface, a new IPA, DHDA-DS, was proposed to form through the displacement of HTMA(+) from HTMA-DS by DHDA(+), leaving HTMA(+) dissociated. The formation of DHDA-DS and the desorption of dissociated HTMA(+) upon the interface compression were supported by the results obtained from designed monolayer experiments with BAM observations, and were discussed by considering the hydrophilicity, packing efficiency, and headgroup charge characteristic of the species. Moreover, the area relaxation curves of spread HTMA-DS/DHDAB monolayers suggested that the formation of DHDA-DS was strongly related to the improved monolayer stability at the interface, which may have implications for the DHDAB-enhanced physical stability of catanionic vesicles composed of HTMA-DS.     

Water-mediated catalyst preactivation: an efficient protocol for C-N cross-coupling reactions

A protocol for forming a highly active Pd(0) catalyst from Pd(OAc) 2, water, and biaryldialkylphosphine ligands has been developed. This protocol generates a catalyst system, which exhibits excellent reactivity and efficiency in the coupling of a variety of amides and anilines with aryl chlorides.     

Multichannel HSO4- recognition promoted by a bound cation within a ferrocene-based ion pair receptor

A ferrocene-based ion pair receptor is shown only to recognise HSO(4)(-) anions in the presence of a cobound Pb(2+) or Zn(2+) cation guest species through a perturbation of the redox potential of the ferrocene unit and a remarkable enhancement of the fluorescence.     

A simple but effective dual redox and fluorescent ion pair receptor based on a ferrocene-imidazopyrene dyad

The ferrocene-imidazopyrene dyad, bearing the imidazole ring as the only receptor site, acts as a redox and optical molecular sensor for ion pairs, exhibiting an easily detectable signal change in the redox potential of the ferrocene/ferrocinium redox couple and in the emission spectrum. Perturbation of the emission spectrum follows the order Pb(2+) > Hg(2+) > Zn(2+) for cations and H(2)PO(4)(-) > AcO(-) for anions.     

An ion pair receptor showing remarkable enhancement of anion-binding strengths in the presence of alkali metal cations

An ion pair receptor was prepared by coupling of a diazacrown ether and a rigid biindole scaffold bearing hydrogen bond donors of two indole NHs. The former serves as the cation-binding site and the latter functions as the anion-binding site. The anion-binding affinities to the receptor, determined by ¹H NMR titration experiments in 10% (v/v) DMSO-d₆/CD₃CN at 24 ± 1 °C, have been greatly improved when an alkali metal cation binds to the adjacent diazacrown ether. For example, the association constant between chloride and receptor alone is 7 M⁻¹, but the magnitudes increase into 120 M⁻¹, 14,000 M⁻¹, and 6200 M⁻¹ in the presence of lithium, sodium, and potassium ions, respectively. The enhanced binding affinities must be attributed to electrostatic interactions by possibly forming contact ion pairs.     

Spectrophotometric determination of ciprofloxacin by ion pair formation

Various aspects of application of derivative spectrophotometry to chemical analysis and investigations of equilibria and kinetics of reactions are scrutinised. In this work the viability of a spectrophotometric technique for the determination of ciprofloxacin has been deliberated. The method is based on the formation of ion-association complexes of ciprofloxacin with nickel(II) tetra thiocyanate, which are extracted into organic solvent (40% n-butanol in methylene chloride) having absorption maxima at 623 nm. The precision and accuracy of the method was checked by UV reference methods. The validation study indicated the parameters, which are in good agreement with the data obtained from standard methods. The proposed method was fruitfully applied to determine ciprofloxacin in their tablet formulations.     

The impact of ion pair association upon the 1H NMR spectra of cationic complexes akin to Grubbs catalysts

A reconsideration of the ¹H NMR spectra of cationic transition metal complexes exhibiting the features of cyclophanes on the basis of Mislow's classification of topic groups arrives at the conclusion that the spectral changes triggered by chiral counterions reflect an intracationic diastereotopication of enantiotopic protons rather than the existence of pairs of long‐lived diastereomeric ion pairs. Copyright © 2010 John Wiley & Sons, Ltd.     

Microscopic hydration of the sodium chloride ion pair

Hydration of ion pairs is an essential process in various physicochemical phenomena occurring in solutions. Isolated clusters of an ion pair solvated with finite number of waters have been considered as a model system for the critical evaluation of microscopic interactions involved in the process, and theoretical studies have contributed exclusively to the subject up to now. Here we report the first experimental characterization of structure and internal dynamics of hydrated ion pairs, NaCl-(H2O)n (n = 1-3). The measurements of their rotational spectra have proven that the clusters have cyclic forms, in which Na+ and Cl- ions are strongly interacted with the O and H atoms of the solvent molecules, respectively. The Na-Cl distance shows a pronounced increase with the successive addition of water molecules. The separation for n = 3 approaches the value predicted for the contact ion-pair state in aqueous solution by recent molecular dynamics simulations.     

Nitrate ion association with Sm3+ ion

A solvent extraction method withTBP as an extractant was used for the determination of the stability constantsK ₁ ^o for the SmNO ₃ ²⁺ complex, for different least approach distanceså of ions. It was established thatå=6.5 Å for SmNO ₃ ²⁺ .

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Zur Assoziation von Nitrat-Ion mit Sm³⁺

Zusammenfassung Die StabilitätskonstantenK ₁ ^o für den SmNO ₃ ²⁺ -Komplex bei verschiedenen Mindestannäherungsdistanzenå der Ionen wurden mittels einer Lösungsmittelextraktionsmethode mitTBP ermittelt. Der beste Wert fürå war 6.5 Å.

     

On the “spatially separated ion pair”

The proof of existence of a new intermediate, the “spatially separated ion pair”, in the pathway of unimolecular heterolysis of organic compounds is critically analysed. It is concluded that the existence of this intermediate is not proved.     

HPLC separation and quantification of anionic surfactants using an automated on-line ion pair extraction system

Summary Aliphatic anionic surfactants, like alkylsulfonates, alkyl sulfates, -sulfo alkanoic acids and their esters, were separated with respect to their alkyl chain length by high performance liquid chromatography (HPLC) using reversed phase (RP) columns. For sensitive and specific detection of these classes of compounds the HPLC separation was combined with a post-column ion-pair extraction system. The limit of detection is in the range of 3–30 ng. Previously reported detection systems of this kind were modified by changing the inner set-up of the phase separator and the extraction capillary and integrating a purge function, which led to a higher system stability and made automatization possible. In order to optimize the experimental set-up, the influence of the reagent concentration as well as different sizes and materials of the extraction capillary were evaluated. The calibration curve of surfactant concentrations versus fluorescence emission is discussed for sodium decylsulfonate. Since both the electrolyte concentration and the percentage of organic solvents in the mobile phase may adversely affect the detection system, different eluent compositions were tested.This article is part of the planned dissertation of Markus Schoester at the Mathematical Natural Science Faculty of the University of Düsseldorf     

Computational study of SN2 reactions promoted by crown ether: Contact ion pair versus solvent‐separated ion pair mechanism

We examined by quantum chemical methods the mechanism of S_N2 reaction using metal bromide MBr (M = Na, K, Cs) and KX (X= F, Cl) in CH₃CN promoted by crown ether (18‐crown‐6). We focus on whether the metal salts react as a contact ion pair (CIP; M⁺ and X^– in close contact) or as a solvent‐separated ion pair (SSIP; M⁺ and X^– at large distance). In SSIP mechanism, X^– is removed far enough from M⁺ for the metal salt to be considered as “separated” by the effects of the crown ether and the solvent. In the CIP picture, conversely, the coordination of 18‐crown‐6 to M⁺ is not sufficient to overcome the powerful Coulombic interactions between M⁺ and X^–. We find that the CIP route is favored for S_N2 bromination processes using MBr (M = Na, K, Cs). For S_N2 reaction using KF, the feasibility of the two pathways is essentially equal, whereas for S_N2 chlorination by KCl the SSIP route is predicted to be favored.     

Use of an immiscible diluent in ionic liquid / ion pair LC for the assay of an injectable analgesic

Injectable solutions used in treatment of intense pain are based on combinations of active ingredients such as metamizole sodium (MTZ), pitofenone hydrochloride (PTF) and fenpiverine bromide (FPB). The simultaneous chromatographic assay of such combinations poses difficulties due to their structural variety, highly polar character, and wide concentration ranges (500 mg mL⁻¹ for MTZ, 2 mg mL⁻¹ for PTF and 0.02 mg mL⁻¹ for FPB). Fast hydrolysis of MTZ on aqueous dilution causes additional problems due to impurity (MTC) formation. Sodium hexane sulphonate (10 mM) was used as ion pairing agent for PTF, FPB and MTC in a mobile phase consisting of 48/52 (v/v) methanol and aqueous 0.2% triethylamine at pH=3. The ionic liquid 1-butyl-1-methyl-pyrrolidinium tetrafluoroborate (10 mM) was used as mobile phase additive to preserve the MTZ peak symmetry. The minor active ingredient FPB was selectively extracted into 1-octanol by ion pair formation with picric acid. A 20 μL aliquot of the organic layer was directly injected into the column.