BODIPY‐Tetrazine Multichromophoric Derivatives

Dumas‐Verdes, Cécile; Miomandre, Fabien; Lépicier, E.; Galangau, Olivier; Vu, Thanh Tung; Clavier, Gilles; Méallet‐Renault, Rachel; Audebert, Pierre

doi:10.1002/ejoc.200900874

Cited by 66 publications

(55 citation statements)

References 51 publications

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“…[1d, 2,12] mono-and disubstitution of 3 can occur. Disubstitution is usually more difficult than monosubstitution, and it was necessary to strengthen the conditions by heating or by using a sealed tube.…”

Section: Synthesismentioning

confidence: 99%

“…[2,4] Indeed, instead of an on-off two-state system, it should be possible to prepare dyads that display off-to-on fluorescent switching upon redox activation. Such dyads should present complementary properties to 3-chloro-6-methoxytetrazine.…”

Section: Introductionmentioning

confidence: 99%

“…[2] These molecules present different photophysical properties according to the redox state of the molecule (neutral, oxidized or reduced). For example, interplay between fluorescence and redox characteristics in the case of 3-chloro-6-methoxytetrazine could lead to a reversible switching of fluorescence (also called electrofluorochromism).…”

Section: Introductionmentioning

confidence: 99%

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Design of New Tetrazine–Triphenylamine Bichromophores – Fluorescent Switching by Chemical Oxidation

et al. 2012

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Original new fluorescent and electroactive compounds have been prepared, which feature two different fluorescent groups linked through an oxygen atom spacer. We describe here the synthesis, photophysical and electrochemical properties and their interplay, and our theoretical calculations. These molecules are composed of two fluorophores, an electron‐rich triphenylamine unit and an electron‐poor tetrazine unit. Although the bichromophores are not fluorescent in the neutral state due to a photoinduced electron transfer from the triphenylamine unit to the tetrazine unit, one can restore the fluorescence by oxydation of the triphenylamine moiety. Thus, a redox‐fluorescent switch has been realized.

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Section: Synthesismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Design of New Tetrazine–Triphenylamine Bichromophores – Fluorescent Switching by Chemical Oxidation

et al. 2012

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“…Distilled water adjusted with aqueous sodium hydroxide solution (1 M) to a pH comprised between 12 and 12.5 was used for nanoparticles synthesis. The BODIPY phenol (Scheme S1, 1), [16] molecular RAFT agent S-1-dodecyl-S 0 -(a, a 0 -dimethyl-a 00 -acetic acid) trithiocarbonate (TTCA) [17] and the TTCA-based macroRAFT agents PEO-TTC-C 12 (M n ¼ 2 420 g Á mol À1 , end-functionality >95%) [18] were synthesized as described elsewhere. Synthetic schemes are available in the Supporting Information.…”

Section: Introductionmentioning

confidence: 99%

One‐Pot Synthesis of Pegylated Fluorescent Nanoparticles by RAFT Miniemulsion Polymerization Using a Phase Inversion Process

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Rieger

Méallet‐Renault

et al. 2011

Macromol. Rapid Commun.

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Water-soluble and fluorescent core-shell nanoparticles (FNP) are synthesized in a miniemulsion reversible addition-fragmentation transfer (RAFT) polymerization and are shown to respond to pH. The particles are obtained from a hydrophilic PEO-b-PAA macromolecular RAFT agent which is block-extended with styrene and a fluorescent BODIPY monomer. A miniemulsion is then formed with the residual hydrophobic monomers. After completion of the polymerization, FNP of ≈ 60 nm in diameter are obtained. The fluorescence of the BODIPY dye in the particles is found to remain (0.2 quantum yield). The particles can be precipitated in acidic pH and redispersed upon addition of base without loss of their integrity or noticeable rearrangement.

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“…Recent work has demonstrated that tetrazines are capable of significantly quenching several bright fluorescent probes, potentially through a resonant energy transfer mechanism. [21] These probes show significant fluorescent "turn-on" after reaction with dienophiles, can be synthesized from commercially available reactive precursors, and use bright, conveniently excited fluorophores that are commonly used in cellular imaging, such as boron dipyrromethane (BODIPY) and Oregon Green. The combination of recently discovered high-quality fluorogenic tetrazine probes, such as tetrazine-BODIPY FL, with small dienophile tags would advance bioorthogonal live-cell imaging.…”

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confidence: 99%

Live‐Cell Imaging of Cyclopropene Tags with Fluorogenic Tetrazine Cycloadditions

et al. 2012

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There is growing interest in the use of inverse Diels-Alder tetrazine cycloadditions as rapid catalyst-free bioorthogonal reactions. [1][2][3] Fluorogenic tetrazines that increase in fluorescence after reaction with dienophiles are particularly useful for live-cell imaging applications. [4] Fluorogenic tetrazines have been recently used for live-cell imaging of small molecules, biomolecules tagged enzymatically with dienophiles, and proteins modified by reactive unnatural amino acids. [4,5] Although fluorogenic tetrazine probes hold great potential for intracellular imaging of small molecules, previous approaches are limited by requiring a large strained dienophile, such as trans-cyclooctene, cyclooctyne, or norbornene. [1,6] This situation is in contrast to Staudinger ligations or strain-promoted azide-cycloalkyne cycloadditions that utilize a small azide functional group. [7,8] This requirement has limited the use of tetrazine reactions in methods that require tags with minimal steric impact or nominal effect on the partition ratio. [2] The development of smaller dienophile partners capable of reacting rapidly with tetrazines would therefore represent a major advance. However, it has been unclear whether small dienophiles could be developed that react rapidly with tetrazines while maintaining their stability. Herein, we demonstrate the applicability of methylcyclopropene tags as dienophiles for reaction with fluorogenic tetrazines. Through systematic synthetic modifications we have optimized the stability, size, and reactivity of the cyclopropene scaffold. We have developed methylcyclopropene derivatives that react rapidly with tetrazines while retaining their aqueous stability and small size. These cyclopropene handles elicit fluorescent responses from quenched tetrazine dyes and are suitable for cellular imaging applications, which we demonstrate by imaging cyclopropene phospholipids distributed in live human breast cancer cells.The use of cyclopropenes offers a possible approach to smaller dienophile partners for tetrazine cycloadditions. It has long been known that cyclopropenes react rapidly with tetrazines to form stable diazanorcaradienes (Figure 1a). [9] In seminal work, Sauer and coworkers demonstrated that unsubstituted cyclopropene reacts with dimethyl 1,2,4,5-** We greatly acknowledge Ralph Mazitschek, Michael Hardy, and Carlos Guerrero for helpful discussions.

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BODIPY‐Tetrazine Multichromophoric Derivatives

Cited by 66 publications

References 51 publications

Design of New Tetrazine–Triphenylamine Bichromophores – Fluorescent Switching by Chemical Oxidation

Design of New Tetrazine–Triphenylamine Bichromophores – Fluorescent Switching by Chemical Oxidation

One‐Pot Synthesis of Pegylated Fluorescent Nanoparticles by RAFT Miniemulsion Polymerization Using a Phase Inversion Process

Live‐Cell Imaging of Cyclopropene Tags with Fluorogenic Tetrazine Cycloadditions

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