Supramolecular control of the structure and receptor properties of an amphiphilic hemicyanine chromoionophore monolayer at the air/water interface

Shokurov, Alexander V.; Alexandrova, Alvina V.; Щербина, М. А.; Bakirov, Artem V.; Rogachev, A.V.; Yakunin, S. N.; Чвалун, С. Н.; Arslanov, V. V.; Selektor, S. L.

doi:10.1039/d0sm01078b

Cited by 9 publications

(13 citation statements)

References 29 publications

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“…The spectral changes recorded during the interaction of this compound with mercury cations in solutions are described in detail in ref . Earlier we − showed that preorganization of the hemicyanine dye HCS monolayer with the help of ″inert″ barium ions contributes to the inhibition of aggregation and considerably enhances the sensory response of the system. Using X-ray reflectometry and X-ray standing waves methods employing synchrotron radiation, the structure of the chromoionophore complexes with mercury cations in the monolayer and the mechanism of the influence of ″inert″ cations on the monolayer structure were established.…”

Section: Resultsmentioning

confidence: 97%

“…An exception is a series of papers by the authors of this article investigating the structural transformations in monolayers of amphiphilic crown-substituted hemicyanine chromoionophores and their effect on the receptor function of the planar system. − In refs − we have described in detail the spectral changes recorded during the interaction of the compound HCS (Scheme ) with mercury cations in solutions and obtained absorption and fluorescence spectra indicating the interaction of precompressed Langmuir monolayers of this compound with mercury cations (Hg 2+ ) at the air/water interface. Based on these data, calibration curves were constructed to quantify the concentration of mercury cations in the aqueous subphase beneath the precompressed monolayer using a ratiometric approach.…”

Section: Introductionmentioning

confidence: 99%

“…Based on these data, calibration curves were constructed to quantify the concentration of mercury cations in the aqueous subphase beneath the precompressed monolayer using a ratiometric approach. Using the method of X-ray reflectometry in combination with the method of standing X-ray waves, it was found − that the preorganization of the Langmuir HCS monolayer with ″inert″ barium cations in the subphase allows the formation of a supramolecular architecture with improved receptor properties with respect to mercury cations. The mechanism of such preorganization has been revealed.…”

Section: Introductionmentioning

confidence: 99%

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Subnanomolar Detection of Mercury Cations in Water by an Interfacial Fluorescent Sensor Achieved by Ultrathin Film Structure Optimization

et al. 2022

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The objectives of this work were to develop and extend the previously proposed approaches to control the structure of nanoscale planar systems based on modular fluorophore compounds capable of efficient analyte binding and to optimize the architecture of ultrathin films formed from them to create a thin-film sensor element for mercury cations. The possibility of applying the ratiometric approach to the fluorescence measurements to obtain a quantitative analytical signal was shown. It was found that films with the Langmuir−Schaefer film architecture, in which the receptor crown ether groups of the fluoroionophore are oriented toward the studied solution, allow the quantitative determination of mercury cations in water at concentrations below the threshold limit value and are especially effective in the analyte concentration range of 10 −10 −10 −5 M. High selectivity of the obtained thin-film sensitive elements with respect to mercury cations and the possibility of regeneration of such elements after quantitative determination of mercury cations in aqueous solutions are demonstrated.

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Subnanomolar Detection of Mercury Cations in Water by an Interfacial Fluorescent Sensor Achieved by Ultrathin Film Structure Optimization

et al. 2022

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“…A good example of a solid-state metal-coordination framework was obtained for the complex of CuI and bisthiacrown receptor IV, which displayed photoluminescence switching [10]. To date, the receptor ability of hydrophobic thioether units remains relatively unexplored at the air-water interface, where Langmuir monolayers are produced, and only a few compounds have been reported [11,12]. Given the outstanding binding characteristics of thioether units preorganized on a calixarene macrocycle, as well as unique coordination features with soft metal ions, understanding the interaction of these ligands with metal ions in confined space is highly demanding for sensor design and related applications.…”

Section: Introductionmentioning

confidence: 99%

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Muravev

Yakupov

Gerasimova

et al. 2022

IJMS

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Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquid-phase complexation of soft metal ions; however, their binding potential was not extensively studied at the air–water interface, and the effect of thioether topology on metal ion binding mechanisms under various conditions was not considered. Herein, we report the interface receptor characteristics of topologically varied thiacalixarene thioethers (linear bis-(methylthio)ethoxy derivative L2, O2S2-thiacrown-ether L3, and O2S2-bridged thiacalixtube L4). The study was conducted in bulk liquid phase and Langmuir monolayers. For all compounds, the highest liquid-phase extraction selectivity was revealed for Ag+ and Hg2+ ions vs. other soft metal ions. In thioether L2 and thiacalixtube L4, metal ion binding was evidenced by a blue shift of the band at 303 nm (for Ag+ species) and the appearance of ligand-to-metal charge transfer bands at 330–340 nm (for Hg2+ species). Theoretical calculations for thioether L2 and its Ag and Hg complexes are consistent with experimental data of UV/Vis, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffractometry of Ag–thioether L2 complexes and Hg–thiacalixtube L4 complex for the case of coordination around the metal center involving two alkyl sulfide groups (Hg2+) or sulfur atoms on the lower rim and bridging unit (Ag+). In thiacrown L3, Ag and Hg binding by alkyl sulfide groups was suggested from changes in NMR spectra upon the addition of corresponding salts. In spite of the low ability of the thioethers to form stable Langmuir monolayers on deionized water, one might argue that the monolayers significantly expand in the presence of Hg salts in the water subphase. Hg2+ ion uptake by the Langmuir–Blodgett (LB) films of ligand L3 was proved by X-ray photoelectron spectroscopy (XPS). Together, these results demonstrate the potential of sulfide groups on the calixarene platform as receptor unit towards Hg2+ ions, which could be useful in the development of Hg2+-selective water purification systems or thin-film sensor devices.

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“…The self‐assembled materials have contributed significantly in the advancement of various fields, such as, the development of nanoscale smart materials, sensor development, nano‐medicines, molecular switches, laboratory‐on‐chip devices, etc [6–12] . Among the various properties of these self‐assembled functional materials, optical properties, specifically fluorescence emission, have been extensively utilized for a range of applications in material science and biology, such as, light emitting diodes, organic electronic devices, fluorescence probes and sensors, imaging agents in biological systems, etc [13–16] . One of the desirable advances for these fluorescent systems is the ability to control and tune the intensity or colour of these fluorescent systems in the simplest possible way.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Control on the Optical Properties of a Dye‐Polyelectrolyte Assembly

2021

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Control of fluorescent molecular assemblies is an exciting area of research with large potential for various important applications, such as, fluorescence sensing/probing, cell imaging and monitoring drug‐delivery. In the present contribution, we have demonstrated control on the extent of aggregation of a dye‐polyelectrolyte assembly using a macrocyclic host molecule, sulfobutylether‐β‐cyclodextrin (SBE‐β‐CD). Initially, a cationic molecular rotor based organic dye, Auramine‐O (AuO), undergoes aggregation in the presence of an anionic polyelectrolyte, polystyrene sulfonate (PSS), and displays a broad intense new emission band along with large variation in its absorption features and excited‐state lifetime. A manipulation of the monomer‐aggregate equilibrium of the dye‐polyelectrolyte assembly has been achieved by introducing a cyclodextrin based supramolecular host, SBE‐β‐CD, which leads to relocation of AuO molecules from polyelectrolyte (PSS) to supramolecular host cavity, owing to the formation of a host‐guest complex between AuO and SBE‐β‐CD. A reversible control on this manipulation of monomer‐aggregate equilibrium is further achieved by introducing a competitive guest for the host cavity i. e., 1‐Adamantanol. Thus, we have demonstrated an interesting control on the dye‐polyelectrolyte aggregate assembly using a supramolecular host molecule which open up exciting possibilities to construct responsive materials using a repertoire of various host‐specific guest molecules.

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Supramolecular control of the structure and receptor properties of an amphiphilic hemicyanine chromoionophore monolayer at the air/water interface

Abstract: Design of sensors for such toxic compounds as mercury salts in aqueous solutions still remains one of the most pressing tasks of the modern chemical ecology, since many existing systems...

Cited by 9 publications

References 29 publications

Subnanomolar Detection of Mercury Cations in Water by an Interfacial Fluorescent Sensor Achieved by Ultrathin Film Structure Optimization

Subnanomolar Detection of Mercury Cations in Water by an Interfacial Fluorescent Sensor Achieved by Ultrathin Film Structure Optimization

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Supramolecular Control on the Optical Properties of a Dye‐Polyelectrolyte Assembly

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