A designed protein binding-pocket to control excited-state intramolecular proton transfer fluorescence

Lampkin, Bryan J.; Monteiro, Cecília; Powers, Evan T.; Bouc, Paige M.; VanVeller, Brett

doi:10.1039/c8ob02673d

Cited by 13 publications

(28 citation statements)

References 35 publications

(31 reference statements)

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“…The vertical excitation energies have been calculated using the S 0 ‐state optimized DHPBC‐enol structure using TDDFT/B3LYP/TZVP theoretical level in CH 2 Cl 2 solvent. The absorption peak of the first transition from S 0 to S 1 state is calculated to be 350.6 nm, which is consistent with previous experimental report . That is to say, the theoretical method used in this work is reasonable for DHPBC system.…”

Section: Resultssupporting

confidence: 90%

“…After fast relaxation, the fluorescence peak of DHPBC‐enol is simulated to become 390.6 nm. Because of the ultrafast ESIPT process mentioned above, the normal fluorescence 390.6 nm was not observed in previous experiment . And after ESIPT reaction, the emission peak of DHPBC‐keto is 504.1 nm, which is in good agreement with experimental report 520 nm .…”

Section: Resultssupporting

confidence: 84%

“…And given the low barrier for ESIPT reaction, it can be concluded that this ESIPT process should be ultrafast. That should be the reason why the normal fluorescence band of DHPBC structure was not observed in previous experiment . To further check whether the hybrid functional could affect describing the excited‐state cases, herein, we also adopt PBE and Cam‐B3LYP functionals to construct the potential energy curves for DHPBC system in both S 0 and S 1 states.…”

Section: Resultsmentioning

confidence: 99%

“…2‐(3,5‐dichloro‐2‐hydroxy‐phenyl)‐benzooxazole‐5‐carboxylicacid (DHPBC), a novel ESIPT chromophore has been designed and synthesized recently . A new protein binding pocket is also designed to discriminate selectively between the two channels of the fluorescence available to the DHPBC fluorophore.…”

Section: Introductionmentioning

confidence: 99%

“…A new protein binding pocket is also designed to discriminate selectively between the two channels of the fluorescence available to the DHPBC fluorophore. And it has been demonstrated that the specific interactions between protein and DHPBC fluorophore are essential to realize strong ratiometric differences between the two possible wavelengths of fluorescence in ESIPT process . It cannot be denied that DHPBC shows abundant photochemical and photobiological properties in previous experimental work.…”

Section: Introductionmentioning

confidence: 99%

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Investigation on the excited state intramolecular proton transfer process for the novel 2‐(3,5‐dichloro‐2‐hydroxy‐phenyl)‐benzooxazole‐5‐carboxylicacid system

Gao

Yang

Zhang

et al. 2019

J of Physical Organic Chem

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In view of the importance of excited state hydrogen bonding interactions and excited state proton transfer (ESPT) dynamical behaviors, in this work, we theoretically explore the excited state process for a novel 2‐(3,5‐dichloro‐2‐hydroxy‐phenyl)‐benzooxazole‐5‐carboxylicacid (DHPBC) system. On the basis of discrete Fourier transform (DFT) and time‐dependent density functional theory (TDDFT) methods, we reappear previous experimental reports with checking the reasonability of our theoretical level. We calculate and compare the primary geometrical parameters and hydrogen bonding energies around hydrogen bonding moieties, which reveals that the intramolecular hydrogen bond OH···N of DHPBC is enhanced in the S1 state. The increased electron densities around N atom contribute to attracting proton of hydroxyl upon the photoexcitation, which plays important roles in strengthening hydrogen bond and in facilitating excited state intra‐ or intermolecular proton transfer (ESIPT) process. Via constructing potential energy curves along with the ESIPT path, we verify that the ESIPT process of DHPBC system is ultrafast because of the low potential energy barrier. That should be the reason why the normal emission of DHPBC cannot be detected in previous experiment. This work not only clarifies the excited state hydrogen bonding interactions and fills the vacancy of specific ESIPT mechanism for DHPBC system in experiment, but also explains the fluorescence quenching phenomenon.

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Investigation on the excited state intramolecular proton transfer process for the novel 2‐(3,5‐dichloro‐2‐hydroxy‐phenyl)‐benzooxazole‐5‐carboxylicacid system

Gao

Yang

Zhang

et al. 2019

J of Physical Organic Chem

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A density functional theory‐time‐dependent density functional theory investigation of photo‐induced hydrogen bond and proton transfer for 2‐(3,5‐dichloro‐2,6‐dihydroxy‐phenyl)‐benzoxazole‐6‐carboxylicacid

Wang

Zhao

et al. 2019

J Chinese Chemical Soc

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Given the paramount importance of excited-state relaxation in the photochemical process, excited-state hydrogen bonding interactions and excited-state intramolecular proton transfer (ESIPT) are always hot topics. In this work, we theoretically explore the excited-state dynamical behaviors for a novel 2-(3,5-dichloro-2,6-dihydroxy-phenyl)-benzoxazole-6-carboxylicacid (DDPBC) system. As two intramolecular hydrogen bonds (O1 H2Á Á ÁN3 and O4 H5Á Á ÁO6) exist in the DDPBC structure, we first check if the double proton transfer form cannot be formed in the S1 state. Then, we explore the changes of geometrical parameters involved in hydrogen bonds, based on which we confirm that the dual intramolecular hydrogen bonds are strengthened on photo-excitation. The O1 H2Á Á ÁN3 hydrogen bond particularly plays a more important role in excited state. When it comes to the photo-induced excitation, we find charge transfer and electronic density redistribution around O1 H2 and N3 atom moieties. We verify the ESIPT tendency arising from the O1 H2Á Á ÁN3 hydrogen bond. In the analysis of the potential energy curves, along with O1 H2Á Á ÁN3 and O4 H5Á Á ÁO6, we demonstrate that the ESIPT reaction should occur along with O1 H2Á Á ÁN3 rather than O4 H5Á Á ÁO6. This work not only clarifies the specific ESIPT mechanism for DDPBC system but also paves the way for further novel applications based on DDPBC structure in the future. K E Y W O R D Sexcited-state intramolecular proton transfer, frontier molecular orbitals, intramolecular hydrogen bond, potential energy curves

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Theoretical investigation into the deciphering effects of atomic electronegativity on 2‐hydroxy‐phenyl‐tafamidis: A time‐dependent density functional theory study

Zhang

Yuan

2022

J Chinese Chemical Soc

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In light of the potential probe applications of 2‐hydroxy‐phenyl‐tafamidis (2HPT) and its derivatives with different atomic electronegativity (2HPT‐O, 2HPT‐S, and 2HPT‐Se), the mechanisms of excited state intramolecular proton transfer (ESIPT) of 2HPT derivatives have been investigated in this work. Via probing into the geometric parameters of hydrogen bond O‐H···N, infrared vibrational spectroscopy, and bond critical point values, we can confirm that hydrogen bonding is enhanced in the first excited state (S1). It is worth mentioning that the enhancement of hydrogen bonding in the S1 state by low atomic electronegativity 2HPT‐Se is particularly important. In light‐induced excitation, by comparing the changed behaviors of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) orbitals, it could be found that photo‐induced charge transfer happens in excited molecules, and charge redistribution facilitates ESIPT reaction. Particularly, the low atomic electronegativity could promote the ESIPT process for 2HPT system. In order to clarify the detailed ESIPT mechanism, we construct the potential energy curves, search for the transition state form, and determine the ESIPT mechanism for 2HPT fluorophores. In this work, we not only elucidated the excited state behavior of 2HPT systems but also proposed a novel mechanism for regulating ESIPT by atomic electronegativity.

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A designed protein binding-pocket to control excited-state intramolecular proton transfer fluorescence

Cited by 13 publications

References 35 publications

Investigation on the excited state intramolecular proton transfer process for the novel 2‐(3,5‐dichloro‐2‐hydroxy‐phenyl)‐benzooxazole‐5‐carboxylicacid system

Investigation on the excited state intramolecular proton transfer process for the novel 2‐(3,5‐dichloro‐2‐hydroxy‐phenyl)‐benzooxazole‐5‐carboxylicacid system

A density functional theory‐time‐dependent density functional theory investigation of photo‐induced hydrogen bond and proton transfer for 2‐(3,5‐dichloro‐2,6‐dihydroxy‐phenyl)‐benzoxazole‐6‐carboxylicacid

Theoretical investigation into the deciphering effects of atomic electronegativity on 2‐hydroxy‐phenyl‐tafamidis: A time‐dependent density functional theory study

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