Dataset Information

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

ABSTRACT: 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.

SUBMITTER: Jagleniec D

PROVIDER: S-EPMC6979319 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

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

Jagleniec Damian D Dobrzycki Łukasz Ł Karbarz Marcin M Romański Jan J

Chemical science 20190821 41

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). <sup>1</sup>H NMR, UV-vis, DOSY-NMR, DLS, and MS experimen ...[more]

PMID: 32055325

Similar Datasets

Project description:The power of sensing molecules is often characterized in part by determining their thermodynamic/dynamic properties, in particular the binding constant of a guest to a host. In many studies, traditional nonlinear regression analysis has been used to determine the binding constants, which cannot be applied to complex systems and limits the reliability of such calculations. Supramolecular sensor systems include many interactions that make such chemical systems complicated. The challenges in creating sensing molecules can be significantly decreased through the availability of detailed mathematical models of such systems. Here, we propose uncovering accurate thermodynamic parameters of chemical reactions using better-defined mathematical modeling-fitting analysis is the key to understanding molecular assemblies and developing new bio/sensing agents. The supramolecular example we chose for this investigation is a self-assembled sensor consists of a synthesized receptor, DPA (DPA = dipicolylamine)-appended phenylboronic acid (1) in combination with Zn2+(1.Zn) that forms various assemblies with a fluorophore like alizarin red S (ARS). The self-assemblies can detect multi-phosphates like pyrophosphate (PPi) in aqueous solutions. We developed a mathematical model for the simultaneous quantitative analysis of twenty-seven intertwined interactions and reactions between the sensor (1.Zn-ARS) and the target (PPi) for the first time, relying on the Newton-Raphson algorithm. Through analyzing simulated potentiometric titration data, we describe the concurrent determination of thermodynamic parameters of the different guest-host bindings. Various values of temperatures, initial concentrations, and starting pHs were considered to predict the required measurement conditions for thermodynamic studies. Accordingly, we determined the species concentrations of different host-guest bindings in a generalized way. This way, the binding capabilities of a set of species can be quantitatively examined to systematically measure the power of the sensing system. This study shows analyzing supramolecular self-assemblies with solid mathematical models has a high potential for a better understanding of molecular interactions within complex chemical networks and developing new sensors with better sensing effects for bio-purposes.

Dataset Information

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

Publications

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

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets