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Tuning the Baird aromatic triplet-state energy of cyclooctatetraene to maximize the self-healing mechanism in organic fluorophores.

ABSTRACT: Bright, photostable, and nontoxic fluorescent contrast agents are critical for biological imaging. "Self-healing" dyes, in which triplet states are intramolecularly quenched, enable fluorescence imaging by increasing fluorophore brightness and longevity, while simultaneously reducing the generation of reactive oxygen species that promote phototoxicity. Here, we systematically examine the self-healing mechanism in cyanine-class organic fluorophores spanning the visible spectrum. We show that the Baird aromatic triplet-state energy of cyclooctatetraene can be physically altered to achieve order of magnitude enhancements in fluorophore brightness and signal-to-noise ratio in both the presence and absence of oxygen. We leverage these advances to achieve direct measurements of large-scale conformational dynamics within single molecules at submillisecond resolution using wide-field illumination and camera-based detection methods. These findings demonstrate the capacity to image functionally relevant conformational processes in biological systems in the kilohertz regime at physiological oxygen concentrations and shed important light on the multivariate parameters critical to self-healing organic fluorophore design.

SUBMITTER: Pati AK

PROVIDER: S-EPMC7533661 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Tuning the Baird aromatic triplet-state energy of cyclooctatetraene to maximize the self-healing mechanism in organic fluorophores.

Pati Avik K AK El Bakouri Ouissam O Jockusch Steffen S Zhou Zhou Z Altman Roger B RB Fitzgerald Gabriel A GA Asher Wesley B WB Terry Daniel S DS Borgia Alessandro A Holsey Michael D MD Batchelder Jake E JE Abeywickrama Chathura C Huddle Brandt B Rufa Dominic D Javitch Jonathan A JA Ottosson Henrik H Blanchard Scott C SC

Proceedings of the National Academy of Sciences of the United States of America 20200910 39

Bright, photostable, and nontoxic fluorescent contrast agents are critical for biological imaging. "Self-healing" dyes, in which triplet states are intramolecularly quenched, enable fluorescence imaging by increasing fluorophore brightness and longevity, while simultaneously reducing the generation of reactive oxygen species that promote phototoxicity. Here, we systematically examine the self-healing mechanism in cyanine-class organic fluorophores spanning the visible spectrum. We show that the ...[more]

PMID: 32913060

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Project description:The aromaticity of cyclic 4nπ-electron molecules in their first ππ* triplet state (T1), labeled Baird aromaticity, has gained growing attention in the past decade. Here we explore computationally the limitations of T1 state Baird aromaticity in macrocyclic compounds, [n]CM's, which are cyclic oligomers of four different monocycles (M = p-phenylene (PP), 2,5-linked furan (FU), 1,4-linked cyclohexa-1,3-diene (CHD), and 1,4-linked cyclopentadiene (CPD)). We strive for conclusions that are general for various DFT functionals, although for macrocycles with up to 20 π-electrons in their main conjugation paths we find that for their T1 states single-point energies at both canonical UCCSD(T) and approximative DLPNO-UCCSD(T) levels are lowest when based on UB3LYP over UM06-2X and UCAM-B3LYP geometries. This finding is in contrast to what has earlier been observed for the electronic ground state of expanded porphyrins. Yet, irrespective of functional, macrocycles with 2,5-linked furans ([n]CFU's) retain Baird aromaticity until larger n than those composed of the other three monocycles. Also, when based on geometric, electronic and energetic aspects of aromaticity, a 3[n]CFU with a specific n is more strongly Baird-aromatic than the analogous 3[n]CPP while the magnetic indices tell the opposite. To construct large T1 state Baird-aromatic [n]CM's, the design should be such that the T1 state Baird aromaticity of the macrocyclic perimeter dominates over a situation with local closed-shell Hückel aromaticity of one or a few monocycles and semilocalized triplet diradical character. Monomers with lower Hückel aromaticity in S0 than benzene (e.g., furan) that do not impose steric congestion are preferred. Structural confinement imposed by, e.g., methylene bridges is also an approach to larger Baird-aromatic macrocycles. Finally, by using the Zilberg-Haas description of T1 state aromaticity, we reveal the analogy to the Hückel aromaticity of the corresponding closed-shell dications yet observe stronger Hückel aromaticity in the macrocyclic dications than Baird aromaticity in the T1 states of the neutral macrocycles.

Dataset Information

Tuning the Baird aromatic triplet-state energy of cyclooctatetraene to maximize the self-healing mechanism in organic fluorophores.

Publications

Tuning the Baird aromatic triplet-state energy of cyclooctatetraene to maximize the self-healing mechanism in organic fluorophores.

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