Dynamics of a photochromic spiropyran under aqueous conditions

Kohl-Landgraf, Jörg; Braun, Markus; Özçoban, Cem; Gonçalves, Diana P. N.; Heckel, Alexander; Wachtveitl, Josef

doi:10.1051/epjconf/20134105009

Cited by 2 publications

(2 citation statements)

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“…Spiropyran is a molecular photoswitch that undergoes a ring-opening and isomerization reaction upon irradiation with UV light. − The photoisomerization process has been investigated spectroscopically using femtosecond vis-pump/vis- and IR-probe spectroscopy, , and previous QM/MM calculations on spiropyran in water demonstrated only a small influence of water on the vertical excitations and photochemistry of spiropyran . The energetically lowest excited states have been characterized as “bright” and “dark” states, indicating the difference in oscillator strengths.…”

Section: Representative Applications Of Fde-adcmentioning

confidence: 99%

Implementation and Application of the Frozen Density Embedding Theory with the Algebraic Diagrammatic Construction Scheme for the Polarization Propagator up to Third Order

Prager

Zech

Wesołowski

et al. 2017

J. Chem. Theory Comput.

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Implementation, benchmarking, and representative applications of the new FDE-ADC(3) method for describing environmental effects on excited states as a combination of frozen density embedding (FDE) and the algebraic-diagrammatic construction scheme for the polarization propagator of third order (ADC(3)) are presented. Results of FDE-ADC(3) calculations are validated with respect to supersystem calculations on test systems with varying molecule-environment interaction strengths from dispersion up to multiple hydrogen bonds. The overall deviation compared to the supersystem calculations is as small as 0.029 eV for excitation energies, which is even smaller than the intrinsic error of ADC(3). The dependence of the accuracy on the choice of method and functional for the calculation of the environment and the nonelectrostatic part of the system-environment interaction is evaluated. In three representative examples, the FDE-ADC method is applied to investigate larger systems and to analyze excited state properties using visualization of embedded densities and orbitals.

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Section: Representative Applications Of Fde-adcmentioning

confidence: 99%

Implementation and Application of the Frozen Density Embedding Theory with the Algebraic Diagrammatic Construction Scheme for the Polarization Propagator up to Third Order

Prager

Zech

Wesołowski

et al. 2017

J. Chem. Theory Comput.

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“…It has been noted that a responsive cross-linking layer can be introduced between the compartments in a core–shell micellar nanostructure to achieve the design of an efficient drug carrier. , In recent years, spiropyran (Figure a) has emerged as a suitable candidate for the responsive layer, which has the capability to switch its structure to zwitterionic merocyanine (Figure b) in response to UV light with the wavelength range of 350–520 nm. Compared to spiropyran, merocyanine has drastically different physicochemical properties because of the intramolecular charge separation inducing a large molecular dipole moment, particularly. − In addition, unlike other photoresponsive molecular moieties such as azobenzene, merocyanine reverts to spiropyran once the UV irradiation stops . Qu et al successfully proposed to build a UV–visible-light-responsive reversible micelle nanoreactor using one-pot synthesis, which is formed from the assembly of amphiphilic poly(2-oxazoline)-based triblock copolymers with a spiropyran cross-linker .…”

Section: Introductionmentioning

confidence: 99%

Structural Transformation of a Multicompartment Micelle Induced by Photo-Switchable Spiropyran–Merocyanine Transition: Dissipative Particle Dynamics Simulation Approach

2022

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This work highlights the structural transformation of a multicompartment micelle consisting of an amphiphilic A-b-(C-spiropyran) diblock copolymer in water, induced by the photo-switched transition between hydrophobic nonionic spiropyran and hydrophilic zwitterionic merocyanine, using a set of computational methods such as density functional theory (DFT), molecular dynamics (MD) simulation, and dissipated particle dynamics (DPD) simulation. By employing a new computational framework for the Flory–Huggins χ-parameter, which is improved by considering solvation free energy, it is demonstrated that the χ-parameter for a merocyanine–water pair is significantly smaller than that for a spiropyran–water pair, indicating that hydrophobic spiropyran becomes hydrophilic merocyanine through the photo-switched transition. Our computational procedure of χ-parameter calculation is further validated by investigating the deprotonation of syndiotactic and isotatic acrylic acid in water. It is revealed that a reasonable χ-parameter of −0.717 and −1.23 can be calculated from a singly deprotonated syndiotactic and isotatic trimer acrylic acid in water, respectively, which is consistent with the weak acidity of acrylic acid. Finally, using a set of calculated χ-parameters, DPD simulations are performed employing two different block copolymers with two different block lengths: A10-b-(C6-Spiro12) (Micelle I) and A6-b-(C10-Spiro12) (Micelle II), demonstrating that both micelles undergo distinctive inside-out transformations as a function of the block length ratio. Through the structure analysis, it turns out that Micelle I keeps a well-defined core–shell structural feature before and after the transformation, whereas Micelle II loses such structural feature because short Block A is not capable of forming the core of micelle.

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Dynamics of a photochromic spiropyran under aqueous conditions

Abstract: Abstract. The dynamics of a water soluble spiropyran is investigated by means of femtosecond transient absorption spectroscopy in the visible and infrared spectral range revealing an ultrafast reversible switching behavior under aqueous conditions with a high fatigue resistance.

Cited by 2 publications

References 10 publications

Implementation and Application of the Frozen Density Embedding Theory with the Algebraic Diagrammatic Construction Scheme for the Polarization Propagator up to Third Order

Implementation and Application of the Frozen Density Embedding Theory with the Algebraic Diagrammatic Construction Scheme for the Polarization Propagator up to Third Order

Structural Transformation of a Multicompartment Micelle Induced by Photo-Switchable Spiropyran–Merocyanine Transition: Dissipative Particle Dynamics Simulation Approach

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