Photoactivatable BODIPYs Designed to Monitor the Dynamics of Supramolecular Nanocarriers

Yang Zhang, Subramani Swaminathan, Sicheng Tang, Jaume Garcia-Amorós, Marcia Boulina, Burjor Captain, James Baker, Francisco Raymo

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Self-assembling nanoparticles of amphiphilic polymers can transport hydrophobic molecules across hydrophilic media and, as a result, can be valuable delivery vehicles for a diversity of biomedical applications. Strategies to monitor their dynamics noninvasively and in real time are, therefore, essential to investigate their translocation within soft matrices and, possibly, rationalize the mechanisms responsible for their diffusion in biological media. In this context, we designed molecular guests with photoactivatable fluorescence for these supramolecular hosts and demonstrated that the activation of the fluorescent cargo, under optical control, permits the tracking of the nanocarrier translocation across hydrogel matrices with the sequential acquisition of fluorescence images. In addition, the mild illumination conditions sufficient to implement these operating principles permit fluorescence activation within developing Drosophila melanogaster embryos and enable the monitoring of the loaded nanocarriers for long periods of time with no cytotoxic effects and no noticeable influence on embryogenesis. These photoresponsive compounds combine a borondipyrromethene (BODIPY) chromophore and a photocleavable oxazine within their covalent skeleton. Under illumination at an appropriate activation wavelength, the oxazine ring cleaves irreversibly to bring the adjacent BODIPY fragment in conjugation with an indole heterocycle. This structural transformation shifts bathochromically the BODIPY absorption and permits the selective excitation of the photochemical product with concomitant fluorescence. In fact, these operating principles allow the photoactivation of BODIPY fluorescence with large brightness and infinite contrast. Thus, our innovative structural design translates into activatable fluorophores with excellent photochemical and photophysical properties as well as provides access to a general mechanism for the real-time tracking of supramolecular nanocarriers in hydrophilic matrices. (Chemical Presented).

Original languageEnglish (US)
Pages (from-to)4709-4719
Number of pages11
JournalJournal of the American Chemical Society
Volume137
Issue number14
DOIs
StatePublished - Apr 15 2015

Fingerprint

Fluorescence
Oxazines
Chemical activation
Lighting
Fluorophores
Hydrogel
Chromophores
Drosophila melanogaster
Structural design
Skeleton
Hydrogels
Nanoparticles
Embryonic Development
Luminance
Polymers
Embryonic Structures
4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
Wavelength
Molecules
Monitoring

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Photoactivatable BODIPYs Designed to Monitor the Dynamics of Supramolecular Nanocarriers. / Zhang, Yang; Swaminathan, Subramani; Tang, Sicheng; Garcia-Amorós, Jaume; Boulina, Marcia; Captain, Burjor; Baker, James; Raymo, Francisco.

In: Journal of the American Chemical Society, Vol. 137, No. 14, 15.04.2015, p. 4709-4719.

Research output: Contribution to journalArticle

Zhang, Yang ; Swaminathan, Subramani ; Tang, Sicheng ; Garcia-Amorós, Jaume ; Boulina, Marcia ; Captain, Burjor ; Baker, James ; Raymo, Francisco. / Photoactivatable BODIPYs Designed to Monitor the Dynamics of Supramolecular Nanocarriers. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 14. pp. 4709-4719.
@article{6af3326c3c074358aabbbcb75f56ce39,
title = "Photoactivatable BODIPYs Designed to Monitor the Dynamics of Supramolecular Nanocarriers",
abstract = "Self-assembling nanoparticles of amphiphilic polymers can transport hydrophobic molecules across hydrophilic media and, as a result, can be valuable delivery vehicles for a diversity of biomedical applications. Strategies to monitor their dynamics noninvasively and in real time are, therefore, essential to investigate their translocation within soft matrices and, possibly, rationalize the mechanisms responsible for their diffusion in biological media. In this context, we designed molecular guests with photoactivatable fluorescence for these supramolecular hosts and demonstrated that the activation of the fluorescent cargo, under optical control, permits the tracking of the nanocarrier translocation across hydrogel matrices with the sequential acquisition of fluorescence images. In addition, the mild illumination conditions sufficient to implement these operating principles permit fluorescence activation within developing Drosophila melanogaster embryos and enable the monitoring of the loaded nanocarriers for long periods of time with no cytotoxic effects and no noticeable influence on embryogenesis. These photoresponsive compounds combine a borondipyrromethene (BODIPY) chromophore and a photocleavable oxazine within their covalent skeleton. Under illumination at an appropriate activation wavelength, the oxazine ring cleaves irreversibly to bring the adjacent BODIPY fragment in conjugation with an indole heterocycle. This structural transformation shifts bathochromically the BODIPY absorption and permits the selective excitation of the photochemical product with concomitant fluorescence. In fact, these operating principles allow the photoactivation of BODIPY fluorescence with large brightness and infinite contrast. Thus, our innovative structural design translates into activatable fluorophores with excellent photochemical and photophysical properties as well as provides access to a general mechanism for the real-time tracking of supramolecular nanocarriers in hydrophilic matrices. (Chemical Presented).",
author = "Yang Zhang and Subramani Swaminathan and Sicheng Tang and Jaume Garcia-Amor{\'o}s and Marcia Boulina and Burjor Captain and James Baker and Francisco Raymo",
year = "2015",
month = "4",
day = "15",
doi = "10.1021/ja5125308",
language = "English (US)",
volume = "137",
pages = "4709--4719",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Photoactivatable BODIPYs Designed to Monitor the Dynamics of Supramolecular Nanocarriers

AU - Zhang, Yang

AU - Swaminathan, Subramani

AU - Tang, Sicheng

AU - Garcia-Amorós, Jaume

AU - Boulina, Marcia

AU - Captain, Burjor

AU - Baker, James

AU - Raymo, Francisco

PY - 2015/4/15

Y1 - 2015/4/15

N2 - Self-assembling nanoparticles of amphiphilic polymers can transport hydrophobic molecules across hydrophilic media and, as a result, can be valuable delivery vehicles for a diversity of biomedical applications. Strategies to monitor their dynamics noninvasively and in real time are, therefore, essential to investigate their translocation within soft matrices and, possibly, rationalize the mechanisms responsible for their diffusion in biological media. In this context, we designed molecular guests with photoactivatable fluorescence for these supramolecular hosts and demonstrated that the activation of the fluorescent cargo, under optical control, permits the tracking of the nanocarrier translocation across hydrogel matrices with the sequential acquisition of fluorescence images. In addition, the mild illumination conditions sufficient to implement these operating principles permit fluorescence activation within developing Drosophila melanogaster embryos and enable the monitoring of the loaded nanocarriers for long periods of time with no cytotoxic effects and no noticeable influence on embryogenesis. These photoresponsive compounds combine a borondipyrromethene (BODIPY) chromophore and a photocleavable oxazine within their covalent skeleton. Under illumination at an appropriate activation wavelength, the oxazine ring cleaves irreversibly to bring the adjacent BODIPY fragment in conjugation with an indole heterocycle. This structural transformation shifts bathochromically the BODIPY absorption and permits the selective excitation of the photochemical product with concomitant fluorescence. In fact, these operating principles allow the photoactivation of BODIPY fluorescence with large brightness and infinite contrast. Thus, our innovative structural design translates into activatable fluorophores with excellent photochemical and photophysical properties as well as provides access to a general mechanism for the real-time tracking of supramolecular nanocarriers in hydrophilic matrices. (Chemical Presented).

AB - Self-assembling nanoparticles of amphiphilic polymers can transport hydrophobic molecules across hydrophilic media and, as a result, can be valuable delivery vehicles for a diversity of biomedical applications. Strategies to monitor their dynamics noninvasively and in real time are, therefore, essential to investigate their translocation within soft matrices and, possibly, rationalize the mechanisms responsible for their diffusion in biological media. In this context, we designed molecular guests with photoactivatable fluorescence for these supramolecular hosts and demonstrated that the activation of the fluorescent cargo, under optical control, permits the tracking of the nanocarrier translocation across hydrogel matrices with the sequential acquisition of fluorescence images. In addition, the mild illumination conditions sufficient to implement these operating principles permit fluorescence activation within developing Drosophila melanogaster embryos and enable the monitoring of the loaded nanocarriers for long periods of time with no cytotoxic effects and no noticeable influence on embryogenesis. These photoresponsive compounds combine a borondipyrromethene (BODIPY) chromophore and a photocleavable oxazine within their covalent skeleton. Under illumination at an appropriate activation wavelength, the oxazine ring cleaves irreversibly to bring the adjacent BODIPY fragment in conjugation with an indole heterocycle. This structural transformation shifts bathochromically the BODIPY absorption and permits the selective excitation of the photochemical product with concomitant fluorescence. In fact, these operating principles allow the photoactivation of BODIPY fluorescence with large brightness and infinite contrast. Thus, our innovative structural design translates into activatable fluorophores with excellent photochemical and photophysical properties as well as provides access to a general mechanism for the real-time tracking of supramolecular nanocarriers in hydrophilic matrices. (Chemical Presented).

UR - http://www.scopus.com/inward/record.url?scp=84927928766&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84927928766&partnerID=8YFLogxK

U2 - 10.1021/ja5125308

DO - 10.1021/ja5125308

M3 - Article

C2 - 25794143

AN - SCOPUS:84927928766

VL - 137

SP - 4709

EP - 4719

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 14

ER -