Solvent effect on heavy metal coordination with thioether ligands: A thermodynamic and theoretical study

Melchior, Andrea; Peralta, Elena; Valiente, Manuel; Tolazzi, Marilena

doi:10.1016/j.poly.2014.03.022

Cited by 13 publications

(6 citation statements)

References 56 publications

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“…The 1 : β-CD (1:2) species was discarded by the fitting software. The obtained positive Δ S value of +32.6 J mol –1 K –1 , related to the desolvation of the reagents − due to the complex formation, and the negative Δ H are frequently found for cyclodextrin-drug interactions …”

Section: Resultsmentioning

confidence: 89%

Differential Metal Ion Sensing by an Antipyrine Derivative in Aqueous and β-Cyclodextrin Media: Selectivity Tuning by β-Cyclodextrin

Selvan¹,

Poomalai²,

Ramasamy³

et al. 2018

Anal. Chem.

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β-Cyclodextrin (β-CD) is a nontoxic cyclic oligosachcharide that can encapsulate all or part of organic molecules of appropriate size and specific shape through noncovalent interaction. Herein, we report the influence of β-CD complex formation of an antipyrine derivative on its metal ion sensing behavior. In aqueous solution, the antipyrine shows a turn-on fluorescence sensing of vanadyl ion, and in cyclodextrin medium it senses aluminum ion. The compound shows an unusual fluorescence quenching on binding with β-cyclodextrin (log K SV = 2.34 ± 0.02). The differential metal ion sensing is due to the partial blocking of the chelating moiety by the cyclodextrin molecule. The structure of the antipyrine− cyclodextrin complex is optimized by two-dimensional rotating-frame Overhauser effect spectroscopy. The binding constant is determined by isothermal titration calorimetry (log K = 2.09 ± 0.004). The metal ion binding site is optimized by quanutm mechanical calculations. The lower limit of detection of vanadyl and aluminum ions, respectively, are 5 × 10 −8 and 5 × 10 −7 mol dm −3 . This is the first report of selectivity of two different cations by a chemosensor in water and in β-CD.

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Section: Resultsmentioning

confidence: 89%

Differential Metal Ion Sensing by an Antipyrine Derivative in Aqueous and β-Cyclodextrin Media: Selectivity Tuning by β-Cyclodextrin

Selvan¹,

Poomalai²,

Ramasamy³

et al. 2018

Anal. Chem.

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“…22b For instance, the stability of the metal-thioether complexes (di-n-alkylsulfide or macrocyclic ligands such as [9]aneS3, [12]aneS4 or [14]aneS4) were found to be much lower in DMSO with respect to acetonitrile mostly because of the much stronger solvation of metals in DMSO. 52 No significant difference could be observed between L2 and L3 in terms of the stability of the Hg 2+ complexes. Our DFT calculations indeed indicate that two of the sulphur atoms of the ligand (S1 and S2) provide the strongest interaction with Hg 2+ , while the remaining one (L2) or two (L3) sulphur donor atoms provide a rather weak coordination (Fig.…”

Section: Heavy Metals Binding Propertiesmentioning

confidence: 92%

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺

et al. 2016

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The syntheses of two new ligands based on a calix[4]arene scaffold in the cone conformation functionalized on the phenolic positions 1 and 3 by diethylthiophosphonates (L1) or tetra(tri)thioethyleneglycol (L2) crowns are described. Together with ligand L3, the parent calix[4]arene substituted by a penta(tetra)thioethyleneglycol crown, the spectroscopic properties of the ligands were determined by means of UV-Vis absorption spectroscopy and steady-state and time-resolved fluorescence spectroscopy, showing that the ligands display modest but non-negligible intrinsic fluorescence properties (ϕ = 0.023; 0.026 and 0.029 for L1, L2 and L3 in CHCl, respectively). The X-ray crystal structures of ligand L1, and of its synthetic precursor were determined and analyzed for their capacity to accommodate the incoming cationic species. The ligands were further investigated for their complexation properties of divalent cations such as Cu, Zn, Hg and Cd (under their nitrate salts) in 1 : 1 CHCN/CHCl solutions (I = 0.01 M EtNNO, T = 25.0(2) °C), in which the additions of cations were monitored by absorption and steady-state fluorescence spectrophotometries. The stoichiometries of the corresponding complexes were assessed by ESI-MS, while insights into the structures of the complexes in solution were obtained with density functional theory (DFT) calculations. The influence of the sulphur and phenol coordinating moieties was addressed to show that the thiocrown compounds L2 and L3 displayed a marked affinity towards the soft mercuric cation (Δlog K ≥ 2), with no particular size selectivity effect, whereas ligand L1 can accommodate both the thio and phenol units to coordinate with Cu(ii). Altogether, these results point to the use of L3 as a selective fluoroionophore for detection of Hg.

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“…The calorimetric data are therefore in agreement with a weaker interaction of Pb 2+ with the SPION@3-MPA particles. Also, adsorption takes place with a positive entropy change (ΔSads) for Ag + , Hg 2+ and Pb 2+ , indicating an increase of the degrees of freedom of the system which is related to the desolvation of the metal ions when interacting with the SPION@3-MPA surface and with the solution reorganization upon charge neutralization [58][59][60]. The obtained ΔSads for the Ag + adsorption process is relatively small with respect to the bipositive ions in agreement with its lower solvation in water [58][59][60].…”

Section: Metal Ions Adsorptionmentioning

confidence: 99%

Thermodynamics of Hg2+ and Ag+ adsorption by 3-mercaptopropionic acid-functionalized superparamagnetic iron oxide nanoparticles

Lanas

Valiente

Tolazzi

et al. 2018

J Therm Anal Calorim

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Superparamagnetic iron nanoparticles (SPION) have been functionalized with 3mercaptopropionic acid (3-MPA), characterized and applied for the removal of Ag + , Hg 2+ and Pb 2+ metal ions from aqueous solutions by iron oxide (Fe3O4). The heavy metal adsorption has been investigated by means of ICP-OES and isothermal titration calorimetry. Experimental data ware better fitted by Langmuir rather than Freundlich isotherms and the thermodynamic parameters for the adsorption process of the metal ions on the functionalized SPION nanoparticles (SPION@3-MPA) were obtained. Isothermal titration calorimetry (ITC) is applied to monitor heavy metal adsorption on SPION@3-MPA: the process results to be exothermic for Hg 2+ , Ag + while it is weakly endothermic in the case of Pb 2+ and the adsorption enthalpies and entropies have been obtained. The values of the thermodynamic parameters suggest that the Ag + and Hg 2+ ions interact strongly with the thiol groups, while the Pb 2+ ions seem to be adsorbed by the material mostly via electrostatic interaction. When compared to other thiol-functionalized materials, the obtained SPION@3-MPA NP can be considered a competitive adsorbent for Ag + and Hg 2+ ions. The comparison between the ICP-OES adsorption rata and the enthalpy trend obtained by ITC supports shows that the latter technique can be a good tool for a fast testing of materials to be applied for heavy metal separation from solutions.

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Solvent effect on heavy metal coordination with thioether ligands: A thermodynamic and theoretical study

Cited by 13 publications

References 56 publications

Differential Metal Ion Sensing by an Antipyrine Derivative in Aqueous and β-Cyclodextrin Media: Selectivity Tuning by β-Cyclodextrin

Differential Metal Ion Sensing by an Antipyrine Derivative in Aqueous and β-Cyclodextrin Media: Selectivity Tuning by β-Cyclodextrin

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺

Thermodynamics of Hg2+ and Ag+ adsorption by 3-mercaptopropionic acid-functionalized superparamagnetic iron oxide nanoparticles

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Solvent effect on heavy metal coordination with thioether ligands: A thermodynamic and theoretical study

Cited by 13 publications

References 56 publications

Differential Metal Ion Sensing by an Antipyrine Derivative in Aqueous and β-Cyclodextrin Media: Selectivity Tuning by β-Cyclodextrin

Differential Metal Ion Sensing by an Antipyrine Derivative in Aqueous and β-Cyclodextrin Media: Selectivity Tuning by β-Cyclodextrin

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg2+over Cu2+, Zn2+and Cd2+

Thermodynamics of Hg2+ and Ag+ adsorption by 3-mercaptopropionic acid-functionalized superparamagnetic iron oxide nanoparticles

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Product

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Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺