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Tripodal, Squaramide-Based Ion Pair Receptor for Effective Extraction of Sulfate Salt.

ABSTRACT: Combining three features-the high affinity of squaramides toward anions, cooperation in ion pair binding and preorganization of the binding domains in the tripodal platform-led to the effective receptor 2. The lack of at least one of these key elements in the structures of reference receptors 3 and 4 caused a lower affinity towards ion pairs. Receptor 2 was found to form an intramolecular network in wet chloroform, which changed into inorganic-organic associates after contact with ions and allowed salts to be extracted from an aqueous to an organic phase. The disparity in the binding mode of 2 with sulfates and with other monovalent anions led to the selective extraction of extremely hydrated sulfate anions in the presence of more lipophilic salts, thus overcoming the Hofmeister series.

SUBMITTER: Jagleniec D

PROVIDER: S-EPMC8125518 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Cooperative Transport and Selective Extraction of Sulfates by a Squaramide-Based Ion Pair Receptor: A Case of Adaptable Selectivity.

Project description:The use of a squaramide-based ion pair receptor offers a solution to the very challenging problem of extraction and transport of extremely hydrated sulfate salt. Herein we demonstrate for the first time that a neutral receptor is able not only to selectively extract but also to transport sulfates in the form of an alkali metal salt across membranes and to do so in a cooperative manner while overcoming the Hofmeister bias. This was made possible by an enhancement in anion binding promoted by cation assistance and by diversifying the stoichiometry of receptor complexes with sulfates and other ions. The existence of a peculiar 4:1 complex of receptor 2 with sulfates in solution was confirmed by UV-vis and 1H NMR titration experiments, DOSY and DLS measurements, and supported by solid-state X-ray measurements. By varying the separation technique and experimental conditions, it was possible to switch the depletion of the aqueous layer into extremely hydrophilic or less lipophilic salts, thus obtaining the desired selectivity.

| S-EPMC7509838 | biostudies-literature

Squaramide-Based Heteroditopic [2]Rotaxanes for Sodium Halide Ion-Pair Recognition.

Project description:A series of squaramide-based heteroditopic [2]rotaxanes consisting of isophthalamide macrocycle and squaramide axle components are synthesized using an alkali metal cation template-directed stoppering methodology. This work highlights the unprecedented sodium cation template coordination of the Lewis basic squaramide carbonyls for interlocked structure synthesis. Extensive quantitative 1 H NMR spectroscopic anion and ion-pair recognition studies reveal the [2]rotaxane hosts are capable of cooperative sodium halide ion-pair mechanical bond axle-macrocycle component recognition, eliciting up to 20-fold enhancements in binding strengths for bromide and iodide, wherein the Lewis basic carbonyls and Lewis acidic NH hydrogen bond donors of the squaramide axle motif operate as cation and anion receptive sites simultaneously in an ambidentate fashion. Notably, varying the length and nature of the polyether cation binding unit of the macrocycle component dramatically influences the ion-pair binding affinities of the [2]rotaxanes, even overcoming direct contact NaCl ion-pair binding modes in polar organic solvents. Furthermore, the cooperative ion-pair binding properties of the squaramide-based heteroditopic [2]rotaxanes are exploited to successfully extract solid sodium halide salts into organic media.

| S-EPMC10946609 | biostudies-literature

Ion-pair induced supramolecular assembly formation for selective extraction and sensing of potassium sulfate.

Project description:Selective extraction of sulfates in the form of alkali metal salts using charge-neutral molecular receptors is one of the holy grails of supramolecular chemistry. Herein we describe, for the first time, a squaramide-based ion pair receptor equipped with a crown ether site that is able to extract potassium sulfate from the aqueous to the organic phase (an analogous monotopic anion receptor lacking the crown ether unit lacks this ability). 1H NMR, UV-vis, DOSY-NMR, DLS, and MS experiments and the solid-state single crystal structure provided evidence of the formation of a supramolecular core-shell like assembly upon interaction of the receptor with potassium sulfate. The presence of monovalent potassium salts, in contrast, promoted the formation of simple 1 : 1 complexes. Unlike the 4 : 1 assembly, the 1 : 1 complexes are poorly soluble in organic media. This feature was utilized to overcome the Hofmeister bias and allow for selective extraction of extremely hydrophilic sulfates over lipophilic nitrate anions, which was unambiguously proved by quantitative AES and ion chromatography measurements. A simple modification of the receptor structure led to a "naked eye" optical sensor able to selectively detect sulfates under both SLE and LLE conditions.

| S-EPMC6979319 | biostudies-literature

Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion-Pair Receptor.

Project description:Current approaches to lowering the pH of basic media rely on the addition of a proton source. An alternative approach is described herein that involves the liquid-liquid extraction-based removal of cesium salts, specifically CsOH and Cs2 CO3 , from highly basic media. A multitopic ion-pair receptor (2) is used that can recognize and extract the hydroxide and carbonate anions as their cesium salts, as confirmed by 1 H?NMR spectroscopic titrations, ICP-MS, single-crystal structural analyses, and theoretical calculations. A sharp increase in the pH and cesium concentrations in the receiving phase is observed when receptor 2 is employed as a carrier in U-tube experiments involving the transport of CsOH through an intervening chloroform layer. The pH of the source phase likewise decreases.

| S-EPMC5694431 | biostudies-literature

Highly Efficient, Tripodal Ion-Pair Receptors for Switching Selectivity between Acetates and Sulfates Using Solid-Liquid and Liquid-Liquid Extractions.

Project description:A tripodal, squaramide-based ion-pair receptor 1 was synthesized in a modular fashion, and 1H NMR and UV-vis studies revealed its ability to interact more efficiently with anions with the assistance of cations. The reference tripodal anion receptor 2, lacking a crown ether unit, was found to lose the enhancement in anion binding induced by presence of cations. Besides the ability to bind anions in enhanced manner by the "single armed" ion-pair receptor 3, the lack of multiple and prearranged binding sites resulted in its much lower affinity towards anions than in the case of tripodal receptors. Unlike with receptors 2 or 3, the high affinity of 1 towards salts opens up the possibility of extracting extremely hydrophilic sulfate anions from aqueous to organic phase. The disparity in receptor 1 binding modes towards monovalent anions and divalent sulfates assures its selectivity towards sulfates over other lipophilic salts upon liquid-liquid extraction (LLE) and enables the Hofmeister bias to be overcome. By changing the extraction conditions from LLE to SLE (solid-liquid extraction), a switch of selectivity from sulfates to acetates was achieved. X-ray measurements support the ability of anion binding by cooperation of the arms of receptor 1 together with simultaneous binding of cations.

| S-EPMC7764408 | biostudies-literature

A C Symmetric Nitrate Complex with a Thiophene-Based Tripodal Receptor.

Project description:A thiophene-based tripodal receptor has been synthesized and its complexes with nitrate and iodide have determined by single-crystal X-ray analysis. In the nitrate complex, one nitrate is encapsulated in a selective orientation forming a C(3) symmetric complex, which is bonded to three protonated secondary amines with six NH···O bonds. The anion is coordinated in a plane perpendicular to the principal rotation axis passing through the tertiary nitrogen of the receptor and the nitrogen of the encapsulated nitrate. High-level DFT calculations support the crystallographic results demonstrating that an adduct with trigonal binding of three oxygen atoms is more stable than that of one oxygen atom of the encapsulate nitrate. On the other hand, in the structure of the iodide complex, all three iodides lie outside the cavity. (1)H NMR titration studies indicate that the receptor forms a 1:1 complex with nitrate with a binding constant of K = 315 M(-1) in chloroform, showing a moderate selectivity over halides and perchlorate.

| S-EPMC3086375 | biostudies-literature

Anion Complexation Studies of 3-Nitrophenyl-Substituted Tripodal Thiourea Receptor: A Naked-Eye Detection of Sulfate via Fluoride Displacement Assay.

Project description:A thiourea-based tripodal receptor L substituted with 3-nitrophenyl groups has been synthesized, and the binding affinity for a variety of anions has been studied by 1H NMR titrations and nuclear Overhauser enhancement spectroscopy experiments in dimethyl sulfoxide-d6. As investigated by 1H NMR titrations, the receptor binds an anion in a 1:1 binding mode, showing the highest binding and strong selectivity for sulfate anion. A competitive colorimetric assay in the presence of fluoride suggests that the sulfate is capable of displacing the bound fluoride, showing a sharp visible color change. The strong affinity of L for sulfate was further supported by UV-vis titrations and density functional theory (DFT) calculations. Time-dependent DFT calculations indicate that the fluoride complex possesses a different optical absorption spectrum (due to charge transfer between the fluoride and the surrounding ligand) than the sulfate complex, reflecting the observed colorimetric change in these two complexes. The receptor was further tested for its biocompatibility on primary human foreskin fibroblasts and HeLa cells, exhibiting an excellent cell viability up to 100 μM concentration.

| S-EPMC6044562 | biostudies-literature

Synthesis and anion binding studies of tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors: Proton transfer-induced selectivity for hydrogen sulfate over sulfate.

Project description:Tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors, tris([(4-cyanophenyl)amino]propyl)urea (L1) and tris([(4-cyanophenyl)amino]propyl)thiourea (L2), have been synthesized and their anion binding properties have been investigated for halides and oxoanions. As investigated by 1H NMR titrations, each receptor binds an anion with a 1:1 stoichiometry via hydrogen-bonding interactions (NH⋯anion), showing the binding trend in the order of F- > H2PO4- > HCO3- > HSO4- > CH3COO- > SO42- > Cl- > Br- > I in DMSO-d6 . The interactions of the receptors were further studied by 2D NOESY, showing the loss of NOESY contacts of two NH resonances for the complexes of F-, H2PO4-, HCO3-, HSO4- or CH3COO- due to the strong NH⋯anion interactions. The observed higher binding affinity for HSO4- than SO42- is attributed to the proton transfer from HSO4- to the central nitrogen of L1 or L2 which was also supported by the DFT calculations, leading to the secondary acid-base interactions. The thiourea receptor L2 has a general trend to show a higher affinity for an anion as compared to the urea receptor L1 for the corresponding anion in DMSO-d6 . In addition, the compound L2 has been exploited for its extraction properties for fluoride in water using a liquid-liquid extraction technique, and the results indicate that the receptor effectively extracts fluoride from water showing ca. 99% efficiency (based on L2).

| S-EPMC5295472 | biostudies-literature

Lithium cation enhances anion binding in a tripodal phosphine oxide-based ditopic receptor.

Project description:A tripodal ditopic receptor presents H-bond donors and a phosphine oxide to potential guests. In the idealized binding conformation, an endohedral P=O functionality provides enhanced halide binding in the presence of lithium with the greatest ΔΔG° observed for bromide, while minimal changes in K(a) are observed in the presence of sodium.

| S-EPMC3344749 | biostudies-literature

Spectroscopic, structural, and theoretical studies of halide complexes with a urea-based tripodal receptor.

Project description:A urea-based tripodal receptor L substituted with p-cyanophenyl groups has been studied for halide anions using (1)H NMR spectroscopy, density functional theory (DFT) calculations, and X-ray crystallography. The (1)H NMR titration studies suggest that the receptor forms a 1:1 complex with an anion, showing a binding trend in the order of fluoride > chloride > bromide > iodide. The interaction of a fluoride anion with the receptor was further confirmed by 2D NOESY and (19)F NMR spectroscopy in DMSO-d(6). DFT calculations indicate that the internal halide anion is held by six NH···X interactions with L, showing the highest binding energy for the fluoride complex. Structural characterization of the chloride, bromide, and silicon hexafluoride complexes of [LH(+)] reveals that the anion is externally located via hydrogen bonding interactions. For the bromide or chloride complex, two anions are bridged with two receptors to form a centrosymmetric dimer, while for the silicon hexafluoride complex, the anion is located within a cage formed by six ligands and two water molecules.

| S-EPMC3399518 | biostudies-literature

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