Photochromic transformations of amphiphilic spiropyran in acetonitrile solutions and at the air/water interface

Ivakhnenko, D. A.; Shokurov, Alexander V.; Lyubimova, G. V.; Zaichenko, N. L.; Arslanov, V. V.; Raitman, Oleg A.

doi:10.1007/s11172-018-2368-0

Cited by 7 publications

(2 citation statements)

References 13 publications

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“…According to the location of the SP/MC unit in the amphiphile structure, the molecules can be classified as the following: The first group represents surfactants with spiropyran/ merocyanine introduced as the head group ( Figure 1 a) [ 9 , 17 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ]. For the second one, SP/MC is a part of the tail of a photoresponsive amphiphile included at its different positions: at the end of the hydrocarbon chain [ 11 , 18 , 19 , 20 , 22 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 ] ( Figure 1 b) or in its middle [ 10 ].…”

Section: Introductionmentioning

confidence: 99%

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Savchenko

Lomadze

Santer

et al. 2022

IJMS

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This joint experimental-theoretical work focuses on molecular and photophysical properties of the spiropyran-containing amphiphilic molecule in organic and aqueous solutions. Being dissolved in tested organic solvents, the system demonstrates positive photochromism, i.e., upon UV stimulus the colorless spiropyran form is transformed into colorful merocyanine isomer. However, the aqueous solution of the amphiphile possesses a negative photochromism: the orange-red merocyanine form becomes thermodynamically more stable in water, and both UV and vis stimuli lead to the partial or complete photobleaching of the solution. The explanation of this phenomenon is given on the basis of density functional theory calculations and classical modeling including thermodynamic integration. The simulations reveal that stabilization of merocyanine in water proceeds with the energy of ca. 70 kJ mol−1, and that the Helmholtz free energy of hydration of merocyanine form is 100 kJ mol−1 lower as compared to the behavior of SP isomer in water. The explanation of such a difference lies in the molecular properties of the merocyanine: after ring-opening reaction this molecule transforms into a zwitterionic form, as evidenced by the electrostatic potential plotted around the opened form. The presence of three charged groups on the periphery of a flat conjugated backbone stimulates the self-assembly of merocyanine molecules in water, ending up with the formation of elongated associates with stack-like building blocks, as shown in molecular dynamics simulations of the aqueous solution with the concentration above critical micelle concentration. Our quantitative evaluation of the hydrophilicity switching in spiropyran/merocyanine containing surfactants may prompt the search for new systems, including colloidal and polymeric ones, aiming at remote tuning of their morphology, which could give new promising shapes and patterns for the needs of modern nanotechnology.

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Section: Introductionmentioning

confidence: 99%

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Savchenko

Lomadze

Santer

et al. 2022

IJMS

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show abstract

“…According to the location of the SP/MC unit in the amphiphile structure, the molecules can be classified as following. The first group represents surfactants with spiropyran/merocyanine introduced as the head group (Figure 1a) [15,25,[31][32][33][34][35][36][37][38][39][40][41][42][43][44]. For the second one, SP/MC is a part of the tail of a photoresponsive amphiphile included at its different positions: at the end of the hydrocarbon chain [17,[26][27][28]30,[45][46][47][48][49][50][51][52] (Figure 1b) or in its middle [16].…”

Section: Introductionmentioning

confidence: 99%

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Savchenko¹,

Lomadze²,

Santer³

et al. 2022

Preprint

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This joint experimental-theoretical work focuses on molecular and photophysical properties of the spiropyran-containing amphiphilic molecule in organic and aqueous solutions. Being dissolved in tested organic solvents, the system demonstrates positive photochromism, i.e. upon UV stimulus the colorless spiropyran form is transformed into colorful merocyanine isomer. However, aqueous solution of the amphiphile possesses a negative photochromism: the orange-red merocyanine form turns to be thermodynamically more stable in water, and both UV and vis stimuli lead to the partial or complete photobleaching of the solution. The explanation of this phenomenon is given on the basis of density functional theory calculations and classical modeling including thermodynamic integration. The simulations reveal that stabilization of merocyanine in water proceeds with the energy of ca. 70 kJ mol−1, and that the Helmholtz free energy of hydration of merocyanine form is 100 kJ mol−1 lower as compared to the behavior of SP isomer in water. The explanation of such a difference lies in the molecular properties of the merocyanine: after ring-opening reaction this molecule transforms into a zwitterionic form, as evidenced by the electrostatic potential plotted around the opened form. The presence of three charged groups on the periphery of a flat conjugated backbone stimulates the self-assembly of merocyanine molecules in water, ending up with the formation of elongated associates with stack-like building blocks, as shown in molecular dynamics simulations of the aqueous solution with the concentration above critical micelle concentration. Our quantitative evaluation of the hydrophilicity switching in spiropyran/merocyanine containing surfactants may prompt the search for new systems, including colloidal and polymeric ones, aiming at remote tuning of their morphology, which could give new promising shapes and patterns for the needs of modern nanotechnology.

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Isomerization and changes of the properties of spiropyrans by mechanical stress: advances and outlook

Pugachev

Муханов

Ozhogin

et al. 2021

Chem Heterocycl Comp

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Photochromic transformations of amphiphilic spiropyran in acetonitrile solutions and at the air/water interface

Cited by 7 publications

References 13 publications

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Isomerization and changes of the properties of spiropyrans by mechanical stress: advances and outlook

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