Separation of Monovalent and Divalent Cations on a Pure Silica Gel Column with Dilute Oxalic Acid Containing 18-Crown-6 as Mobile Phase

Summary Pure silica gel (Pia Seed 5S-60-SIL) has been investigated as a cation-exchange stationary phase for ion chromatography of common monovalent and divalent cations (Li⁺, Na⁺, NH₄⁺, K⁺, Mg²⁺, and Ca²⁺) with conductimetric detection; dilute oxalic acid (0.05 mm oxalic acid, pH 4.1, to 1 mm oxalic acid, pH 3.0) was used as mobile phase. The Pia Seed 5S-60-SIL silica gel acted as a cation-exchange stationary phase for these cations when 0.2 mm oxalic acid at pH 3.6 was used as the mobile phase. Excellent simultaneous separation and highly sensitive indirect conductimetric detection of these cations were achieved in 20 min on a 150 mm × 4.6 mm i.d. Pia Seed 5S-60-SIL silica gel column with 0.2 mm oxalic acid containing 4 mm 18-crown-6 (1,4,7,10,13,16-hexaoxacycloctadecane), pH 3.7, as mobile phase (detection limits (signal-to-noise ratio, 3, injection volume, 20 L), were 0.15 m for Li⁺, 0.16 m for Na⁺, 0.21 m for NH₄⁺, 1.0 m for K⁺, 0.17 m for Mg²⁺, and 0.25 m for Ca²⁺). The proposed IC–CD method was successfully applied to the separation and detection of major cations (Na⁺, NH₄⁺, K⁺, Mg²⁺, and Ca²⁺) in rain and river water samples.     

A hybrid mesoporous material functionalized by 1,8-naphthalimide-base receptor and the application as chemosensor and absorbent for Hg2+ in water

A novel hybrid material (SBA-P1) is prepared through the functionalization of mesoporous silica (SBA-15) with a 1,8-naphthalimide-based dye by sol-gel reaction. The characterization results of elemental analysis (EA), X-ray powder diffractometer (XRD) and spectroscopic methods demonstrate the fluorescence dye P1 is successfully grafted onto the inner surface of SBA-15 and the organized structure is preserved. SBA-P1 can detect Hg²⁺ with high selectivity to Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, Mn²⁺, Ni²⁺, Co²⁺, Ag⁺, Cr³⁺, and Mg²⁺, Ca²⁺, Li⁺, Na⁺, K⁺ in water and sensitivity to environmentally relevant mercury in complex natural samples. The quenching fluorescence detection is also reversible by treating with EDTA/base. Furthermore, its fluorescence intensity keeps stable in the physiologically relevant pH range. The extraction ability of SBA-P1 is also estimated by inductively coupled plasma source mass spectrometer (ICP), showing that approximately 90% of the Hg²⁺ ion is extracted. These results imply that the hybrid material has potential application for sensing and removing of Hg²⁺ ions in waste water and working as toxicide for acute mercury poisoning.     

Paper‐Based Electronic Tongue

We present a low cost paper‐based electronic tongue capable of discriminating forged water samples. System comprises of 4 paper‐based potentiometric sensors (sensitive to Cl^?, Na⁺/K⁺, Ca²⁺/Mg²⁺, ) and a traditional Ag/AgCl reference electrode. Different electrode materials and methods of insulation were tested with best results obtained for pencil graphite and lamination. The presented electronic tongue was able to distinguish tap and lake water from mineral water samples (PCA – Principal Component Analysis and KNN ? K‐nearest neighbour). In total 14 different water samples were used in this study. Sensors presented good signal repeatability, selectivity and reasonable sensitivity.     

Estimation of Silica Species’ Concentrations in Lithium and Magnesium Chloride Solutions from the Peak Intensities Observed by FAB-MS

The concentrations of dissolved silica species in electrolyte solutions were derived from the relative intensities of silica species, obtained from FAB-MS measurements (fast atom bombardment mass spectrometry), and the total concentration of dissolved silica. Generally, silica species in aqueous solutions form various complexes with cations such as sodium (Na⁺) or calcium (Ca²⁺), and it has been difficult to determine the concentration of each species. From the observed results from FAB-MS, the chemical species of silica dissolved in lithium chloride (LiCl) and magnesium chloride (MgCl₂) solutions do not include complexes with these cations, and thus Li⁺ and Mg²⁺ do not replace protons of the silanol groups in silica. Therefore, in LiCl and MgCl₂ solutions, all of the simple structures of silicate species can be identified. The concentration of each silica species was estimated on the basis of its mass spectra peak intensities and the total concentration of silica as determined by colorimetry. This study yields the concentration of each silica species within small errors, whereas conventional methods (such as ²⁹Si-NMR) have not yielded the concentrations of individual silica species. From these results, dimers and cyclic tetramers are concluded to be the main species in silica solutions with concentrations of at most 0.1 to 0.2 μmol⋅dm⁻³. This tendency should also occur in NaCl and CaCl₂ solutions, which are major electrolytes in natural waters.     

A new sulfonamide derivative as magnesium ion receptor: N-tosyl-2,6-diisopropyl-4-(2,3-dimethoxylbenzoylamide)aniline

N-Tosyl-2,6-diisopropyl-4-(2,3-dimethoxylbenzoylamide)aniline (1) has been synthesized and its metal ion (Na⁺, K⁺, Ca²⁺, Mg²⁺) coordinating properties investigated by FT-IR, ESI-MS, and ¹H NMR methods. Among the tested metal ions, the overall stability constant (log K) for Mg²⁺ (6.89) is the highest (Na⁺, 5.64; K⁺, 5.43; Ca²⁺, 5.51) in 10% water/THF at 25.0 ± 0.5 °C determined by UV-vis spectroscopy, indicating that 1 is a potent ionophore for Mg²⁺ ion.     

Adsorption ability of Ga5N10 nanomaterial for removing metal ions contamination from drinking water by DFT

The electronic, magnetic, and thermodynamic properties of alkali/alkaline earth metal ion-adsorbed gallium nitride nanocage (Ga₅N₁₀_NC) have been investigated using density functional theory. The results denote that alkali/alkaline earth-metal ion-adsorbed Ga₅N₁₀_NC systems are stable compounds, with the most stable adsorption site being the center of the cage ring. The partial density of states (PDOS) can estimate a certain charge assembly between Li⁺, Na⁺, K⁺/ Be²⁺, Mg²⁺, Ca²⁺ and Ga₅N₁₀_NC which indicate the complex dominant of metallic features as: Ca²⁺ > Mg²⁺ > Be²⁺ >> K⁺ > Na⁺ > Li⁺. For confirmation of magnetic-alignment of Ga₅N₁₀_NC, monovalent (M⁺) and divalent (M²⁺) metal ions were added to the sample to measure the effects of metals on the magnetic-alignment properties of Ga₅N₁₀_NC. Furthermore, the reported results of NMR spectroscopy have exhibited that both M⁺ and M²⁺ can be optimized to achieve optimal alignment of nanocage in the presence of an applied magnetic field; however, chemical shift anisotropy spans for Ca²⁺– and Mg²⁺–containing samples is due to Ca²⁺ and Mg²⁺ ions binding to Ga₅N₁₀_NC. Regarding IR spectroscopy, Li⁺@ Ga₅N₁₀_NC and Be²⁺@ Ga₅N₁₀_NC with more electronegativity appear the most fluctuations through adsorption process. Moreover, based on NQR analysis, Ca²⁺ has shown a different graph of electric potential during trapping in Ga₅N₁₀_NC compared to other metal cations. Based on the results of $$ amounts in this research, the selectivity of metal ion adsorption by gallium nitride nanocage (ion sensor) has been approved as: K⁺>Na⁺> Li⁺ in alkali metals and Ca²⁺>Mg²⁺> Be²⁺ in alkaline earth metals.     

Influence of composition on corroding process of Na<Subscript>2</Subscript>O-K<Subscript>2</Subscript>O-CaO-ZrO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glasses

The corroding process of six glasses of the Na₂O-K₂O-CaO-ZrO₂-SiO₂ system with ZrO₂content 0–2.13 mass % by water was observed during static tests at 121°C and pressure of 0.25 MPa in steam sterilizer. Significant increase of Na⁺ and K⁺ content in leachates was observed after the addition of ZrO₂ into glass. Further increase of the content of ZrO₂ in glasses slowed down the rate of Na⁺ and K⁺ leaching. The leaching process of SiO₂ as well as Na⁺, K⁺, and Ca²⁺ ions was evaluated on the basis of comparison with model leaching processes. Variation of the concentrations of Na⁺, K⁺, Ca²⁺, and SiO₂ in leachates with time was described by empirical equation. Observed changes in the initial leaching rates of Na⁺, K⁺, Ca²⁺, and SiO₂ can be ascribed to the content of ZrO₂ in glasses. The presence of ZrO₂ in glasses reduced the overall rate of glass dissolution.     

Ion-transfer polarographic study of the distribution of alkali and alkaline-earth metal complexes with 3m-crown-m ether derivatives (m = 6, 8) between water and nitrobenzene phases

Stability constants ( ₁ ^NB ) of the 1:1 cationic complexes of Li⁺ Na⁺, K⁺ Ca²⁺ Sr²⁺ and Ba²⁺ with benzo-18-crown-6 (B18C6), Ca²⁺ and Sr²⁺ with 18C6 and dibenzo-18C6 and Li⁺, Na⁺, Ca²⁺, Sr²⁺ and Ba²⁺ with dibenzo-24-crown-8 in a nitrobenzene (NB) solution saturated with water (w) were determined at 25°C by ion-transfer polarography. From these values, distribution constants (K _D,ML) of the 18C6-derivative complex cations between the w- and NB-phases were evaluated using the thermodynamic relation:K _D,ML =K ₁ ^NB , whereK (mol dm^–3) is an overall equilibrium constant of the processes related to the complexation in the w-phase. The data on the distribution of the 18C6-derivative complex cations between the two phases and the complexation in the NB-phase were examined on the basis of an increase in the number of water molecules hydrated to the species relevant to these processes. The 18C6 derivatives showed higher solubilities in the NB-phase than in the w-phase by complexing with the univalent-metal ions, while, for the divalent-metal ions, the derivatives showed lower solubilities in the NB-phase.     

Zn selective luminescent ‘off-on’ probes derived from diaryl oxadiazole and aza-15-crown-5

New photo-induced electron transfer (PET) probes OMOX and OBOX, carrying an additional binding site in the form of ‘oxadiazole nitrogen’ have been designed to evaluate binding interactions with biologically significant Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, and Zn²⁺ including environmentally toxic Ba²⁺ and Cd²⁺ using optical spectral techniques. While Li⁺, Na⁺, and K⁺ did not appreciably perturb either the absorption or emission spectra, Ba²⁺, Ca²⁺, Mg²⁺, Zn²⁺, and Cd²⁺ induced slight red shifts (2-8 nm) in the UV-visible spectra as well as pronounced chelation induced enhanced fluorescence (CHEF). Both OMOX and OBOX exhibited the highest CHEF in contact with the zinc ion, whereas Ba²⁺, Ca²⁺, Mg²⁺, and Cd²⁺ induced relatively less emission enhancements. OBOX, which is a poorer emitter (Φ_f=0.0062) than OMOX (Φ_f=0.015), showed highly promising 160-fold emission enhancement in the presence of Zn²⁺. Potential, therefore is available in OBOX to function as a selective luminescent ‘off-on’ sensor for Zn²⁺ in the presence of coordinatively competing Ba²⁺, Ca²⁺, Mg²⁺, and Cd²⁺ ions.     

Speciation analysis of mercury contaminants in water samples by RP-HPLC after solid phase extraction on modified C18 extraction disks with 1,3-bis(2-cyanobenzene)triazene

A highly sensitive and accurate method for preconcentration and determination of ultra trace amounts of inorganic mercury and organomercury compounds in different water samples is proposed. The preconcentration is achieved using octadecyl silica (C₁₈) extraction disks modified with 1,3-bis(2-cyanobenzene)triazene (CBT). The retained analytes as their triazenide complexes on the solid phase was eluted with 10 ml acetonitrile and measured by reversed-phase high-performance liquid chromatography (RP-HPLC). Type and amount of eluent, pH, amount of CBT, flow rates of sample solution and eluent have been optimized in order to obtain quantitative recovery of the analytes. The effect of interfering ions, such as Cu²⁺, Mn²⁺, Fe²⁺, Al³⁺, Zn²⁺, Cd²⁺, Ca²⁺, Mg²⁺, Ba²⁺, Pb²⁺, K⁺ and Na⁺ usually present in water samples on the recovery of the analytes has also been investigated. The enrichment factor of 100 was obtained for all mercury species and the analytical detection limits of phenylmercury, methylmercury and Hg²⁺ were found as 0.8, 1.0 and 1.3 ng l^− 1, respectively. Stability of mercury species after extraction on the modified disks was studied and the results showed that complexes collected on the disks were stable for at least 5 days. The proposed method has been applied to the quantitative determination of mercury species in natural and synthetic water samples with recoveries more than 90%.     

Ion transport,ion extraction,and ion binding by synthetic cyclic octapeptide

Cyclic octapeptide, cyclo[Gly-L-Lys(Z)-Sar-L-Pro]₂, (CGLSP2) was synthesized as an ionophore model. Its ion-transport ability through a chloroform membrane was investigated in connection with ion extractability (K_ex) and conformational properties. CGLSP2 transported the picrate salts of Ba²⁺ and Ca²⁺ efficiently. The K_ex sequences were Ba²⁺>Ca²⁺Mg²⁺ and K⁺>Rb⁺>Na⁺, showing good agreement with the selectivity in ion transport. In addition, cation-binding properties of CGLSP2 to alkali and alkaline earth metal ion were investigated in acetonitrile by CD and NMR spectroscopy. Titration curves obtained from CD data revealed three kinds of CGLSP2/cation complexes. The values of 1:1 complex-formation constants (K₁) decreased in the order Ba²⁺>Ca²⁺>Mg²⁺>Li⁺Na⁺K⁺.¹H- and¹³C-NMR data showed that free CGLSP2 exists in at least five different conformational states in acetonitrile. After the addition of equimolar amounts of Ba(ClO₄)₂, these conformations converged into a single C₂-symmetric conformation with all-trans peptide bonds.     

Synthesis and binding studies ofN-(2-Hydroxy-l-phenoxyacetyl) glycylglycine

The synthesis ofN-(2-hydroxy-l-phenoxyacetyl)glycylglycine3 from 2-acetoxyphenoxyacetic acid is described. Compound3, a simple model for the carboxy-containing ionophore, Lasalocid, binds cations in methanol in the order: Ca²⁺ Ba²⁺ > Sr²⁺ 2>> Li⁺ > Na⁺, K⁺.     

New ICT probes: synthesis and photophysical studies of N-phenylaza-15-crown-5 aryl/heteroaryl oxadiazoles under acidic condition and in the presence of selected metal ions

Molecular probes 6 and 7, incorporating N-phenylaza-15-crown-5 and aryl/heteroaryl oxadiazole have been designed to function as the new intramolecular charge transfer (ICT) probes. Photophysical properties have been studied under acidic condition as well as in the presence of selected metal ions, Ca²⁺, Ba²⁺, Mg²⁺, Na⁺, K⁺, and Li⁺. The changes in the ICT character of the probes, following the addition of trifluoroacetic acid, were interpreted in terms of site and degree of protonations. Based on the cation affinity, the ICT bands in both UV-vis and emission spectra experienced varying degrees of blue shifts due to removal of the aza-crown ether nitrogen from conjugation. The cation-induced spectral shifts and the stability constants revealed binding strength in the order Ca²⁺>Ba²⁺?Li⁺>Na⁺>K⁺>Mg²⁺. Competitive experiments performed in a matrix of ions also indicated superior interaction of 6 and 7 with Ca²⁺. The excited state decay profiles remained largely unperturbed in the presence of metal ions. The studied probes displayed positive solvatochromism and the Stokes shifts and excited state lifetimes increased with increasing solvent polarity. These findings can be rationalized by invoking highly polar nature of the emittive states. The chemoionophores 6 and 7 constitute potentially interesting Ca²⁺ sensitive probes due to their relatively high binding interaction for Ca²⁺ (log K_s=3.55-3.10) vis-a-vis that of biologically interfering Mg²⁺ (log K_s=1.67-1.30).     

Spectroscopic Study of Azo- and Azoxycrowns Binding with Cations of Similar Ionic Radius

The complexation of 13- and 16-memberedazo- and azoxycrowns with metal cations of similarionic diameter (Na⁺ and Ca²⁺; and K⁺,Ba²⁺, Ag⁺ and Pb²⁺) was studied byuv/visible spectroscopic titration in acetonitrile andMeOH. In MeOH the 13-membered azo- and azoxycrowns 1 and 2 are weakly and non-selectively bound tohard cations of similar ionic diameter, but differentcharge (Na⁺ and Ca²⁺). At the same time thebinding to the soft cation Ag⁺ of larger sizethan the macrocycle cavity is considerably stronger.In contrast to solutions in acetonitrile no bindingwith the small Li⁺ cation was found.The 16-membered azocrowns 3 and 4 alsodiscriminate silver cation in MeOH withlog K = 3.65 ± 0.1 for both compounds.Unexpectedly low bindingwith the hard barium divalent cation of similar size(log K = 1.55 ± 0.4 and 1.95 ± 0.2, respectively)was found for these compounds. Similarly to13-membered compounds no binding with the smallLi⁺ cation was detected. A reverse order ofselectivity was observed for these crowns inacetonitrile with binding constant for association of3 with Ba²⁺ (log K 5.3) considerablyhigher than for other cations. The previously observedstrong binding with the smaller Li⁺ and Na⁺cations is confirmed.     

Benzimidazole-based optical probe for selective detection of multiple-cations via dual-channel analysis

A benzimidazole-based optical probe having pendant carboxyl, amine, and imine groups as ionophore has been prepared for screening various metal ions. The 4-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-5-carboxylic acid (1) has been obtained in good yield and characterized by full battery of complementary physico-chemical techniques including ¹H NMR, UV-Vis, fluorescence spectroscopy, and single crystal X-ray crystallography. Metal ion-binding properties of 1 have been studied using ppm level concentration of representative alkali metal (Na⁺, K⁺), alkaline earth metal (Mg²⁺, Ca²⁺), and transition metal (Zn²⁺, Co²⁺, Fe³⁺, Cd²⁺, Hg²⁺, Pb²⁺, Cu²⁺, Ag⁺) ions and the output signal was monitored via two different channels viz chromogenically and fluorogenically. Selective recognition of Hg²⁺ has been explored with absorption spectra whereas emission spectra of 1 display differential response for multiple cations at parts-per-million (ppm) level concentration that allow selective detection of Ca²⁺, Mg²⁺, and Na⁺ ions. The results have been discussed in light of selectivity, sensitivity, response time, mode of binding/interactions, and sensing properties.     

Study on the Salting-out Effect using Silica Species by FAB-MS

The salting-out effect has been characterized on the basis of the relative peak intensity of silica species, observed by FAB-MS (fast atom-bombardment mass spectrometry) in solutions of sodium chloride, sodium nitrate, sodium sulfate, calcium chloride, lithium chloride and magnesium chloride. A critical change in the peak intensity ratios of the linear and cyclic tetramers of silica against the sodium ion (Na⁺) concentrations was observed at Na⁺ concentration between 0.1 and 1 mol⋅dm⁻³. The degrees of the changes of these peak intensity ratios increased in the order NaNO₃ < Na₂SO₄ < NaCl. In CaCl₂ solutions, these peak intensity ratios changed significantly at Ca²⁺ concentrations between 0.05 and 0.5 mol⋅dm⁻³. The salting-out effect observed is the total change in the concentration of silica brought about by complex factors, such as the changing solubility of silicate complexes, the increases in the concentrations of different kinds of soluble silicate complexes induced by changes in the hydrophobicity and hydrophilicity of the solution, and the contribution of hydrolysis.     

Cation-crown ether complex formation in water. II. Alkali and alkaline earth cations and 12-crown-4, 15-crown-5, and 18-crown-6

The stability constants and the partial molal volume and isentropic partial molal compressibility changes of complex formation between cations and crown ethers in water at 25°C are presented. The cations involved are Na⁺, K⁺, Rb⁺, Cs⁺, Ca²⁺, and Ba²⁺, and the crown ethers are 12-crown-4, 15-crown-5, and 18-crown-6. Values of V of complex formation have been discussed in terms of two simple models, one based on the scaled particle theory, and the others on the Drude-Nernst continuum model. The results indicate that the charge of the potassium cation in 18-crown-6 is especially well screened from the water. On this basis hydration numbers of complexed cations have been calculated. This shows that the size of the cation compared to the crown ether hole is important for the contacts between complexed cations and water.     

Bienzyme-based visual and spectrophotometric aptamer assay for quantitation of nanomolar levels of mercury(II)

The article describes a bienzyme visual system for aptamer-based assay of Hg(II) at nanomolar levels. The detection scheme is based on the finding that Hg(II) ions captured by aptamer-functionalized magnetic beads are capable of inhibiting the enzymatic activity of uricase and thus affect the formation of H₂O₂ and the blue product, i.e., oxidized tetramethylbenzidine. This strategy allows for a visual detection of Hg(II) at nanomolar levels without additional amplification procedure. Measuring the absorbance at 650 nm, the logarithmic calibration plot is linear in the concentration range of 0.5–50 nM and the limit of detection (LOD) is 0.15 nM. This is as low as the LOD obtained by atomic fluorescence spectrometry (AFS). The ions K⁺, Mg²⁺, Na⁺, Ca²⁺, Cu²⁺, Zn²⁺, Fe³⁺, Al³⁺, Co²⁺, AsO₂ ^?, Ni²⁺, Cd²⁺ and Pb²⁺ do not have a significant effect on color formation. The method was applied to the analysis of (spiked) river water, lake water, mineral water, tap water and certified reference water samples, and the results agreed well with those obtained by AFS or certified values, with recoveries ranging from 97% to 109%. The relative standard deviation for five parallel detections at a 10 nM Hg(II) level is 5.2%.

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Graphical abstract A bienzyme-based visual aptasensor was fabricated for label-free detection of nanomolar Hg²⁺ in water samples without any amplification or enrichment procedure.

     

Novel versatile imine—enamine chemosensor based on 6-nitro-4-oxo-4H-chromene for ion detection in solution, solid and gas-phase: synthesis, emission, computational and MALDI-TOF-MS studies

A new versatile emissive molecular probe (3) derived from 1,5-bis(2-aminophenoxy)-3-oxopenthane bearing two units of 6-nitro-4-oxo-4H-chromene- has been prepared by a Schiff-base condensation method using conventional and green, ultrasound-aided, methods. The dry yellow powder was characterized as the imine species (3). These imine species, however, where found to rapidly convert to their enamine form (4) in solution, under the presence of water traces. This reaction was computationally studied through Density Functional Theory (DFT) in order to investigate the relative stability of the molecular pair 3/4. The sensing properties of the enamine (4) towards various metal ions were investigated via absorption and fluorometric titrations in solution in dichloromethane, acetonitrile and DMSO. The compound shows a fluorescent turn-off response in the presence of Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Ag⁺ over the other metal ions studied, such as Li⁺, Na⁺, K⁺, Ca²⁺, Co²⁺ and Ni²⁺, being stronger for Cu²⁺ and Hg²⁺. The gas phase chemosensing abilities of (3) were also explored suggesting (3) as new active MALDI-TOF-MS matrix by two dry methods showing a strong selectivity towards Cu²⁺ and Ag⁺. Our preliminary results show promising uses of (3) supported in PPMA films as metal ion solid chemosensor.