Selective Complexation of S‐block Cations with Nanotubular Silk Type Cyclopeptides: A DFT Study

Density functional theory (DFT) was used to study the interaction of alkali metal cations (Li⁺, Na⁺ and K⁺) with cyclic peptides constructed from silk type macrocycles ( Silk1, Silk2, Silk3, Silk4, Silk5 and Silk6 ). The calculated binding energies were used as a base for investigating the selectivity of the cyclic peptides in biniding to considered metals ions. The highest cation selectivity for Li⁺ compared to the other alkali metal ions was observed. The orbital nature of different interactions between the metal cations and the cyclic peptides was analyzed using NBO analysis. The main types of driving force for host‐guest interactions was investigated and it was found that the electron‐donating O offers lone pair electrons to the contacting LP* of alkali metal cations     

Liquid-liquid extraction of silver ion with benzothiacrown ether derivatives

The extraction behavior of mono-, poly-, anal bis-(benzothiacrown ether)s is studied for alkali, alkaline-earth, heavy, and transition metal ions in the presence of picrate. These ethers show high selectivity for silver ion. Silver extractions from binary and quaternary mixtures of silver with heavy or transition metal ions were successful, except for mixtures with mercury(II) ion. Silver was extracted from a copper ore with ca. 80% recovery.     

Chromogenic and fluorogenic sensing of Cu based on coumarin

A new highly selective, reversible, chromogenic, and fluorogenic chemosensor (4) based on thiazole-coumarin moieties for quantification of copper ions in aqueous-DMSO was designed and synthesized. The mechanism of fluorescence was based on ICT, which was modified by the introduction of an electron-donating diethylamino group making it chromogenic and increasing the binding affinity. The selectivity toward copper ions was not affected by the presence of representative alkali metals, alkali earth metals, or other transition metals.     

Shape-persistent macrocycles: efficient extraction towards lanthanide and actinide elements

The extraction of three shape-persistent aromatic oligoamide macrocycles (cycloaramides) bearing either apolar or polar side chains at the periphery of the rings has been investigated towards some representative lanthanide and actinide ions, and alkali metal ions. The results from the liquid–liquid extraction of lanthanide and thorium ions from aqueous solutions into dichloromethane revealed remarkably high extractability of up to 99% and selectivity over alkali metal cations. The stoichiometry of the complex formed between the macrocycle and Eu³⁺ or Th⁴⁺ was determined to be 1:1.     

Improvement of selective d-cation binding by tetrathiacalix[4]arene hydrazides: synthesis and extraction properties

New de-tert-butyltetrathiacalix[4]arenes with acetylhydrazide substituents in cone and 1,3-alternate conformations have been synthesised with good yield by the hydrazinolysis of calix[4]arene ester derivatives. The recognition ability of synthesised macrocycles towards transition and alkali metals has been investigated by the picrate extraction method. The stoichiometry of complexes and the extraction constants have been determined. It has been found that tetrahydrazides do not extract alkali metal ions, but show an excellent affinity towards transition and heavy metal cations. The 1,3-alternate conformer of de-tert-butyltetrathiacalix[4]arene has revealed a remarkable selectivity for Ni²⁺ and Ag⁺ in the row of d-elements and for Cd²⁺ ion among the toxic heavy metals. The experimental data show that the removal of tert-butyl groups from tetrathiacalix[4]arene framework leads to the drastic improvement of extraction efficiency and selectivity of new tetrahydrazides.     

Comparative analysis of the binding of thiacalix[4]arene-monocrown-ethers with monovalent metal salts using MALDI mass spectrometry

MALDI mass spectrometry is used for the first time for the rapid assessment of the binding of thiacalix[4]arene-monocrown-ethers with metal cations (Li, Na, K, Cs, Cu, Ag). The work is performed on examples of thiacalix[4]arene-monocrown-ethers in 1,3-alternate conformation with various numbers (m) of ethylene oxide units and various substituents in phenol groups. It is shown that thiacalix[4]arene-monocrown- ethers with m = 3, 4, 5, and 6 bind lithium, sodium, potassium, and cesium cations, respectively; in addition, the binding of cesium cations is stronger in the presence of aromatic substituents in the lower rim of thiacalix[4]arene-monocrown-ethers. Silver cations bind with calixarenes under study more intensely than copper ions. When aromatic substituents are present, the binding of silver cations is stronger than that of alkali metal ions with the studied thiacalix[4]arene-monocrown-ethers.     

Dynamic combinatorial libraries for the recognition of heavy metal ions

We present the use of hydrazone dynamic combinatorial libraries (DCLs) to identify macrocyclic receptors that are selective for alkaline earth metal ions over alkali metal ions. In particular, the toxic heavy metal ions Sr(2+) and Ba(2+) induce characteristic changes in the DCLs. Four macrocycles were isolated and characterised by LCMS, HRMS, NMR and X-ray crystallography; binding studies by UV-Vis spectroscopy confirm the selectivity observed in the DCLs.     

Application of chitosan and its derivatives for solid-phase extraction of metal and metalloid ions: a mini-review

Here we review chitosan-based materials for solid-phase extraction of metal and metalloid ions prior to their determination by atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, mass spectrometry, and some other spectrometric techniques. We show that nearly zero affinity of chitosan and its derivatives to alkali and alkali-earth metal ions is very beneficial for separation of analytes from the salt matrix, which is always present in natural waters, waste streams, and geological samples and interferes with analytical signals. Applicability of chitosan to selective recovery of different metal and metalloid ions can be significantly improved via functionalization with N-, S-, and O-containing groups imparting chitosan with additional electron donor atoms and capability to form stable five- and six-membered chelate rings with metal ions. Among most promising materials for analytical preconcentration, we discussed chitosan-based composites; carboxyalkyl chitosans; chitosan derivatives containing residues of aminoacids, iminodiacetic acid, ethylenediaminetetraacetic and diethylenetriaminepentaacetic acids; chitosans modified with aliphatic and aromatic amines, heterocyclic fragments (pyridyl, imidazole), and crown ethers. We have shown that most chitosan derivatives provide only group selectivity toward metal ions; however, optimization of recovery conditions allows metals and metalloids speciation and efficient separation of noble and transition metal ions.     

Evaluation of alkali and alkaline earth metal cation selectivities of lariat ether amides by electrospray ionization mass spectrometry

Lariat ethers with pendant amide groups have shown promise as new ion sensors because of their selectivity towards particular metal ions. In this study we report alkali and alkaline earth metal binding selectivities of dibenzo-16-crown-5 and fifteen dibenzo-16-crown-5 lariat ether amides (LEAs) as determined by electrospray ionization mass spectrometry (ESI-MS). Additionally, the influence of the acid/base nature of the solution on metal cation selectivity is investigated. The validity of using ESI-MS for determination of selectivities is established by analogous experiments using hosts with known binding constants for the same metal cations and solvent systems. Collisionally activated dissociation (CAD) is used to evaluate the influence of the alkali metal cation binding on the fragmentation of the LEAs.     

Sorption Capacity and Selectivity Relative to Metal Ions for Oxidized Carbon Sorbents with Different Numbers of Oxygen-Containing Groups

We have determined the sorption capacity and selectivity for a broad range of metal ions (alkali, alkaline-earth, transition metal, noble metals, etc.) in two-component and multicomponent mixtures of oxidized carbon sorbents with different numbers of oxygen-containing surface functional groups. We discuss the reasons for the observed changes, their connection with the nature and number of oxygen-containing surface functional groups, and the possibilities for practical application.     

Synthesis and Properties of 5-Chloro-8-hydroxyquinoline-Substituted Azacrown Ethers: A New Family of Highly Metal Ion-Selective Lariat Ethers

New 5-chloro-8-hydroxyquinoline (CHQ)-substituted aza-18-crown-6 (4), diaza-18-crown-6 (1), diaza-21-crown-7 (2), and diaza-24-crown-8 (3) ligands, where CHQ was attached through the 7-position, and aza-18-crown-6 (11) and diaza-18-crown-6 (10) macrocycles, where CHQ was attached through the 2-position, were prepared. Thermodynamic quantities for complexation of these CHQ-substituted macrocycles with alkali, alkaline earth, and transition metal ions were determined in absolute methanol at 25.0 degrees C by calorimetric titration. Two isomers, 1 and 10, which are different only in the attachment positions of the CHQ to the parent macroring, exhibit remarkable differences in their affinities toward the metal ions. Compound 1 forms very stable complexes with Mg(2+), Ca(2+), Cu(2+), and Ni(2+) (log K = 6.82, 5.31, 10.1, and 11.4, respectively), but not with the alkali metal ions. Ligand 10 displays strong complexation with K(+) and Ba(2+) (log K = 6.61 and 12.2, respectively) but not with Mg(2+) or Cu(2+). The new macrocycles and their complexes have been characterized by means of UV-visible and (1)H NMR spectra and X-ray crystallography. New peaks in the UV spectrum of the Mg(2+)-1 complex could allow an analytical determination of Mg(2+) in very dilute solutions in the presence of other alkali and alkaline earth metal cations. (1)H NMR spectral and X-ray crystallographic studies indicate that ligand 10 forms a cryptate-like structure when coordinated with K(+) and Ba(2+), which induces an efficient overlap of the two hydroxyquinoline rings. Such overlapping forms a pseudo second macroring that results in a significant increase in both complex stability and cation selectivity.     

杯芳烃银离子敏感场效应晶体管传感器

报道了硫醚取代的杯「４」芳烃化合物的合成,以此化合物为敏感材料,研制了聚氯乙烯膜的银离子敏感场效应晶体管传感器。Ａｇ＾＋－ＩＳＦＥＴ传感器对银离子表现出了优良的能斯特呼应,响应斜率为５８ｍＶ／ｐＡｇ,同时该传感器对碱金属、碱土金属及过渡金属离子有极高的选择性,在１０＾－２－１０＾－５ｍｏｌ／Ｌ范围内有良好的线性关系,检测限为１０＾－５．４ｍｏｌ／Ｌ。     

Cyclitol-based metal-complexing agents. Effect of the relative orientation of oxygen atoms in the ionophoric ring on the cation-binding ability of myo-inositol-based crown ethers

myo-Inositol-derived crown ethers having varying relative orientations (1,3-diaxial, 1,2-diequatorial, and 1,2-axial-equatorial) of the oxygen atoms in the ionophoric ring were synthesized and the extent of their binding with picrates of alkali metals, ammonia, and silver were estimated. These crown ethers bind very well with potassium and silver picrates and show good to moderate binding toward lithium, sodium, cesium, and ammonium picrates. These myo-inositol-derived crown ethers exhibit very strong binding for silver, even though they do not have sulfur or nitrogen coordinating sites in them, which are known to have high affinity for silver. The ratio of binding constants for silver to other ions tested varies from 10(2) to 10(5). The ion selectivity and the strength of binding are dependent on the relative orientation of the oxygen atoms in the ionophoric ring as well as on the size of the macrocyclic ring.     

Silver(I)-selective coated-wire electrode based on an octahydroxycalix[4]arene derivative.

The performance of octahydroxycalix[4]arene derivative used as a neutral carrier for silver polymeric membrane electrode was studied. The sensor gave a good Nernstian response of 58 +/- 1 mV per decade for silver ion in the activity range 3.3 x 10(-6) to 3.3 x 10(-2) M Ag+. The limit of detection reached 2.1 x 10(-6) M Ag+ and exhibited high selectivity for silver ion against the alkali, alkaline earth and transition metal ions. The sensor can be used in wide pH range from 1.5 to 6.5. The response time of the sensor is less than 20 s. The potentiometric sensor was used as the indicator electrode in the titration of Ag+ ions by sodium chloride solution.     

Ditopic Ligands. The Synthesis of a Series of Phosphine-Functionalised Macrocycles

The synthesis of a series of phosphine-functionalised macrocycles, 1–6 , is described. The combination of N-and O-sites with P- and S-sites provides ligands which may bind transition or non-transition metal ions; as a consequence, they give access to dinuclear complexes containing both a Lewis acid and a redox metallic site. Compounds 1,2 and 6 are heterodinucleating ligands capable of binding two dissimilar metals in proximity. Macrocycles 3–5 are homotopic ligands which may form homodinuclear complexes of transition metals.     

Silver(I) ion-selective membrane based on Schiff base-p-tert-butylcalix[4]arene

A PVC membrane electrode for silver(I) ion based on Schiff base-p-tert-butylcalix[4]arene is reported. The electrode works well over a wide range of concentration (1.0 x 10(-5)-1.0 x 10(-1) mol dm-3) with a Nernstian slope of 59.7 mV per decade. The electrode shows a fast response time of 20 s and operates in the pH range 1.0-5.6. The sensor can be used for more than 6 months without any divergence in the potential. The selectivity of the electrode was studied and it was found that the electrode exhibits good selectivity for silver ion over some alkali, alkaline earth and transition metal ions. The silver ion-selective electrode was used as an indicator electrode for the potentiometric titration of silver ion in solution using a standard solution of sodium chloride; a sharp potential change occurs at the end-point. The applicability of the sensor to silver(I) ion measurement in water samples spiked with silver nitrate is illustrated.     

Selective electrodes for silver based on polymeric membranes containing cali

Silver ion-selective electrodes were prepared with polymeric membranes based on two calix[4]arene derivatives functionalized by two hydroxy and two benzothiazolylthioethoxy groups. The electrodes all gave a good Nernstian response of 58mV decade(-1) for silver in the activity range 5 x 10(-6)-10(-1) M, the limits of detection reached 10(-5.8) M and exhibited high selectivity towards alkali, alkaline earth and some transition metal ions. The electrode was used as indicator electrode in titrations of Ag+ with Cl- ion.     

Diazo-coupled calix[4]arenes for qualitative analytical screening of metal ions

New chromogenic diazophenylcalix[4]arenes 1 and 2 were synthesized in cone conformation. Compound 1 with the ortho-carboxyl groups in CH₃CN solution preferentially binds with alkaline earth and transition metal ions, whereas no significant changes in absorption spectra are observed in the presence of alkali metal ions. While 2 with the ortho-ester groups shows selective complexation properties towards transition metal ions over alkali and alkaline earth metal ions. The detection of metal ions gives rise to bathochromic shifts in the absorption spectra (from orange/yellow to red), which is clearly visible even to the naked eye. According to the selective color changes using both receptors upon cation complexation, one can set up a qualitative analytical routine to screen alkali, alkaline earth, and transition metal ions.     

Ion exchange properties of monolithic and particle type iminodiacetic acid modified silica

A 10 cm silica monolith has been modified with iminodiacetic acid (IDA) groups and characterised for its selectivity toward alkali, alkaline earth, and selected transition metal cations. Physical characterisation of the modified monolith found non-homogeneous modification along the length of the monolith, although sufficient capacity was achieved to facilitate significant retention of alkaline earth and transition/heavy metal ions over a range of eluent pH and ionic strength conditions. For alkaline earth and transition/heavy metal ions, selectivity of the 10 cm IDA monolith closely matched that seen with a 25 cm IDA modified silica gel particle packed column, although the separation of alkali metal ions was noticeably poorer on the monolithic column. Peak efficiencies for most metal ions were of a similar order for both column types, except for Zn(II), which showed significant peak broadening on the IDA monolithic column.     

Determination of thallium(I) in solutions containing cations interfering in potentiometric ion-pair formation-based titrations

The possibility of the use of simple potentiometric coated-wire sensors in the analysis of mixtures of ions, the determination of which is based on the ion-pairing principle, was studied. Attention was especially paid on the determination of thallium(I) in the presence of alkali metal ions, mercury(II), copper(II) and silver(I). It was found that thallium(I) can selectively be titrated with sodium tetraphenylborate in diluted solutions. Interferences of ions of the alkali metals are practically negligible if their concentrations are lower than 10(-3) mol dm(-3). Interference of Cu(II) is minimized using EDTA as a masking agent, Hg(II) and Ag(I) ions are sufficiently screened by additions of sodium cyanide. In mixtures containing higher concentrations of alkali metals, thallium(I) can be oxidized to thallium(III) and selectively titrated as TlCl(-)(4) with a cationic titrant.