Trans-cis Photoisomerization of a Biomimetic Cyclocurcumin Analogue Rationalized by Molecular Modelling

<div> <p>Cyclocurcumin is a natural compound extracted from turmeric and showing, in addition to antiinfective, antibacterial, and intinflammatory capabilities, solvent-dependent phtoswitching ability. The solvent-dependent photochemistry of cyclocurcumin has been rationalized on the basis of a competition between π-π* and n-π* states. Recently we have reported the synthesis of a biomimetic analogue showing enhanced photochemical properties and in particular presenting photoswitching capacity in various media. In the present contribution we rely on the use of molecular modeling and simulation, incuding density functional and wavefunction based methods to explore the excited states potential energy surface landscape. We see that the addition of a carbon-carbon double bond to the core of the natural compounds favors the population of the π-π* state, whatever the choice of the solvent, and hence leads to photoisomerisation, with fluorescence reduced to only a minor channel, rationalizing the experimental observations. In addition, the two photon absorption cross section is also strongly increased compared to the parent compound, paving the way to the use in biologically oriented applications.</p></div>

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Trans-cis Photoisomerization of Biomimetic Cyclocurcumin Analogous Rationalized by Molecular Modelling

10.26434/chemrxiv.14248550 ◽

2021 ◽

Author(s):

Raúl Losantos ◽

Jeremy Pecourneau ◽

Maxime Mourer ◽

Stephane Parant ◽

Andreea Pasc ◽

...

Keyword(s):

Excited States ◽

Density Functional ◽

Parent Compound ◽

Photon Absorption ◽

Present Contribution ◽

Two Photon Absorption ◽

Two Photon ◽

Photochemical Properties ◽

A Minor ◽

Π State

Cyclocurcumin is a natural compound extracted from turmeric and showing, in addition to antiinfective, antibacterial, and intinflammatory capabilities, solvent-dependent phtoswitching ability. The solvent-dependent photochemistry of cyclocurcumin has been rationalized on the basis of a competition between π-π* and n-π* states. Recently we have reported the synthesis of a biomimetic analogous showing enhanced photochemical properties and in particular presenting photoswitching capacity in various media. In the present contribution we rely on the use of molecular modeling and simulation, incuding density functional and wavefunction based methods to explore the excited states potential energy surface landscape. We see that the addition of a carbon-carbon double bond to the core of the natural compounds favors the population of the π-π* state, whatever the choice of the solvent, and hence leads to photoisomerisation, with fluorescence reduced to only a minor channel, rationalizing the experimental observations. In addition, the two photon absorption cross section is also strongly increased compared to the parent compound, paving the way to the use in biologically oriented applications.

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Trans-cis Photoisomerization of Biomimetic Cyclocurcumin Analogous Rationalized by Molecular Modelling

10.26434/chemrxiv.14248550.v1 ◽

2021 ◽

Author(s):

Raúl Losantos ◽

Jeremy Pecourneau ◽

Maxime Mourer ◽

Stephane Parant ◽

Andreea Pasc ◽

...

Keyword(s):

Excited States ◽

Density Functional ◽

Parent Compound ◽

Photon Absorption ◽

Present Contribution ◽

Two Photon Absorption ◽

Two Photon ◽

Photochemical Properties ◽

A Minor ◽

Π State

Cyclocurcumin is a natural compound extracted from turmeric and showing, in addition to antiinfective, antibacterial, and intinflammatory capabilities, solvent-dependent phtoswitching ability. The solvent-dependent photochemistry of cyclocurcumin has been rationalized on the basis of a competition between π-π* and n-π* states. Recently we have reported the synthesis of a biomimetic analogous showing enhanced photochemical properties and in particular presenting photoswitching capacity in various media. In the present contribution we rely on the use of molecular modeling and simulation, incuding density functional and wavefunction based methods to explore the excited states potential energy surface landscape. We see that the addition of a carbon-carbon double bond to the core of the natural compounds favors the population of the π-π* state, whatever the choice of the solvent, and hence leads to photoisomerisation, with fluorescence reduced to only a minor channel, rationalizing the experimental observations. In addition, the two photon absorption cross section is also strongly increased compared to the parent compound, paving the way to the use in biologically oriented applications.

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Bisporphyrin connected by tetrathiafulvalene

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424609000073 ◽

2009 ◽

Vol 13 (01) ◽

pp. 114-121 ◽

Cited By ~ 8

Author(s):

Kazuya Ogawa ◽

Yasunori Nagatsuka

Keyword(s):

Cross Section ◽

Density Functional ◽

Polar Solvent ◽

Soret Band ◽

Oxidation Potential ◽

Time Dependent ◽

Photon Absorption ◽

Functional Theory ◽

Two Photon Absorption ◽

Two Photon

A new porphyrintetrathiafulvalene composite, where two porphyrins are bridged by te trathiafulvalene (TTF) using acetylene bonds was synthesized. The Q-band of the monomeric porphyrin appears at 590 nm whereas that of the composite is red-shifted to 620 nm and intensified. The Soret band is also red-shifted from 427 nm to 435 nm and much broadened, indicating the expansion of π-conjugation over the porphyrin and tetrathiafulvalene units. The HOMOs and LUMOs were calculated using time-dependent density functional theory. Voltammetric experiments revealed that the first oxidation potential of the TTF moiety in the composite was shifted by +155 mV compa red with TTF in the absence of composite. The effective two-photon absorption (2PA) cross section values were measured by using a nanosecond open aperture Z-scan method. The maximum effective 2PA cross section values were obtained at 760 nm, as 7300 GM in benzonitrile and 5900 GM in toluene. The values obtained in the polar solvent were 1.2 to 1.5 times larger than those in the nonpolar solvent.

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Theoretical studies on the one- and two-photon absorption of tetrabenzoporphyrins and phthalocyanines

Canadian Journal of Chemistry ◽

10.1139/v03-175 ◽

2004 ◽

Vol 82 (1) ◽

pp. 19-26 ◽

Cited By ~ 16

Author(s):

Xin Zhou ◽

Ai-Min Ren ◽

Ji-Kang Feng ◽

Xiao-Juan Liu

Keyword(s):

Dipole Moment ◽

Cross Sections ◽

Density Functional ◽

Transition Dipole Moment ◽

Photon Absorption ◽

Transition Dipole ◽

Two Photon Absorption ◽

Two Photon ◽

Order Of Magnitude ◽

The One

The one-photon absorption (OPA) properties of tetrabenzoporphyrins (TBPs) and phthalocyanines (Pcs) were studied using the semiempirical ZINDO method and time-dependent density functional theory (TDDFT), respectively. The compared results confirmed that the semiempirical ZINDO method was reasonably reliable when calculating the OPA of tetrabenzoporphyrins and phthalocyanines. On the basis of the OPA properties obtained from the ZINDO method, two-photon absorption (TPA) properties of two series of molecules were investigated, using ZINDO and sum-over-states (SOS) methods. The results showed that the TPA cross-sections of all molecules were in the range of 220.6 × 1050 345.9 × 1050 cm4·s·photon1, which were in the same order of magnitude as the values reported in the literature. The relatively larger δ(ω) value for Pcs with respect to that for corresponding TBPs originates from larger intramolecular charge transfer, which can be characterized by the difference of dipole moment between S0 and S1 and the transition dipole moment between S1 and S5.Key words: two-photon absorption, ZINDO, sum-over-states, tetrabenzoporphyrin, phthalocyanines.

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Fluorescence anisotropy in indole under two-photon excitation in the spectral range 385–510 nm

Physical Chemistry Chemical Physics ◽

10.1039/c8cp02708k ◽

2018 ◽

Vol 20 (30) ◽

pp. 19922-19931 ◽

Cited By ~ 6

Author(s):

M. E. Sasin ◽

A. G. Smolin ◽

K.-H. Gericke ◽

E. Tokunaga ◽

O. S. Vasyutinskii

Keyword(s):

Propylene Glycol ◽

Excited States ◽

Spectral Range ◽

Ground State ◽

Fluorescence Anisotropy ◽

Photon Absorption ◽

Two Photon Absorption ◽

Two Photon ◽

Photon Excitation ◽

Molecular Ground State

This paper presents the detailed study of two-photon excited fluorescence in indole dissolved in propylene glycol produced by two-photon absorption from the molecular ground state to several high lying excited states.

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Tuning of Hyperpolarizability, One- and Two-Photon Absorption of D-A and D-A-A Type Intramolecular Charge Transfer Based Sensors

10.26434/chemrxiv.7869062 ◽

2019 ◽

Author(s):

Pralok K. Samanta ◽

Md Mehboob Alam ◽

Ramprasad Misra ◽

Swapan K. Pati

Keyword(s):

Charge Transfer ◽

Gas Phase ◽

Density Functional ◽

Intramolecular Charge Transfer ◽

Photon Absorption ◽

First Hyperpolarizability ◽

Two Photon Absorption ◽

Two Photon ◽

Nlo Response ◽

Donor Acceptor

Solvents play an important role in shaping the intramolecular charge transfer (ICT) properties of π-conjugated molecules, which in turn can affect their one-photon absorption (OPA) and two-photon absorption (TPA) as well as the static (hyper)polarizabilities. Here, we study the effect of solvent and donor-acceptor arrangement on linear and nonlinear optical (NLO) response properties of two novel ICT-based fluorescent sensors, one consisting of hemicyanine and dimethylaniline as electron withdrawing and donating groups (molecule 1), respectively and its boron-dipyrromethene (BODIPY, molecule 2)-fused counterpart (molecule 3). Density functional theoretical (DFT) calculations using long-range corrected CAM-B3LYP and M06-2X functionals, suitable for studying properties of ICT molecules, are employed to calculate the desired properties. The dipole moment (µ) as well as the total first hyperpolarizability (β<sub>total</sub>) of the studied molecules in the gas phase is dominantly dictated by the component in the direction of charge transfer. The ratios of vector component of first hyperpolarizability (β<sub>vec</sub>) to β<sub>total</sub> also reveal unidirectional charge transfer process. The properties of the medium significantly affect the OPA, hyperpolarizability and TPA properties of the studied molecules. Time dependent DFT (TDDFT) calculations suggest interchanging between two lowest excited states of molecule 3 from the gas phase to salvation. The direction of charge polarization and dominant transitions among molecular orbitals involved in the OPA and TPA processes are studied. The results presented are expected to be useful in tuning the NLO response of many ICT-based chromophores, especially those with BODIPY acceptors.<br>

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Synthesis, DNA photocleavage, singlet oxygen photogeneration and two photon absorption properties of ruthenium-phenanthroline porphyrins

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424615500790 ◽

2015 ◽

Vol 19 (09) ◽

pp. 1046-1052 ◽

Cited By ~ 13

Author(s):

Ze-Bin Xu ◽

Fa-Quan Yu ◽

Fengshou Wu ◽

Heng Zhang ◽

Kai Wang ◽

...

Keyword(s):

Singlet Oxygen ◽

Cross Section ◽

Therapeutic Agents ◽

Photon Absorption ◽

Quantum Yields ◽

Absorption Properties ◽

Dna Photocleavage ◽

Two Photon Absorption ◽

Two Photon ◽

Photochemical Properties

Through a new synthetic route, three ruthenium-phenanthroline porphyrins (RPP1, RPP2 and RPP3) were prepared. Their photophysical and photochemical properties, such as DNA photocleavage activity, singlet-oxygen photogeneration and two-photon absorption (2PA) were evaluated. These porphyrins 1–3 had substantial photocleavage activities, with 71%, 74% and 38% observed at 20 μM. The porphyrins with different substituents on phenathroline group had similar singlet oxygen quantum yields, with ΦΔ values at 0.52, 0.47 and 0.41, respectively. The 2PA cross-section (σ(2)) values of RPP 1–3, measured by the Z-scan method, were calculated to be 152, 172 and 135 GM, respectively, which were around 5-fold higher than that of H2TPP . Thus, these porphyrins, with their good photocleavage activities, 1 O 2 quantum yields and high 2PA cross section, suggest great potential as photodynamic therapeutic agents.

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