Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space | Sciact - CRIS-system of Boreskov Institute of Catalysis

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

Journal

International Journal of Molecular Sciences
ISSN: 1422-0067 , E-ISSN: 1661-6596

Output data

Year: 2022, Volume: 23, Number: 4, Article number : 2341, Pages count : 21 DOI: 10.3390/ijms23042341

Tags

thiacalix[4]arenes; Langmuir monolayers; thiacrown-ethers; X-ray photoelectron spectroscopy; Ag+ and Hg2+ complexes

Authors

Muravev Anton ¹ , Yakupov Ayrat ² , Gerasimova Tatiana ¹ , Islamov Daut ¹ , Lazarenko Vladimir ³ , Shokurov Alexander ⁴ , Ovsyannikov Alexander ¹ , Dorovatovskii Pavel ³ , Zubavichus Yan ⁵ , Naumkin Alexander ^4,6 , Selektor Sofiya ⁴ , Solovieva Svetlana ¹ , Antipin Igor ²

Affiliations

1	Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, Russia
2	Butlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, Russia
3	National Research Centre “Kurchatov Institute”, Kurchatov Square 1, 123182 Moscow, Russia
4	Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky Pr. 31, 119071 Moscow, Russia
5	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Nikolskii Pr. 1, 630559 Koltsovo, Russia
6	Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119334 Moscow, Russia

Funding (2)

1	Ministry of Science and Higher Education of the Russian Federation	075-00216-20-03 (АААА-А20-120060890029-3) 0671-2020-0063
2	Ministry of Science and Higher Education of the Russian Federation

Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquidphase 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.

Muravev A. , Yakupov A. , Gerasimova T. , Islamov D. , Lazarenko V. , Shokurov A. , Ovsyannikov A. , Dorovatovskii P. , Zubavichus Y. , Naumkin A. , Selektor S. , Solovieva S. , Antipin I.
Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space
International Journal of Molecular Sciences. 2022. V.23. N4. 2341 :1-21. DOI: 10.3390/ijms23042341 WOS Scopus РИНЦ ANCAN PMID OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Dec 30, 2021
Accepted:	Feb 18, 2022
Published print:	Feb 20, 2022
Published online:	Feb 20, 2022

Web of science:	WOS:000762275300001
Scopus:	2-s2.0-85124882626
Elibrary:	48151487
Chemical Abstracts:	2022:592487
Chemical Abstracts (print):	178:149223
PMID:	35216456
OpenAlex:	W4214769485
publication_identifier.sciact_skif_identifier_type:	517

DB	Citing
Scopus	11
Web of science	10
OpenAlex	9