Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces

Autor: V. V. Syakaev, Olga Babaeva, S. E. Solovieva, Igor S. Antipin, Ayrat Yakupov, Ekaterina Trushina, Sergey A. Katsyuba, Guliya Nizameeva, Tatiana P. Gerasimova, R. I. Nugmanov, A. A. Murav’ev, Sofiya L. Selektor
Jazyk: angličtina
Rok vydání: 2021
Předmět:
Magnetic Resonance Spectroscopy
Alkylation
Molecular Conformation
01 natural sciences
lcsh:Chemistry
Coordination Complexes
Crown Ethers
Calixarene
lcsh:QH301-705.5
Spectroscopy
Langmuir monolayers
Chemistry
Air
General Medicine
Computer Science Applications
Metals
visual_art
visual_art.visual_art_medium
Selectivity
surface potential
Absorption spectroscopy
Metal ions in aqueous solution
Liquid-Liquid Extraction
liquid-phase extraction
Sulfides
thiacalix[4]arene monocrowns
010402 general chemistry
Catalysis
Article
Ion
Inorganic Chemistry
Metal
Ion binding
Phenols
stomatognathic system
UV/visible reflection–absorption spectroscopy
Physical and Theoretical Chemistry
Molecular Biology
Ions
010405 organic chemistry
Organic Chemistry
Water
Dynamic Light Scattering
0104 chemical sciences
Crystallography
ion binding
lcsh:Biology (General)
lcsh:QD1-999
Solvents
Calcium
Spectrophotometry
Ultraviolet
Zdroj: International Journal of Molecular Sciences
Volume 22
Issue 7
International Journal of Molecular Sciences, Vol 22, Iss 3535, p 3535 (2021)
ISSN: 1422-0067
1661-6596
DOI: 10.3390/ijms22073535
Popis: Understanding the interaction of ions with organic receptors in confined space is of fundamental importance and could advance nanoelectronics and sensor design. In this work, metal ion complexation of conformationally varied thiacalix[4]monocrowns bearing lower-rim hydroxy (type I), dodecyloxy (type II), or methoxy (type III) fragments was evaluated. At the liquid–liquid interface, alkylated thiacalixcrowns-5(6) selectively extract alkali metal ions according to the induced-fit concept, whereas crown-4 receptors were ineffective due to distortion of the crown-ether cavity, as predicted by quantum-chemical calculations. In type-I ligands, alkali-metal ion extraction by the solvent-accessible crown-ether cavity was prevented, which resulted in competitive Ag+ extraction by sulfide bridges. Surprisingly, amphiphilic type-I/II conjugates moderately extracted other metal ions, which was attributed to calixarene aggregation in salt aqueous phase and supported by dynamic light scattering measurements. Cation–monolayer interactions at the air–water interface were monitored by surface pressure/potential measurements and UV/visible reflection–absorption spectroscopy. Topology-varied selectivity was evidenced, towards Sr2+ (crown-4), K+ (crown-5), and Ag+ (crown-6) in type-I receptors and Na+ (crown-4), Ca2+ (crown-5), and Cs+ (crown-6) in type-II receptors. Nuclear magnetic resonance and electronic absorption spectroscopy revealed exocyclic coordination in type-I ligands and cation–π interactions in type-II ligands.
Databáze: OpenAIRE