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Protein Dynamics in Living Cells01:19

Protein Dynamics in Living Cells

Different fluorescence-based techniques are used to study the protein dynamics in living cells. These techniques include FRAP, FRET, and PET.
Fluorescent recovery after photobleaching (FRAP) is a fluorescent-protein-based detection technique used to quantify protein movement rates within the cell. This method exposes a small portion of the cell to an intense laser beam. The laser beam causes permanent photobleaching of the fluorophore-tagged proteins in the exposed region. As the bleached...

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Light-driven radical catch-and-release with BODIPY photocages.

Anna Poryvai1,2, Anna Vasiļevska2,3, Karolína Bangievská2

  • 1École Polytechnique Fédérale de Lausanne, SB ISIC SCI-SB-SG Station 6 CH-1015 Lausanne Switzerland anna.poryvai@epfl.ch.

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Researchers explored how light triggers chemical reactions in photocages, discovering that high fluorescence can lead to controlled radical release. This breakthrough enables new applications in polymerization and precise payload delivery.

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Area of Science:

  • Photochemistry and Materials Science
  • Chemical Biology

Background:

  • Photocages offer spatiotemporal control via light-induced payload release, typically through heterolytic processes.
  • Unintended radical generation via homolytic pathways can cause off-target effects in photocage applications.
  • Controlled radical photorelease remains underexplored due to unknown governing molecular factors.

Purpose of the Study:

  • To investigate the influence of photophysics and payload identity on heterolytic versus homolytic reactivity in BODIPY photocages.
  • To establish a structure-reactivity framework for predictable light-controlled radical generation.

Main Methods:

  • Investigated BODIPY photocages with varying substituents to analyze photophysical properties and photorelease pathways.
  • Quantified radical photorelease quantum yields and compared them with heterolytic uncaging.
  • Demonstrated Type I photoinitiation of RAFT polymerization using the developed radical photorelease system.

Main Results:

  • High fluorescence quantum yields in BODIPY photocages correlate with efficient homolytic cleavage, enabling reversible radical catch-and-release.
  • Introduction of iodide or boron-methyl substituents suppresses radical release by promoting intersystem crossing.
  • Achieved a record 0.5% photorelease quantum yield for green-light-driven radical generation, exceeding heterolytic carboxylate uncaging.

Conclusions:

  • Established a structure-reactivity framework for predictable light-controlled radical generation from photocages.
  • Demonstrated suppression of unwanted radical effects and enabled controlled radical photorelease.
  • Opened new avenues for late-stage photochemical payload installation and radical-based applications like polymerization.