Bodipy Derivatives as Triplet Photosensitizers and the Related Intersystem Crossing Mechanisms

Chen, Kepeng; Yu, Dong Sik; Zhao, Xiaoyu; Imran, Muhammad; Tang, Geliang; Zhao, Jianzhang; Liu, Qingyun

doi:10.3389/fchem.2019.00821

Cited by 84 publications

(70 citation statements)

References 119 publications

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“…The measured autocorrelation curve is best fitted to a diffusion model with one triplet component (Eq. 5 , with no quenching terms), and the triplet lifetime obtained (τ t = 3 ± 1 μs) is in agreement with previous reports (2–8 μs) 40 . For the global analysis of FCS data of the receptor under different ligand conditions, the BODIPY-FL triplet lifetime was used as a shared fitting parameter (Eq.…”

Section: Resultssupporting

confidence: 93%

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Ligand modulation of the conformational dynamics of the A2A adenosine receptor revealed by single-molecule fluorescence

Fernandes

Neale

Gomes

et al. 2021

Sci Rep

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G protein-coupled receptors (GPCRs) are the largest class of transmembrane proteins, making them an important target for therapeutics. Activation of these receptors is modulated by orthosteric ligands, which stabilize one or several states within a complex conformational ensemble. The intra- and inter-state dynamics, however, is not well documented. Here, we used single-molecule fluorescence to measure ligand-modulated conformational dynamics of the adenosine A2A receptor (A2AR) on nanosecond to millisecond timescales. Experiments were performed on detergent-purified A2R in either the ligand-free (apo) state, or when bound to an inverse, partial or full agonist ligand. Single-molecule Förster resonance energy transfer (smFRET) was performed on detergent-solubilized A2AR to resolve active and inactive states via the separation between transmembrane (TM) helices 4 and 6. The ligand-dependent changes of the smFRET distributions are consistent with conformational selection and with inter-state exchange lifetimes ≥ 3 ms. Local conformational dynamics around residue 2296.31 on TM6 was measured using fluorescence correlation spectroscopy (FCS), which captures dynamic quenching due to photoinduced electron transfer (PET) between a covalently-attached dye and proximal aromatic residues. Global analysis of PET-FCS data revealed fast (150–350 ns), intermediate (50–60 μs) and slow (200–300 μs) conformational dynamics in A2AR, with lifetimes and amplitudes modulated by ligands and a G-protein mimetic (mini-Gs). Most notably, the agonist binding and the coupling to mini-Gs accelerates and increases the relative contribution of the sub-microsecond phase. Molecular dynamics simulations identified three tyrosine residues (Y112, Y2887.53, and Y2907.55) as being responsible for the dynamic quenching observed by PET-FCS and revealed associated helical motions around residue 2296.31 on TM6. This study provides a quantitative description of conformational dynamics in A2AR and supports the idea that ligands bias not only GPCR conformations but also the dynamics within and between distinct conformational states of the receptor.

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Section: Resultssupporting

confidence: 93%

“…1 , see above). In particular, the sub-millisecond protein dynamics captured by PET-FCS could be associated to the on/off behavior of the ionic-lock for the salt-bridge between R102 3.50 of TM3 and E228 6.30 of TM6 4 , 40 .…”

Section: Resultsmentioning

confidence: 99%

Ligand modulation of the conformational dynamics of the A2A adenosine receptor revealed by single-molecule fluorescence

Fernandes

Neale

Gomes

et al. 2021

Sci Rep

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“…This is due to the versatile photophysical properties, high chemical stability, as well as easy and versatile chemical modification of BODIPY. [30,31] Consequently, BODIPY derivatives have been employed in light-driven hydrogen evolution, [32] CO 2 reduction, [33] and water oxidation. [34] Taking inspiration from these studies, we here report a CLICK-chemistry based system which enables the covalent linkage of an azide-functionalized Anderson type polyoxometalate 1 with two alkyne-functionalized BODIPY 2 to give a covalent BODIPY-Anderson-dyad 3.…”

Section: Introductionmentioning

confidence: 99%

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

Çetindere

Clausing

Anjass

et al. 2021

Chemistry A European J

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The covalent attachment of molecular photosensitizers (PS) to polyoxometalates (POMs) opens new pathways to PS‐POM dyads for light‐driven charge‐transfer and charge‐storage. Here, we report a synthetic route for the covalent linkage of BODIPY‐dyes to Anderson‐type polyoxomolybdates by using CLICK chemistry (i. e. copper‐catalyzed azide‐alkyne cycloaddition, CuAAC). Photophysical properties of the dyad were investigated by combined experimental and theoretical methods and highlight the role of both sub‐components for the charge‐separation properties. The study demonstrates how CLICK chemistry can be used for the versatile linkage of organic functional units to molecular metal oxide clusters.

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“…The fast process contributes more in DMF or DMSO than it does in CH 2 Cl 2 or THF ( Figure 5). These observations can be explained by proposing that the singlet emission only occurs from selective environments on the polymer, which do not facilitate intersystem crossing (ISC) to the triplet surface (Chen et al, 2019). The proportion of the excited BODIPY centres, which undergo singlet emission, is strongly affected by the interaction between the polymer and the solvent.…”

Section: Fluorescence Lifetime Analysis Using Tcspcmentioning

confidence: 99%

A Time-Resolved Spectroscopic Investigation of a Novel BODIPY Copolymer and Its Potential Use as a Photosensitiser for Hydrogen Evolution

et al. 2020

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A novel 4,4-difuoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) copolymer with diethynylbenzene has been synthesised, and its ability to act as a photosensitiser for the photocatalytic generation of hydrogen was investigated by time-resolved spectroscopic techniques spanning the ps-to ns-timescales. Both transient absorption and time-resolved infrared spectroscopy were used to probe the excited state dynamics of this photosensitising unit in a variety of solvents. These studies indicated how environmental factors can influence the photophysics of the BODIPY polymer. A homogeneous photocatalytic hydrogen evolution system has been developed using the BODIPY copolymer and cobaloxime which provides hydrogen evolution rates of 319 µmol h −1 g −1 after 24 h of visible irradiation.

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Bodipy Derivatives as Triplet Photosensitizers and the Related Intersystem Crossing Mechanisms

Cited by 84 publications

References 119 publications

Ligand modulation of the conformational dynamics of the A2A adenosine receptor revealed by single-molecule fluorescence

Ligand modulation of the conformational dynamics of the A2A adenosine receptor revealed by single-molecule fluorescence

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

A Time-Resolved Spectroscopic Investigation of a Novel BODIPY Copolymer and Its Potential Use as a Photosensitiser for Hydrogen Evolution

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