Ultrasensitive Detection of Cu<Superscript>2+</Superscript> Using a Microcantilever Sensor Modified with L-Cysteine Self-Assembled Monolayer

A microcantilever was modified with a self-assembled monolayer (SAM) of L-cysteine for the sensitively and selectively response to Cu(II) ions in aqueous solution. The microcantilever undergoes bending due to sorption of Cu(II) ions. The interaction of Cu(II) ions with the L-cysteine on the cantilever is diffusion controlled and does not follow a simple Langmuir adsorption model. A concentration of 10^?10 M Cu(II) was detected in a fluid cell using this technology. Other cations, such as Ni²⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ca²⁺, K⁺, and Na⁺, did not respond with a significant deflection, indicating that this L-cysteine-modified cantilever responded selectively and sensitively to Cu(II).     

Transport of Ca2+, Sr2+, Ba2+, Na+, K+ and Cs+ through hollow fiber supported liquid membrane

The transport of metal ions (Ca²⁺, Sr²⁺, Ba²⁺, Na⁺, K⁺, Cs⁺) through hollow fiber supported dichlorobenzene liquid membrane has been studied. The transport of cations using 8-crown-6 ether as a carrier and picrate as co-counter ion as well as a pertraction device and capillary isotachophoresis (ITP) measurement of the cation concentration is described.     

Facilitated Transfer of Alkali and Alkaline‐Earth Metal Ions by a Calix[4]arene Derivative Across Water/1,2‐Dichloroethane Microinterface: Amperometric Detection of Ca2+

The host–guest complexation reactions between 5,11,17,23‐tetra‐tert‐butyl‐25,27‐diethoxycarbonylmethoxy‐26,28‐dimethoxy calix[4]arene (BDDC4) and alkali and alkaline‐earth metal ions were investigated by facilitated ion transfer processes across water/1,2‐dichloroethane microinterface by using steady‐state cyclic voltammetry and differential pulse voltammetry. The obtained facilitated transfers for Li⁺, Na⁺, K⁺, Rb⁺ and Ca²⁺ were evaluated under the different experimental conditions, at the excess concentrations of metal ions with respect to BDDC4 and vice versa. The association constants having 1 : 1 stoichiometry for Li⁺, Na⁺, K⁺ and Rb⁺ in 1,2‐DCE were determined. Also, we demonstrated that BDDC4 can play an important role for the development of highly selective chemical sensor for Ca²⁺ among alkaline‐metal ions in the concentration range of 0.1–1.0 mM in aqueous solution.     

Use of Ionic liquids as additives in ion exchange chromatography for the analysis of cations

The behavior of acids (citric acid, nitric acid, oxalic acid, tartaric acid) as a mobile phase and imidazolium ionic liquids (the bromides, tetrafluoroborates and hexafluorophosphates of 1‐ethyl, 1‐butyl, and 1‐hexyl‐3‐methylimidazolium) as additives in ion exchange chromatography for cations (Na⁺, K⁺, Mg²⁺, Ca²⁺) separation were studied. The results showed that nitric acid and 1‐hexyl‐3‐methyl‐imidazolium hexafluorophosphate offered the most interesting features in the separation of cations, such as lower retention time and better resolution. The selected optimal conditions were achieved by adding 0.10 mM 1‐hexyl‐3‐methyl‐imidazolium hexafluorophosphate in 4.0 mM HNO₃ mobile phase for the separation of four cations with the flow rate of 0.9 mL/min at room temperature (25°C). The linear regression equations of Na⁺, K⁺, Mg²⁺, Ca²⁺ were S  = 4.4763c  + 0.0209, S  = 3.8903c  – 0.0087, S  = 6.3974c  – 0.0173, and S  = 7.601c  – 0.0339 and the limits of detection of Na⁺, K⁺, Mg²⁺, Ca²⁺ were 0.296, 4.98, 0.0970, and 1.22 μg/L, respectively. In this work, four cations in samples were successfully detected.     

Highly Selective Artificial Cholesteryl Crown Ether K+‐Channels

The bacterial KcsA channel conducts K⁺ cations at high rates while excluding Na⁺ cations. Herein, we report an artificial ion‐channel formed by H‐bonded stacks of crown‐ethers, where K⁺ cation conduction is highly preferred to Na⁺ cations. The macrocycles aligned along the central pore surround the K⁺ cations in a similar manner to the water around the hydrated cation, compensating for the energetic cost of their dehydration. In contrast, the Na⁺ cation does not fit the macrocyclic binding sites, so its dehydration is not completely compensated. The present highly K⁺‐selective macrocyclic channel may be regarded as a biomimetic of the KcsA channel.     

Sorption characteristics of Am(III), Sr(II) and Cs(I) on bentonite and granite

The ability of the back-fill and the host rock materials to take up radioisotopes like ²⁴¹Am, ^85,89Sr and ¹³⁷Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na⁺, K⁺, Ca²⁺ and Mg²⁺ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V _m ,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated.     

Equilibria and heats of exchange of alkaline-earth metal ions on the Na form of mordenite

Sorption-analytic studies of ion exchange equilibria combined with direct calorimetric measurements of the heats of ion exchange sorption of the Ca²⁺, Sr²⁺, and Ba²⁺ cations were performed over the whole range of solid phase fillings with sorbed cations on the Na forms of two mordenites prepared from natural specimens rich in Na⁺ and Ca²⁺ cations. Ion exchange constants were determined and the Gibbs energies and entropies of ion exchange were calculated. The thermodynamic characteristics obtained were analyzed taking into account the preferable localization of alkaline-earth metal ions on certain exchange centers in the structure of mordenite. The presence of natural mordenite memory effects with respect to extra-framework Ca²⁺ cations in the presence of which these zeolites were crystallized in nature was established.     

Affinity capillary electrophoresis employed for determination of stability constants of antamanide complexes with univalent and divalent cations in methanol

Affinity capillary electrophoresis (ACE) and pressure‐assisted ACE were employed to study the noncovalent molecular interactions of antamanide (AA), cyclic decapeptide from the deadly poisonous fungus Amanita phalloides, with univalent (Li⁺, Na⁺, K⁺, and NH₄⁺) and divalent (Mg²⁺ and Ca²⁺) cations in methanol. The strength of these interactions was quantified by the apparent stability constants of the appropriate AA‐cation complexes. The stability constants were calculated using the nonlinear regression analysis of the dependence of the effective electrophoretic mobility of AA on the concentration of the above ions in the BGE (methanolic solution of 20 mM chloroacetic acid, 10 mM Tris, pH_MeOH 7.8, containing 0–50 mM concentrations of the above ions added in the form of chlorides). Prior to stability constant calculation, the AA effective mobilities measured at actual temperature inside the capillary and at variable ionic strength of the BGEs were corrected to the values corresponding to the reference temperature of 25°C and to the constant ionic strength of 10 mM. From the above ions, sodium cation interacted with AA moderately strong with the stability constant 362 ± 16 L/mol. K⁺, Mg²⁺, and Ca²⁺ cations formed with AA weak complexes with stability constants in the range 37–31 L/mol decreasing in the order K⁺ > Ca²⁺ > Mg²⁺. No interactions were observed between AA and small Li⁺ and large NH₄⁺ cations.     

Solvation of Calcium–Phosphate Headgroup Complexes at the DPPC/Aqueous Interface

The effects of sodium (Na⁺) and calcium (Ca²⁺) cations on model zwitterionic dipalmitoylphosphatidylcholine (DPPC) monolayers spread on metal chloride salt solutions are investigated by means of vibrational sum frequency generation (VSFG) and heterodyne‐detected (HD)‐VSFG spectroscopy. VSFG and HD‐VSFG spectra in the OH stretching region reveal cation‐specific effects on the interfacial water′s H‐bonding network, knowledge of which has been limited to date. It is found that low‐concentrated Ca²⁺ more strongly perturbs interfacial water organization relative to highly concentrated Na⁺. At higher Ca²⁺ concentrations, the water H‐bonding network at the DPPC/CaCl₂ interface reorganizes and the resulting spectrum closely follows that of the bare air/CaCl₂ interface up to ～3400 cm^?1. Most interesting is the appearance of a negative band at ～3450 cm^?1 in the DPPC/CaCl₂ Im χ_s⁽²⁾ spectra, likely arising from an asymmetric solvation of Ca²⁺–phosphate headgroup complexes. This gives rise to an electric field that orients the net OH transition moments of a subset of OH dipoles toward the bulk solution.     

Ions Can Move a Proton‐Coupled Electron‐Transfer Reaction into Tunneling Regime

The effects of charged species on proton‐coupled electron‐transfer (PCET) reaction should be of significance for understanding/application of important chemical and biological PCET systems. Such species can be found in proximity of activated complex in a PCET reaction, although they are not involved in the charge transfer process. Reported here is the first study of the above‐mentioned effects. Here, the effects of Na⁺, K⁺, Li⁺, Ca²⁺, Mg²⁺, and Me₄N⁺ observed in PCET reaction of ascorbate monoanions with hexacyanoferrate(III) ions in H₂O reveal that, in presence of ions, this over‐the‐barrier reaction entered into tunneling regime. The observations are: a) dependence of the rate constant on the cation concentration, where the rate constant is 71 (at I = 0.0023), and 821 (at 0.5M K⁺), 847 (at 1.0M Na⁺), and 438 M ^?1 s^?1 (at 0.011M Ca²⁺); b) changes of kinetic isotope effect (KIE) in the presence of ions, where k_H/k_D=4.6 (at I = 0.0023), and 3.4 (in the presence of 0.5M K⁺), 3.3 (at 1.0M Na⁺), 3.9 (at 0.001M Ca²⁺), and 3.9 (at 0.001M Mg²⁺), respectively; c) the isotope effects on Arrhenius pre‐factor where A_H/A_D=0.97 (0.15) in absence of ions, and 2.29 (0.60) (at 0.5M Na⁺), 1.77 (0.29) (at 1.0M Na⁺), 1.61 (0.25) (at 0.5M K⁺), 0.42 (0.16) (at 0.001M Ca²⁺) and 0.16 (0.19) (at 0.001M Mg²⁺); d) isotope differences in the enthalpies of activation in H₂O and in D₂O, where ΔΔH^?(D,H)=3.9 (0.4) kJ mol^?1 in the absence of cations, 1.3 (0.6) at 0.5M Na⁺, 1.8 (0.4) at 0.5M K⁺, 1.5 (0.4) at 1.0M Na⁺, 5.5 (0.9) (at 0.001M Ca²⁺), and 7.9 (2.8) (at 0.001M Mg²⁺) kJ mol^?1; e) nonlinear proton inventory in reaction. In the H₂O/dioxane 1 : 1, the observed KIE is 7.8 and 4.4 in the absence and in the presence of 0.1M K⁺, respectively, and A_H/A_D=0.14 (0.03). The changes when cations are present in the reaction are explained in terms of termolecular encounter complex consisting of redox partners, and the cation where the cation can be found in a near proximity of the reaction‐activated complex thus influencing the proton/electron double tunneling event in the PCET process. A molecule of H₂O is involved in the transition state. The resulting ‘configuration’ is more ‘rigid’ and more appropriate for efficient tunneling with Na⁺ or K⁺ (extensive tunneling observed), i.e., there is more precise organized H transfer coordinate than in the case of Ca²⁺ and Mg²⁺ (moderate tunneling observed) in the reaction.     

Untersuchung der Komplexierung von Na+, K+, Ca2+ und Ba2+ mit einigen elektrisch neutralen Liganden durch Messung von 13C-chemischen Verschiebungen und Spin-Gitter-Relaxationszeiten

Investigation of the complexing of Na⁺, K⁺, Ca²⁺ and Ba²⁺ with some uncharged ligands by ¹³C-chemical shift and spin-lattice relaxation time measurements The influence of Na⁺, K⁺, Ca²⁺ and Ba²⁺ ions on ¹³C chemical shifts and on spin-lattice relaxation times of some electrically neutral ion carriers was investigated. In the solvents CD₃CN and CD₃OD and in presence of an excess of metal ions ligand 4 (see the Scheme) forms complexes of 1:1 stoichiometry. All four oxygen atoms of the ligand as well as solvent molecules take part in the coordination. In CDCl₃ as solvent, for all ions investigated except sodium, only 1:2 complexes (metal/ligand) were observed with 4 . Sodium ions form both 1:1 and 1:2 complexes in this solvent. In the 1:2 complexes of the investigated monovalent ions only one, in those of the divalent ions both amide carbonyl groups of ligand 4 take part in the coordination.     

Adsorption of Co2+ and Zn2+ on cryptomelane-type hydrous managese dioxide

Co²⁺ and Zn²⁺ ions are adsorbed on cryptomelane-type MnO₂ by exchange with surface protons and with structural ions (probably K⁺ and/or Mn²⁺) in the oxide. The latter sites are responsible for the much higher capacity to these cations, compared to Na⁺. At all pH values, two straight lines expressing the presence of mainly two groups of sites with distinctly different adsorption energies are located in the Langmuir plots for both Co²⁺ and Zn²⁺. The apparent capacities of the two groups increase with the increase of pH, indicating the involvement of protons in the adsorption process over the whole concentration range. The higher Co²⁺ capacity at relatively low pH, compared to the Zn²⁺ capacity, is probably due to a more exchange with the structural ions. Crytomelane type MnO₂ seems to be a quite heterogenous ion adsorbent whose adsorption sites could be approximated to two groups only.     

Sensitivity and Selectivity of Polypyrrole Based AC‐Amperometric Sensors for Electroinactive Ions – Frequency and Applied Potential Influence

Oxidation/reduction of polypyrrole films coupled with ion exchange on the polymer/solution interface can be utilized for amperometric sensing of electroinactive ions. Anion or cation exchanging films (polypyrrole doped by chloride or poly(4‐styrenesulfonate) ions, respectively) can be used to determine common anions (as Cl^?, NO , SO etc) or cations (K⁺, Na⁺, Li⁺, Ca²⁺, Mg²⁺) under conditions of alternating current (AC) amperometry in the range 10^?4–1 M. A sensitivity can be tuned by choosing appropriate electrode potential, corresponding to polypyrrole oxidation (anion‐exchanging films) or reduction (cation‐exchangers). Electrochemical impedance spectroscopy and AC‐voltammetry studies have shown that applied frequency and potential could also affect the observed dependence of the signal (admittance or AC‐current) on ion concentration. For high frequency the sensitivity is higher but selectivity lower, due to influence of solution conductivity on the response. For low frequencies the sensitivity is lower; however, a selectivity increase was observed due to diverse mobility of ions in the polymer film. Selectivity of AC‐amperometric responses was studied both in separate and mixed solutions.     

Chirality Transfer in Propeller‐Shaped Cyclen?Calcium(II) Complexes: Metal‐Coordinating and Ion‐Pairing Anion Procedures

A series of quadruple‐stranded Na⁺ and Ca²⁺ complexes with octadentate cyclen ligands was synthesized to produce complexes that contained four different side‐arm combinations (one triazole? coumarin group and three pyridine groups ( 1 ), four pyridine groups ( 2 ), one triazole? coumarin group and three quinoline groups ( 3 ), and four quinoline groups ( 4 )). X‐ray crystallographic analysis revealed that no significant changes occurred in the stereostructure of these complexes upon replacing one pyridine group with a triazole? coumarin moiety, or by replacing Na⁺ ions with Ca²⁺ ions, although the coordination number of the complexes in the solid state decreased when pyridine groups were replaced by quinoline groups. In solution, all of the side arms were arranged in a propeller‐like pattern to yield an enantiomer pair of Δ and Λ forms in each metal complex. The addition of a tert‐butoxycarbonyl (Boc)‐protected amino acid anion, that is, a coordinative chiral carboxylate anion, to the cyclen? Ca²⁺ complex induced circular dichroism (CD) signals in the aromatic region by forming a 1:1 mixture of diastereomeric ternary complexes with opposite complex chirality, whilst the corresponding Na⁺ complexes rarely showed any response. In complexes 1 ‐Ca²⁺ and 3 ‐Ca²⁺, this chirality‐transfer process was efficiently followed by considering the induction of the CD signals at two different wavelengths, that is, the coumarin‐chromophore region and the aza‐aromatic region. The sign and intensity of the CD signal were significantly dependent on both the nature of the aza‐aromatic moiety and the enantiomeric purity of the external anion. These Ca²⁺ complexes worked as effective probes for the determination of the enantiomeric excess of the chiral anion. The cyclen? Ca²⁺ complexes also interacted with the non‐coordinative Δ‐TRISPHAT anion through an ion‐pairing mechanism to achieve chirality transfer from the anion to the metal complex; both complexes 1 ‐Ca²⁺ and 3 ‐Ca²⁺ clearly showed induced CD signals in the coumarin‐chromophore region, owing to ion‐paring interactions with the Δ‐TRISPHAT anion. Thus, the proper combination of an octadentate cyclen ligand and a metal center demonstrated effective chirality transfer.     

Glu 87 of Channelrhodopsin‐1 Causes pH‐dependent Color Tuning and Fast Photocurrent Inactivation†

Channelrhodopsins (ChR1 and ChR2) are directly light‐gated ion channels acting as sensory photoreceptors in the green alga Chlamydomonas reinhardtii. These channels open rapidly after light absorption and both become permeable for cations such as H⁺, Li⁺, Na⁺, K⁺ and Ca²⁺. K_m for Ca²⁺ is 16.6 mm in ChR1 and 18.3 mm in ChR2 whereas the K_m values for Na⁺ are higher than 100 mm for both ChRs. Action spectra of ChR1 peak between 470 and 500 nm depending on the pH conditions, whereas ChR2 peaks at 470 nm regardless of the pH value. Now we created two chimeric ChRs possessing helix 1–5 of ChR1 and 6, 7 of ChR2 (ChR1/2_5/2), or 1, 2 from ChR1 and 3–7 from ChR2 (ChR1/2_2/5). Both ChR‐chimera still showed pH‐dependent action spectra shifts. Finally, a mutant ChR1E87Q was generated that inactivated only slowly in the light and showed no spectral shift upon pH change. The results indicate that protonation/deprotonation of E87 in helix 1 alters the chromophore polarity, which shifts the absorption and modifies channel inactivation accordingly. We propose a trimodal counter ion complex for ChR1 but only a bimodal complex for ChR2.     

Host‐Guest Complexes of Dodeka(ethylene)octamine: Prediction of Ion Selectivity by Quantum Chemical Calculations IX

In this contribution we investigated the ion complexation of Bühl's cryptand, dodeka(ethylene)octamine by quantum chemical methods (B3LYP/LANL2DZp). This cryptand is an isomer of a well‐known Lehn‐type cryptand [TriPip222]. The ion selectivity was determined based on the energetic criteria derived by model reactions starting from solvated metal ions and empty dodeka(ethylene)octamine, and by comparing the M–N bond length in [M ? dodeka(ethylene)octamine]^m+ and [M(NH₃)₆]^m+. We calculated that Bühl's cryptand will complex best Na⁺ followed by Li⁺ as alkaline cations and Ca²⁺ followed by Mg²⁺ as alkaline earth metal ions. Based on this data we conclude that Bühl's cryptand offers a smaller cavity to nest ions than the Lehn‐type [TriPip222].     

A New Fluorescent Chemosensor for Cu2+ Based on 1,2,3,4,5,6,7,8,9,10‐Decahydroacridine‐1,8‐dione Fluorophore

A new chemosensor for Cu²⁺ was synthesized based on 1,2,3,4,5,6,7,8,9,10‐decahydroacridine‐1,8‐dione dyes, which exhibited an obvious fluorescent selectivity to the sensing of Cu²⁺ ions over other cations, such as Na⁺, K⁺, Ca²⁺, Cd²⁺, Co²⁺, Hg²⁺, Mg²⁺, Mn²⁺, Ni²⁺, Zn²⁺, Ag⁺ and Pb²⁺. Moreover, it presented a fluorescent switch function when EDTA was added to the compound‐Cu²⁺ complex in examined systems.     

Silver(I)‐Selective PVC Membrane Potentiometric Sensor Based on a Recently Synthesized Calix[4]arene

A new PVC membrane potentiometric sensor for Ag(I) ion based on a recently synthesized calix[4]arene compound of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dihydroxy‐calix[4]arene‐thiacrown‐4 is developed. The electrode exhibits a Nernstian response for Ag(I) ions over a wide concentration range (1.0×10^?2?1.0×10^?6 M) with a slope of 53.8±1.6 mV per decade. It has a relatively fast response time (5–10 s) and can be used for at least 2 months without any considerable divergence in potentials. The proposed electrode shows high selectivity towards Ag⁺ ions over Pb²⁺, Cd²⁺, Co²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Sr²⁺, Mg²⁺, Ca²⁺, Li⁺, K⁺, Na⁺, NH₄⁺ ions and can be used in a pH range of 2–6. Only interference of Hg²⁺ is found. It is successfully used as an indicator electrode in potentiometric titration of a mixture of chloride, bromide and iodide ions.     

Sorption thermodynamics of cobalt(II) cations on iron-manganese concretions

Isotherm of ion exchange of Co²⁺ and Na⁺ cations on iron-manganese concretions is thermodynamically described using a modified Langmuir equation. The thermodynamic characteristics of the ion exchange are determined.     

Cation exchange, interlayer spacing, and thermal analysis of Na/Ca-montmorillonite modified with alkaline and alkaline earth metal ions

Na-montmorillonites were exchanged with Li⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, while Ca-montmorillonites were treated with alkaline and alkaline earth ions except for Ra²⁺ and Ca²⁺. Montmorillonites with interlayer cations Li⁺ or Na⁺ have remarkable swelling capacity and keep excellent stability. It is shown that metal ions represent different exchange ability as follows: Cs⁺?>?Rb⁺?>?K⁺?>?Na⁺?>?Li⁺ and Ba²⁺?>?Sr²⁺?>?Ca²⁺?>?Mg²⁺. The cation exchange capacity with single ion exchange capacity illustrates that Mg²⁺ and Ca²⁺ do not only take part in cation exchange but also produce physical adsorption on the montmorillonite. Although interlayer spacing d ₀₀₁ depends on both radius and hydration radius of interlayer cations, the latter one plays a decisive role in changing d ₀₀₁ value. Three stages of temperature intervals of dehydration are observed from the TG/DSC curves: the release of surface water adsorbed (36?C84?°C), the dehydration of interlayer water and the chemical-adsorption water (47?C189?°C) and dehydration of bound water of interlayer metal cation (108?C268?°C). Data show that the quantity and hydration energy of ions adsorbed on montmorillonite influence the water content in montmorillonite. Mg²⁺-modified Na-montmorillonite which absorbs the most quantity of ions with the highest hydration energy has the maximum water content up to 8.84%.