Combined TDDFT and AIM Insights into Photoinduced Excited State Intramolecular Proton Transfer (ESIPT) Mechanism in Hydroxyl- and Amino-Anthraquinone Solution

Zheng, Daoyuan; Zhang, Mingzhen; Zhao, G.

doi:10.1038/s41598-017-14094-5

Cited by 33 publications

(16 citation statements)

References 78 publications

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“…S4. A similar excited state rearrangement is observed for the closely related compound 1,8-dihydroxy-9,10-anthraquinone (chrysazin, an oxidation product of A) as reported by Smulevich and coworkers (Smulevich et al, 1987;Marzocchi et al, 1998) and recently studied theoretically by Mohammed et al (2014) and by Zheng, Zhang & Zhao (2017).…”

Section: Excited State Intramolecular Proton Transfer (Esipt)supporting

confidence: 81%

UV synchrotron radiation linear dichroism spectroscopy of the anti-psoriatic drug anthralin

Nguyen

Jones

Hoffmann

et al. 2019

PeerJ Physical Chemistry

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Anthralin (1,8-dihydroxyanthrone, 1,8-dihydroxy-9(10H)-anthracenone), also known as dithranol and cignolin, is one of the most efficient drugs in the treatment of psoriasis and other skin diseases. The precise mode of biochemical action is not fully understood, but the activity of the drug is increased by the influence of UV radiation. In the present investigation, the UV absorption of anthralin is studied by synchrotron radiation linear dichroism (SRLD) spectroscopy on molecular samples partially aligned in stretched polyethylene, covering the near and vacuum UV regions with wavenumbers ranging from 23,000 to 58,000 cm–1(430–170 nm). The observed polarization spectra are well predicted by quantum chemical calculations using time-dependent density functional theory (TD–DFT). About a dozen spectral features are assigned to computed electronic transitions. The calculations support interpretation of the anomalous fluorescence of anthralin as a result of barrier-less excited state intramolecular proton transfer (ESIPT) to the tautomer 8,9-dihydroxy-1(10H)-anthracenone.

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Section: Excited State Intramolecular Proton Transfer (Esipt)supporting

confidence: 81%

UV synchrotron radiation linear dichroism spectroscopy of the anti-psoriatic drug anthralin

Nguyen

Jones

Hoffmann

et al. 2019

PeerJ Physical Chemistry

View full text Add to dashboard Cite

show abstract

“…A similar excited state rearrangement is observed for the closely related compound 1,8dihydroxy-9,10-anthraquinone (chrysazin, an oxidation product of A) as reported by Smulevich and coworkers (Smulevich et al, 1987;Marzocchi et al, 1998) and recently studied theoretically by Mohammed et al (Mohammad et al, 2014) and by Zheng et al (Zheng, Zhang & Zhao, 2017).…”

Section: Excited State Intramolecular Proton Transfer (Esipt)supporting

confidence: 79%

Peer Review #2 of "UV synchrotron radiation linear dichroism spectroscopy of the anti-psoriatic drug anthralin (v0.1)"

2019

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Anthralin (1,8-dihydroxyanthrone, 1,8-dihydroxy-9(10H)-anthracenone), also known as dithranol and cignolin, is one of the most efficient drugs in the treatment of psoriasis and other skin diseases. The precise mode of biochemical action is not fully understood, but the activity of the drug is increased by the influence of UV radiation. In the present investigation, the UV absorption of anthralin is studied by synchrotron radiation linear dichroism (SRLD) spectroscopy on molecular samples partially aligned in stretched polyethylene, covering the near and vacuum UV regions with wavenumbers ranging from 23000 to 58000 cm -1 (430-170 nm). The observed polarization spectra are well predicted by quantum chemical calculations using time-dependent density functional theory (TD-DFT). About a dozen spectral features are assigned to computed electronic transitions.The calculations support interpretation of the anomalous fluorescence of anthralin as a result of barrier-less excited state intramolecular proton transfer (ESIPT) to the tautomer 8,9-dihydroxy-1(10H)-anthracenone.

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“…The normal and twist conformations from the S 0 and S 1 states of the AYAAQs derivatives (Figure ) and the AAQ dye (Figure ) are optimized using the CAM-B3LYP/TD-CAM-B3LYP/6-31G(d,p)/PCM/acetonitrile level. There is no discussion of the proton transfer conformations (Supporting Information) in this article, owing to that the intramolecular proton transfer reaction of AYAAQs has been widely investigated before. − The corresponding primary structural parameters of AYAAQs and AAQ are summarized in Table , in which the stable normal conformations in the S 0 state and the twist conformation in the S 1 state are abbreviated as S 0 (N) and S 1 (T), respectively. The dihedral angles of C 4 –C 5 –N 1 –C 6 (around −150°) and C 4 –C 5 –N 1 –H 6 (around −180°) show that the optimized geometries of AYAAQs and AAQ are near planar in the S 0 state, and the distance of H 2 ···O 3 (around 1.8 Å) indicates that the intramolecular hydrogen bond N 1 –H 2 ···O 3 of AYAAQs is relatively weak.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Subsequently, Nagaoka et al studied the ESIPT and 1 O 2 quenching activities of AYAAQs by the static and laser spectroscopic techniques. , Their work demonstrated that the ESIPT positively and linearly correlated with 1 O 2 quenching activities. Recently, Ma and Zheng et al investigated the effects of different substituted groups in intramolecular proton transfer in the S 1 state of AYAAQs by the DFT/TD-DFT/B3LYP level. , Among the previous experimental and theoretical studies, researches mainly focused on the characteristics of excited state fluorescence and the ESIPT reactions of the AYAAQs derivatives. However, their low fluorescence efficiency (Table ) has not been well explained.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Fluorescence Quenching by Acylamino Twist in the Excited State for 1-(Acylamino)anthraquinones

et al. 2018

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Nitrogen-containing anthraquinone derivatives are widely applied in vegetable fiber dyes. In this paper, the fluorescence quenching mechanism by an acylamino group twist in the excited state for the 1-(acylamino)anthraquinones (AYAAQs) derivatives in acetonitrile is investigated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The calculated Stokes shift is in good agreement with the experimental data. The energy profiles show that each AYAAQs derivative reveals a barrierless twist process, indicating that the involvement of acylamino group rotation in addition to proton transfer becomes as another important coordinate in the excited state relaxation pathway. The effects of electron-substituted group promote twist process compared with 1-aminoanthraquinone (AAQ). Then, the cross points are searched by the constructed linearly interpolated internal coordinate (LIIC) pathways for AYAAQs, demonstrating that the potential energy curves of the S and T states intersect each other and are in accord with the El-Sayed rules. So one can conclude that the acylamino group twist and following intersystem crossing (ISC) processes are important nonradiative inactivation channel for the S state of the AYAAQs derivatives, which is more prone to proton transfer process and can explain the low fluorescence efficiency. In addition, we have measured the phosphorescence spectra of AAQ, and on this basis, it can be predicted that the phosphorescence may occur for the AYAAQs derivatives.

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Combined TDDFT and AIM Insights into Photoinduced Excited State Intramolecular Proton Transfer (ESIPT) Mechanism in Hydroxyl- and Amino-Anthraquinone Solution

Cited by 33 publications

References 78 publications

UV synchrotron radiation linear dichroism spectroscopy of the anti-psoriatic drug anthralin

UV synchrotron radiation linear dichroism spectroscopy of the anti-psoriatic drug anthralin

Peer Review #2 of "UV synchrotron radiation linear dichroism spectroscopy of the anti-psoriatic drug anthralin (v0.1)"

Mechanism of Fluorescence Quenching by Acylamino Twist in the Excited State for 1-(Acylamino)anthraquinones

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