Adsorption of Kryptate Complexes of Alkali Metals in Electrolytes of Different Compositions and in the Presence of 1-Adamantanol

Data on the adsorption of kryptates of alkali metals on a mercury electrode are obtained for the first time by a method of the measurement of the differential capacitance as a function of potential and are compared to one another. Shown is that there takes place a deep mutual relationship between the structure of a complex and the regularities of its adsorption. An assumption is put forth about the possibility of adsorption of a free ligand in solutions of lithium kryptate, which possesses relatively low strength. The co-adsorption of sodium kryptate with 1-adamantanol, which forms a two-dimensional condensed layer, is investigated. Established is that the C vs. E curves, obtained in 1 M Na₂SO₄ at a constant activity of 1-adamantanol and a varying concentration of Kryptofix^R 222, exhibit two distinctly pronounced portions, each of which corresponds to predominant adsorption of one of the surface-active components. The region of predominant adsorption of Kryptofix^R 222 expands with its concentration.     

Silver Cation Reduction on a Mercury Electrode: Effect of Two-Dimensional Condensed Layer of 1-AdOH during Individual Adsorption and Coadsorption with Tetraalkyl Cations

Effect of a condensed layer (CL) of 1-adamantanol (1-AdOH) during individual adsorption and coadsorption with tetraalkyl cations on the kinetics of the electroreduction (ER) of cation Ag⁺ at a mercury electrode is studied with the aim of revealing the link between the rate of electrode processes and the structure of two-dimensional CL. It is shown that ER of Ag⁺ occurs by means of penetration of the depolarizer particles through the adsorption layer. Polarization curves are calculated under the assumption that the potential barrier for ER of Ag⁺ in the presence of CL of 1-AdOH is defined by the work for overcoming two-dimensional pressure in the layer. Satisfactory agreement between experimental and calculated dependences in the region of ascending branches of polarization curves is demonstrated. It is established that the degree of the inhibiting action of mixed adsorption layers (as compared with individual CL of 1-AdOH) on ER of Ag⁺ depends on the 1-AdOH activity in solution and the nature of the organic cation. It is assumed that the latter effect is caused by the surface activity of cations studied.     

Determining Sodium Kryptate Adsorption Parameters on a Mercury Electrode in 1 M Na2SO4

The adsorption of a complex of sodium cations with a macrocyclic ligand (Kryptofix^R 222, composition C₁₈H₃₆N₂O₆) as a function of its concentration in 1 M Na₂SO₄ is studied by measuring the differential capacitance on a stationary Hg drop. Adsorption parameters of sodium kryptate are found using a regression analysis method and various versions of a model of two parallel capacitors complemented with the Frumkin adsorption isotherm. The differential capacitance curves, calculated on the basis of these, are compared with experimental data. The difference in model versions that most adequately describe the adsorption data, established for systems in 0.1 and 1 M Na₂SO₄, is explained by the influence of the supporting electrolyte on the adsorption layer structure. Conclusions are made on the absence in the system under study of the salting-out from the bulk solution and on a change in the properties of an adsorption layer of sodium kryptate in the region of potentials of the anodic adsorption–desorption peak following expansion of the adsorption region.     

Conductance and Thermodynamic Study of Thallium and Silver Ion Complexes with Crown Ethers in Different Binary Acetonitrile–Water Solvent Mixtures

The complexation reactions between Ag⁺ andTl⁺ ions with 15-crown-5 (15C5) and phenyl-aza-15-crown-5(PhA15C5) have been studied conductometrically in 90%acetonitrile-water and 50% acetonitrile - water mixed solvents attemperatures of 293, 298, 303 and 308 K. The stability constants of theresulting 1 : 1 complexes were determined, indicating that theTl⁺ complexes are more stable than the Ag⁺complexes. The enthalpy and entropy of crown complexation reactions were determined from the temperature dependence of the complexation constants.The enthalpy and entropy changes depend on solvent composition and the T S⁰ _o–H⁰ plotshows a good linear correlation, indicating the existence of entropy –enthalpy compensation in the crown complexation reactions.     

Conductance study of complex formation of thallium and silver ions with several crown ethers in acetonitrile,acetone and dimethylformamide solutions

The complexation reactions between Tl⁺ and Ag⁺ ions and several crown ethers have been studied conductometrically in acetonitrile, acetone and dimethylformamide solutions at 25°C. The stability constants of the resulting 1:1 complexes were determined, and found to decrease in the order DA18C6>DC18C6>DB30C10>18C6>DB21C7>DB24C8>DB18C6>B15C5 >12C4, in the case of Tl⁺ complexes, and in the order DA18C6>DC18C6>18C6>DB18C6 >DB24C8>DB30C10B15C5>DB21C7 for Ag⁺ complexes. There is an inverse relationship between the stabilities of the complexes and the Gutamnn donicity of the solvents. The influence of a number of atoms in the macrocycle and of substituents in the polyether ring on the stability of the complexes is discussed.     

A convenient synthesis of new thiaazacrown ethers and study of their complexation reactions with some transition metal cations in binary acetonitrile–chloroform mixture using the conductometric method

Three novel thiaazacrown ethers 1, 2 and 3 were synthesized in a simple way and in high yield. The complex formation between Ag⁺, Cu²⁺, Zn²⁺, Pb²⁺, Hg²⁺ and Cd²⁺ metal cations with thiaazacrown ethers 1, 2 and 3 have been studied in acetonitrile:chloroform (1:1) binary solvent system using conductometric technique. The conductance data show that the stochiometry of the complexes with Ag⁺, Cu²⁺ and Zn²⁺ cations is 1:1 (L:M), but in the case of Pb²⁺ and Hg²⁺ cations, a 1:2 (L:M) complex is formed in solutions. The formation constants of the resulting 1:1 complexes were determined from the molar conductance-mole ratio data at 25 °C. It was found that the stability constants of 1-Ag²⁺, 2-Ag⁺ and 3-Ag⁺ complexes are higher than those of their corresponding Zn²⁺ and Cu²⁺ complexes and found to vary in order 3 > 1 > 2 for Ag⁺.     

All-Solid-State PVC Membrane Ag+-Selective Electrodes Based on Diaza-18-Crown-6 Compounds

Two diaza-crown ether compounds were synthesized and evaluated as Ag⁺-selective carriers in polyvinylchloride (PVC) membrane electrodes of solid-state type. The all-solid-state PVC membrane electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 exhibited a super-Nernstian response (75±10mV per decade) over the concentration range of 1×10^–1 to 7×10^–6M of Ag⁺ ion and a detection limit of 3×10^–6M, at a wide range of pH (pH 4–7). The response time of the electrode was fast (less than 10s), and it can be used for three months without any significant deviation in potential. The proposed all-solid-state PVC membrane electrodes revealed high selectivity toward Ag⁺ ion with respect to alkali, alkaline earth, heavy and transition metal ions. A flow-through cell of all-solid-state PVC membrane Ag⁺-selective electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 has also been prepared and applied for flow-injection analysis of Ag⁺ ion in solution.     

Dissociations of Complexes Between Monovalent Metal Ions and Aromatic Amino Acid or Histidine

The fragmentations of [AA + M]⁺ complexes, where AA = Phe, Tyr, Trp, or His, and M is a monovalent metal (Li, Na, or Ag), have been exhaustively studied through collision-induced dissociation (CID) and through deuterium labeling. Dissociations of the Li- and Ag-containing complexes gave a large number of fragment ions; by contrast, the sodium/amino acid complexes have lower binding energies, and dissociation resulted in much simpler spectra, with loss of the entire ligand dominating. Unambiguous assignments of these fragment ions were made and formation mechanisms are proposed. Of particular interest are fragmentations in which the charge was retained on the organic fragment and the metal was lost, either as a metal hydride (AgH) or hydroxide (LiOH) or as the silver atom (Ag^?).

Fourier transform infrared spectroscopy study of the effect of pH on anion and cation adsorption onto poly(acrylo‐amidino diethylenediamine)

The role of hydrogen bonding in the chemistry of transition‐metal complexes remains a topic of intense scientific and technological interest. Poly(acrylo‐amidino diethylenediamine) was synthesized to study the effects of hydrogen bonding on complexes at different pHs. The polymer was synthesized through the coupling of diethylene triamine with polyacrylonitrile fiber in the presence of AlCl₃ · 6H₂O addition. The adsorption capacity of this polymer was 11.4 mequiv/g. The ions used for the adsorption test were CrO, PO, Cu²⁺, Ni²⁺, Fe²⁺, and Ag⁺. All experiments were confirmed with Fourier transform infrared. In the study of anion adsorption, at low pHs, only ionic bonds existed, whereas at high pHs, no bonds existed. However, in the middle pH region, both ionic bonds and hydrogen bonds formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion or phosphate ion. When poly(acrylo‐amidino diethylenediamine) and metal ions (Cu²⁺, Ni²⁺, Fe²⁺, and Ag⁺) formed complexes, a hydrogen‐bonding effect was not observed with Fourier transform infrared. The quantity of metal ions adsorbed onto poly(acrylo‐amidino diethylenediamine) followed the order Ag⁺ > Cu²⁺ > Fe²⁺ > Ni²⁺. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2010–2018, 2004     

Study of monensin complexes with monovalent metal lons in anhydrous methanol solutions

Potentiometric and cyclo-voltammetric studies have been carried out on monensin anion (Mon^–) complexes with the alkali ions as well as with Tl⁺ and Ag⁺ in absolute methanol solutions. The log K_f values obtained for the complexity constants and corrected for the activity effects are: Li⁺, 3.3±0.1; Na⁺, 6.72±0.05; K⁺, 5.18±0.05; Rb⁺, 4.58±0.05; Cs⁺, 3.75±0.05; Tl⁺, 5.31±0.05; Ag⁺, 8.2±0.2. It is seen that for the alkali, the most stable complex is formed with Na⁺. The enthalpy and entropy of complexation with the sodium ion were found to be H^o=–5.47±0.24 kcal-mole^–1 and S^o=+12.4±0.7 e.u. The complex, therefore, is enthalpy and entropy stabilized.     

Complexation of silver(I) with benzylpenicilline and oxacilline

The complexation of Ag⁺ ions with anions of β-lactam antibiotics, such as benzylpenicilline (Bzp^?) and oxacilline (Oxa^?), in aqueous solution at 25°C and an ionic strength of 0.1 (KNO₃) was studied potentiometrically using a silver indicator electrode. The formation constants of the complexes AgBzp (logβ = 2.21 ± 0.01), AgBzp ₂ ^? (logβ = 3.91 ± 0.02), Ag₂Oxa⁺ (logβ = 4.89 ± 0.01), AgOxa (logβ = 2.88 ± 0.01), (logβ = 5.43 ± 0.01) were determined.     

Electronic structures of organo-transition-metal complexes I. Silver(I)-Olefin complexes

By using the closed-shell SCF-MO method with the CNDO type approximation for all valence electron systems, the electronic structures of some Ag⁺-olefin complexes are investigated. The calculated values of -H increase with the increasing number of methyl groups on the double bond and this trend agrees with the experimental result. Also calculation reproduces many experimental results, such as the infrared, Raman, and¹³C NMR spectra. These experimental results are discussed on the basis of the calculated electronic structures of Ag⁺-olefin complexes.     

Study of complexation of phenylaza-15-crwon-5, 4-nitrobenzo- 15-crown-5, and benzo-15-crown-5 with Ag+, Tl+ and Pb2+ ions in methanol by competitive potentiometry

The complexation reaction of phenylaza-15-crwon-5, 4- nitrobenzo- 15-crown-5, and benzo-15-crown-5 with Ag⁺, Tl⁺ and Pb²⁺ ions in methanol solution have been studied by a competitive potentiometric method. The Ag⁺/Ag electrode used both as an indicator and reference electrode in a concentration cell. The emf of cell monitored as the crown ethers concentration varies through the titration. The stoichiometry and stability constants of resulting complexes have been evaluated by MINIQUAD. The stoichiometry for all resulting complexes was 1:1. The stability of these metal ions with derivatives of 15-crown-5 are in order phenylaza-15-crown-5 > Benzo-15-crown-5 > 4-nitrobenzo-15-crown-5, and for the each used crown ethers are as Pb²⁺ > Ag⁺ > Tl⁺. The effect of the substituted group on the stability of resulting complexes was considered. The obtained results are novel and interesting.     

Allosteric bindings of thiacalix[4]arene-based receptors with 1,3-alternate conformation having two different side arms

A novel ditopic receptor possessing two complexation sites such as crown ether and 2-pyridylmethyl groups bearing 1,3-alternate conformation based on thiacalix[4]arene was prepared. The binding behaviors with Li⁺ and Ag⁺ have been examined by ¹H NMR titration experiment. The exclusive formation of mononuclear complexes of 1,3-alternate-5 with Li⁺ and Ag⁺ was observed even though the formation of the heterogeneous dinuclear complexes was expected. The decomplexation of Li⁺ from the crown moiety of 1:1 complex 1,3-alternate-5?Li⁺ to form the Ag⁺?1,3-alternate-5 complex by addition of AgSO₃CF₃ clearly shows that pyridyl moiety works as an efficient switch-off of the recognition ability of the crown moiety. We have also developed the construction of hydrogen-bonding self-assembly heterodimeric systems based on bis(4-pyridyl) and dicarboxylic acid thiacalix[4]arene derivatives in 1,3-alternate conformation. Their supramolecular behaviors are studied by ¹H NMR titration experiments with K⁺ and Ag⁺ ions. Although the values of the dimerization constants are relatively small, the stability of the dimers is strong enough to overcome only small conformational changes upon complex formation.     

A Cryptate Reference Electrode for Ionic Liquids

The cryptate electrode (Ag/Ag⁺222), prepared by immersing silver wire in a solution of silver(I) salt and the cryptand 222 (4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) in ionic liquids have been studied. The potential of the electrode is stabilized by the equilibrium of the Ag⁺ ion complexation by the cryptand, similarly to the potential stabilization by the ionic product of slightly soluble salts, used in aqueous electrodes of the second kind. The Ag/Ag⁺222 cryptate electrode (concentration of the cryptate was much higher than the silver(I) cation concentration, [222]>[Ag⁺]) may be used as a reference electrode in room temperature ionic liquids. The potential of the Ag/Ag⁺222 electrode is less sensitive to the presence of impurities, such as halides or water, in comparison to the Ag/Ag⁺ electrode. After anodic or cathodic polarization, the potential of the Ag/Ag⁺222 electrode comes back to the initial open circuit potential quickly. Preparation of the Ag/Ag⁺222 reference electrode is very easy: a silver wire is immersed in a solution of Ag⁺ salt and cryptand 222 (both available commercially) in the ionic liquid under study.     

Novel metal cluster complexes synthesized by matrix deposition of mass-selected clusters

Metal complexes produced by depositing size selected Fe and Ag cluster cations in N₂ and O₂ matrices respectively are studied by infrared spectroscopy. Unknown species such as Fe(N₂)x, Fe₃ (N₂)x and Ag₃(O₂)x are observed. The IR spectra of Ag⁺, Ag ₂ ⁺ and Ag ₉ ⁺ in excess O₂ indicate that no complexes involving molecular oxygen are formed. However, the strong silver cluster UV-visible absorptions detected in Ar matrices disappear in the oxygen matrices, suggesting that silver-oxygen complexes are formed with dissociated oxygen.     

Sensitive electrochemical DNA-based biosensors for the determination of Ag<Superscript>+</Superscript> and Hg<Superscript>2+</Superscript> ions and their application in analysis of amalgam filling

In the present paper, we used single-stranded poly-T (100% thymine bases) and poly-C (100% cytosine bases) nucleic acids as DNA probes for selective and sensitive individual electrochemical determination of Hg²⁺ and Ag⁺_, respectively, on the multi-walled carbon nanotube paste electrodes (MWCNTPEs) using [Fe(CN)₆]^3?/4? as electroactive labels. In the presence of Hg²⁺ and Ag⁺, the probe–Hg²⁺/Ag⁺ interactions through T–Hg²⁺–T and C–Ag⁺–C complexes formation could cause the formation of a unimolecular hybridized probe. This structure of probe led to its partial depletion from electrode surface and facilitation of electron transfer between [Fe(CN)₆]^3?/4? redox couple and electrode surface, resulting in the enhanced differential pulse voltammetry (DPV) oxidation current of [Fe(CN)₆]^3?/4? at the probe-modified electrode surface. We applied the difference in the oxidation peak currents of [Fe(CN)₆]^3?/4? before and after Hg²⁺/Ag⁺–DNA probe bonding (?I) for electrochemical determination of these heavy metal ions. Detection limits were 8.0?×?10^?12 M and 1.0?×?10^?11 M for Hg²⁺ and Ag⁺ ions determination, respectively. The biosensors were utilized to determine the weight percent of toxic metals, i.e., silver and mercury in dental amalgam filling composition. The results of their practical applicability in analysis of the amalgam sample were satisfactory.     

Preconcentration and voltammetric behaviour of Ag+ at carbon paste electrodes modified by N-benzoyl-N′,N′-di-i-butyl-thiourea

The preconcentration of silver at carbon paste electrodes (CPE) modified with N-benzoyl-N,N-di-i-butyl-thiourea and its subsequent voltammetric determination is studied with test solutions. The preconcentration of silver at the surface of the modified CPE succeeds as well with open circuits as with applied potentials. The amount preconcentrated depends on the electrode potential with a maximum at +0.1 V vs. Ag/AgCl, thus enabling the preconcentration of silver without cathodic treatment. The detection limit is in the order of 10^–4 mmol/l Ag⁺. The surface reactions during the preconcentration are discussed. It is assumed that silver complexes of the modifier are formed in a fast reaction followed by a slow reaction with participation of silver and of carbon surface groups.     

Adsorption properties of amidoximated porous acrylonitrile/methyl acrylate copolymer beads for Ag (I)

Porous a crylonitrile (AN)/methyl acrylate (MA) copolymer beads were synthesized by suspended emulsion polymerization and amidoximated for the purpose of Ag⁺ adsorption. Optimum amidoximation temperature and time were determined by following the adsorption capacity for Ag⁺. The results showed that amidoximated AN/MA (AO AN/MA) with the amidoximation temperature 70°C and amidoximation time 20 hr had a relatively higher adsorption capacity for Ag⁺. The effect of pH on adsorption for Ag⁺ was studied; the highest adsorption capacity presented at pH 5.0. Adsorption kinetics and isotherms of AO AN/MA copolymer beads for Ag⁺ were also investigated. The kinetics data indicated that the adsorption process was governed by the film diffusion and followed both pseudo‐first‐order and pseudo‐second‐order rate model. The isotherms indicated that adsorption capacities increased with equilibrium concentration and temperature. The Langmuir model and Sips model could describe the isothermal process. Thermodynamic analysis revealed that the adsorption behaviors of Ag⁺ ions on AO AN/MA could be considered as endothermic and physical sorption process. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of Transition Metal Cationization versus Sodium Cationization and Protonation on the Gas-Phase Tautomeric Conformations and Stability of Uracil: Application to [Ura+Cu]<Superscript>+</Superscript> and [Ura+Ag]<Superscript>+</Superscript>

The gas-phase conformations of transition metal cation-uracil complexes, [Ura+Cu]⁺ and [Ura+Ag]⁺, were examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra were measured over the IR fingerprint and hydrogen-stretching regions. Structures and linear IR spectra of the stable tautomeric conformations of these complexes were initially determined at the B3LYP/6-31G(d) level. The four most stable structures computed were also examined at the B3LYP/def2-TZVPPD level to improve the accuracy of the predicted IR spectra. Two very favorable modes of binding are found for [Ura+Cu]⁺ and [Ura+Ag]⁺ that involve O2N3 bidentate binding to the 2-keto-4-hydroxy minor tautomer and O4 monodentate binding to the canonical 2,4-diketo tautomer of Ura. Comparisons between the measured IRMPD and calculated IR spectra enable elucidation of the conformers present in the experiments. These comparisons indicate that both favorable binding modes are represented in the experimental tautomeric conformations of [Ura+Cu]⁺ and [Ura+Ag]⁺. B3LYP suggests that Cu⁺ exhibits a slight preference for O4 binding, whereas Ag⁺ exhibits a slight preference for O2N3 binding. In contrast, MP2 suggests that both Cu⁺ and Ag⁺ exhibit a more significant preference for O2N3 binding. The relative band intensities suggest that O4 binding conformers comprise a larger portion of the population for [Ura+Ag]⁺ than [Ura+Cu]⁺. The dissociation behavior and relative stabilities of the [Ura+M]⁺ complexes, M⁺ = Cu⁺, Ag⁺, H⁺, and Na⁺) are examined via energy-resolved collision-induced dissociation experiments. The IRMPD spectra, dissociation behaviors, and binding preferences of Cu⁺ and Ag⁺ are compared with previous and present results for those of H⁺ and Na⁺.

Open image in new window

Graphical Abstract ?