Control of self-organization of thiacalix[4]crown-ethers in cone and 1,3-alternate forms in nanofilms on quartz substrate

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Morphological characteristics of the nanolayers of amphiphilic tert-butylthiacalix[4]crown-4-ether in cone stereoisomeric form 1 and bolaamphiphilic nitrothiacalix[4]biscrown-5-ether in 1,3-alternate form 2 deposited onto quartz substrate at varying solvent, temperature, and concentration of compounds is analyzed. Quantum-chemical calculations of the considered calix[4]arenes reveal a favorable micellar aggregation (the packing factor p < 0.3). During AFM visualization of calixarene nanolayers prepared through evaporation of solvent on substrate, spherical associates that are 200–800 nm in size are detected for compound 1, which enlarge with a decrease in the concentration of compound and an increase in solvent polarity and environmental temperature. At the same time, the dispersity of the sizes of associates increases with a decrease in temperature, but has a mixed dependence on solvent and concentration. The most uniform size distribution of spherical particles is achieved upon Langmuir monolayer formation at the air–water interface upon deposition of the solution of compound 1 in 10–5 M solution in chloroform onto water subphase and upon vertical transfer onto substrate. In the case of bolaamphiphile 2, spherical associates are formed at t = 23°C in 10–5 М solution in toluene and at 4°С in 10–4 М solution in chloroform, while under other combinations of conditions, the nanofilm is represented by thread-like structures (at 23°С) and tactoid aggregates (at 4°С). Dynamic light scattering study of the solutions of amphiphile 1 in chloroform allows to detect spherical aggregates (particle size is 202 ± 92 nm), which indicates the decisive role of solvent in the formation of spherical aggregates in nanolayers, while in other cases the supramolecular organization of calixarenes is presumably affected by the interaction with substrate.

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作者简介

I. Chetinel

Научно-образовательный центр инфохимии, Университет ИТМО

Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург

A. Botnar

Научно-образовательный центр инфохимии, Университет ИТМО

Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург

A. Novikov

Научно-образовательный центр инфохимии, Университет ИТМО

Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург

E. Muraveva

Научно-образовательный центр инфохимии, Университет ИТМО

Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург

A. Ireddy

Научно-образовательный центр инфохимии, Университет ИТМО

Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург

P. Zun

Научно-образовательный центр инфохимии, Университет ИТМО

Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург

S. Solovieva

Институт органической и физической химии, ФИЦ КазНЦ РАН

Email: muravev@itmo.ru
俄罗斯联邦, Казань

I. Antipin

Институт органической и физической химии, ФИЦ КазНЦ РАН

Email: muravev@itmo.ru
俄罗斯联邦, Казань

E. Skorb

Научно-образовательный центр инфохимии, Университет ИТМО

Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург

A. Muravev

Научно-образовательный центр инфохимии, Университет ИТМО; Институт органической и физической химии, ФИЦ КазНЦ РАН

编辑信件的主要联系方式.
Email: muravev@itmo.ru
俄罗斯联邦, Санкт-Петербург; Казань

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2. Scheme 1.

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3. Scheme 2

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4. Fig. 1. 1H NMR spectrum of nitrothiacalix[4]crown-5-ether 2 in CDCl3 at T = 303 K. Red arrows on the structural formula highlight the nuclear Overhauser effects. The insets show fragments of the 1H/1H COSY and 1H/1H NOESY spectra of compound 2.

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5. Fig. 2. Structural formulas of thiacalix[4]crown ether conjugates (hydrophobic and hydrophilic fragments of molecules are highlighted in yellow and blue, respectively) (a). Possible types of surfactant aggregation depending on the value of the packing factor in a non-polar medium (b). Scheme of formation of nanolayers from solutions of the studied thiacalix[4]crown ether conjugates and a list of variable parameters of the solutions (c). Methods used to determine the particle size of thiacalix[4]crown ether conjugates formed in solution and on a solid support (d).

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6. Fig. 3. Scheme for calculating the packing factor based on the results of quantum-chemical calculations (a) and description of the van der Waals surface of atoms using a solvent in the form of a sphere-probe (b). Visualization of overlapping regions of hydrophobic and hydrophilic fragments for calixarene molecules (hydrophobic and hydrophilic fragments of molecules are indicated by yellow and blue backgrounds, respectively) (c). Example of calculating the volume of the hydrophilic volume of an amphiphilic molecule taking into account the presence of overlapping regions (d). Calculated values ​​of the packing factor p for amphiphile 1 and bolaamphiphile 2 in different solvents (d).

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7. Fig. 4. AFM images of compounds 1 (a–h) and 2 (i–n) obtained by evaporation from solutions in chloroform (a–g, i, j, n, o) and toluene (g, h, l, m) or by Langmuir monolayer transfer (e, f). The initial concentration in the solution is 10–4 mol/L (a–c, e, g, i, l, n, o), 10–5 mol/L (d, f, h, j, l). The solvent temperature is 23°C (a, c–m, o), 4°C (b, m). The temperature of the dissolved precipitate is 23°C (a, b, d–n), 4°C (c, o).

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