Thiacalix[4]monocrowns Substituted by Sulfur-Containing Anchoring Groups: New Ligands for Gold Surface Modification

Muravev, Anton A.; Solovieva, Svetlana E.; Kochetkov, Evgenii N.; Мельникова, Н. Б.; Сафиуллин, Р. А.; Kadirov, Marsil K.; Latypov, Shamil K.; Антипин, И. С.; Коновалов, А. И.

doi:10.6060/mhc131269m

Cited by 13 publications

(11 citation statements)

References 21 publications

(35 reference statements)

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“…Similarly, partial cone analog II with dithiolane fragments on the lower rim displayed potentiometric recognition of alkaline-earth vs. alkali metal ions (although the role of crown-ether moiety in such discrimination is not evident) [16]. A different approach was employed in our group to facilitate enzyme adhesion to gold substrate by amphiphilic 1,3-alternate thiacalix [4]monocrown-5 III in Langmuir monolayers [17]. A significant advance in covalent confinement of calixcrowns was achieved through immobilization of thiacrown IV-Au nanoparticles onto polymer membrane to give an ultrasensitive response towards Ag + [18].…”

Section: Introductionmentioning

confidence: 99%

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

Muravev

Yakupov

Gerasimova

et al. 2021

IJMS

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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.

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Section: Introductionmentioning

confidence: 99%

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

Muravev

Yakupov

Gerasimova

et al. 2021

IJMS

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“…However, electron-withdrawing substituents decrease nucleophilicity of phenolate-anion and require higher temperatures and longer reaction time to access type III structures. Due to the base-promoted ether-group cleavage in distally disubstituted thiacalixarenes, which is enhanced at elevated temperatures and longer reaction times [26,27], nitrocalixarene 1 was alkylated with 1-dodecanol and 1-octanol (synthesis, monolayer formation, and optical characteristics of the product 2b was published as a preliminary result in [28]) (Scheme 1). Interestingly, the extent of lower rim substitution could be controlled by reaction temperature.…”

Section: Synthesis Of the Chromophoresmentioning

confidence: 99%

Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior

Muravev

Gerasimova

Fayzullin

et al. 2020

IJMS

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Achieving high thermal stability and control of supramolecular organization of functional dyes in sensors and nonlinear optics remains a demanding task. This study was aimed at the evaluation of thermal behavior and Langmuir monolayer characteristics of topologically varied nitrothiacalixarene multichromophores and phenol monomers. A nitration/azo coupling alkylation synthetic route towards partially O-substituted nitrothiacalixarenes and 4-nitrophenylazo-thiacalixarenes was proposed and realized. Nuclear magnetic resonance (NMR) spectroscopy and X-ray diffractometry of disubstituted nitrothiacalix[4]arene revealed a rare 1,2-alternate conformation. A synchronous thermal analysis indicated higher decomposition temperatures of nitrothiacalixarene macrocycles as compared with monomers. Through surface pressure/potential-molecular area measurements, nitrothiacalixarenes were shown to form Langmuir monolayers at the air–water interface and, through atomic force microscopy (AFM) technique, Langmuir–Blodgett (LB) films on solid substrates. Reflection-absorption spectroscopy of monolayers and electronic absorption spectroscopy of LB films of nitrothiacalixarenes recorded a red-shifted band (290 nm) with a transition from chloroform, indicative of solvatochromism. Additionally, shoulder band at 360 nm was attributed to aggregation and supported by gas-phase density functional theory (DFT) calculations and dynamic light scattering (DLS) analysis in chloroform–methanol solvent in the case of monoalkylated calixarene 3. Excellent thermal stability and monolayer formation of nitrothiacalixarenes suggest their potential as functional dyes.

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“…[1,2] Calixarenes, even without distinct hydrophilic and hydrophobic regions, are capable of self-organization and the formation of supramolecular assemblies of various types. [1][2][3][4][5] In the last decade, much attention has been paid to the study of the synthesis methods, properties and applications of azosulfonate calix [4] arenes (ASC) and their derivatives. [6,7] Water-soluble ASC are promising compounds that may have photo-switching properties, [8,9] which allows managing the self-organization and physicochemical properties of the substance in solution.…”

Section: Introductionmentioning

confidence: 99%

Self-Organization and Physicochemical Properties of Aqueous Solutions of the Sodium Salt of Azosulphonate Calix[4]arene

Муртазина¹,

Рыжкина²,

Shevelev³

et al. 2019

MHC

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The self-organization and physicochemical properties of aqueous solutions of the sodium salt of azosulfonate calix[4] arene (1) were studied in a wide range of concentrations 1•10-10-1•10-1 M using a complex of methods. It has been found that the solutions of macrocycle 1 are in fact complex disperse systems, the nature of disperse phase in which changes with dilutions-from micelles (CMC = 2.5•10-2 М) and premicellar aggregates (1•10-2-1•10-3 М) of the size of 1 nm to supramolecular domains (1•10-3-1•10-6 М) with sizes of tens and hundreds of nm. Jointly using the methods of dynamic light scattering and UV spectroscopy it was shown for the first time that the nonlinear character of the concentration dependence of the optical absorbance (A 360) in the concentration range 1•10-6-1.5•10-5 М is a result of the rearrangements of supramolecular domains of 1, accompanied by the transition from bi-to monomodal pattern of particles' size distribution, as well as by non-monotonic change in their size and ζ-potential. It was established that molecules of 1 are not capable of photoisomerization of the azobenzene group, which may be due to steric hindrances to the process of isomerization of closely located azoarylsulfonate groups located on one side of the plane of macrocycle 1.

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Thiacalix[4]monocrowns Substituted by Sulfur-Containing Anchoring Groups: New Ligands for Gold Surface Modification

Cited by 13 publications

References 21 publications

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

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

Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior

Self-Organization and Physicochemical Properties of Aqueous Solutions of the Sodium Salt of Azosulphonate Calix[4]arene

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