Fast and stable photochromic oxazines for fluorescence switching

Erhan Deniz, Massimiliano Tomasulo, Janet Cusido, Salvatore Sortino, Francisco Raymo

Research output: Contribution to journalArticle

55 Citations (Scopus)

Abstract

The stringent limitations imposed by diffraction on the spatial resolution of fluorescence microscopes demand the identification of viable strategies to switch fluorescence under optical control. In this context, the photoinduced and reversible transformations of photochromic compounds are particularly valuable. In fact, these molecules can be engineered to regulate the emission intensities of complementary fluorophores in response to optical stimulations. On the basis of this general design logic, we assembled a functional molecular construct consisting of a borondipyrromethene fluorophore and a nitrospiropyran photochrome and demonstrated that the emission of the former can be modulated with the interconversion of the latter. This fluorophore-photochrome dyad, however, has a slow switching speed and poor fatigue resistance. To improve both parameters, we developed a new family of photochromic switches based on the photoinduced opening and thermal closing of an oxazine ring. These compounds switch back and forth between ring-closed and -open isomers on nanosecond-microsecond timescales and tolerate thousands of switching cycles with no sign of degradation. In addition, the attachment of appropriate chromophoric fragments to their switchable oxazine ring can be exploited to either deactivate or activate fluorescence reversibly in response to illumination with a pair of exciting beams. Specifically, we assembled three dyads, each based on either a borondipyrromethene or a coumarin fluorophore and an oxazine photochrome, and modulated their fluorescence in a few microseconds with outstanding fatigue resistance. The unique photochemical and photophysical properties of our fluorophore-photochrome dyads can facilitate the development of switchable fluorophores for superresolution imaging and, ultimately, provide valuable molecular probes for the visualization of biological samples on the nanometer level.

Original languageEnglish
Pages (from-to)11773-11783
Number of pages11
JournalLangmuir
Volume27
Issue number19
DOIs
StatePublished - Oct 4 2011

Fingerprint

Oxazines
Fluorophores
Fluorescence
fluorescence
rings
switches
logic design
Switches
optical control
closing
stimulation
Fatigue of materials
attachment
Molecular Probes
Logic design
isomers
Plant shutdowns
spatial resolution
illumination
microscopes

ASJC Scopus subject areas

  • Electrochemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Materials Science(all)
  • Spectroscopy

Cite this

Deniz, E., Tomasulo, M., Cusido, J., Sortino, S., & Raymo, F. (2011). Fast and stable photochromic oxazines for fluorescence switching. Langmuir, 27(19), 11773-11783. https://doi.org/10.1021/la201062h

Fast and stable photochromic oxazines for fluorescence switching. / Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Sortino, Salvatore; Raymo, Francisco.

In: Langmuir, Vol. 27, No. 19, 04.10.2011, p. 11773-11783.

Research output: Contribution to journalArticle

Deniz, E, Tomasulo, M, Cusido, J, Sortino, S & Raymo, F 2011, 'Fast and stable photochromic oxazines for fluorescence switching', Langmuir, vol. 27, no. 19, pp. 11773-11783. https://doi.org/10.1021/la201062h
Deniz E, Tomasulo M, Cusido J, Sortino S, Raymo F. Fast and stable photochromic oxazines for fluorescence switching. Langmuir. 2011 Oct 4;27(19):11773-11783. https://doi.org/10.1021/la201062h
Deniz, Erhan ; Tomasulo, Massimiliano ; Cusido, Janet ; Sortino, Salvatore ; Raymo, Francisco. / Fast and stable photochromic oxazines for fluorescence switching. In: Langmuir. 2011 ; Vol. 27, No. 19. pp. 11773-11783.
@article{eae2b8a5fa294ee189b28193a1ceecc5,
title = "Fast and stable photochromic oxazines for fluorescence switching",
abstract = "The stringent limitations imposed by diffraction on the spatial resolution of fluorescence microscopes demand the identification of viable strategies to switch fluorescence under optical control. In this context, the photoinduced and reversible transformations of photochromic compounds are particularly valuable. In fact, these molecules can be engineered to regulate the emission intensities of complementary fluorophores in response to optical stimulations. On the basis of this general design logic, we assembled a functional molecular construct consisting of a borondipyrromethene fluorophore and a nitrospiropyran photochrome and demonstrated that the emission of the former can be modulated with the interconversion of the latter. This fluorophore-photochrome dyad, however, has a slow switching speed and poor fatigue resistance. To improve both parameters, we developed a new family of photochromic switches based on the photoinduced opening and thermal closing of an oxazine ring. These compounds switch back and forth between ring-closed and -open isomers on nanosecond-microsecond timescales and tolerate thousands of switching cycles with no sign of degradation. In addition, the attachment of appropriate chromophoric fragments to their switchable oxazine ring can be exploited to either deactivate or activate fluorescence reversibly in response to illumination with a pair of exciting beams. Specifically, we assembled three dyads, each based on either a borondipyrromethene or a coumarin fluorophore and an oxazine photochrome, and modulated their fluorescence in a few microseconds with outstanding fatigue resistance. The unique photochemical and photophysical properties of our fluorophore-photochrome dyads can facilitate the development of switchable fluorophores for superresolution imaging and, ultimately, provide valuable molecular probes for the visualization of biological samples on the nanometer level.",
author = "Erhan Deniz and Massimiliano Tomasulo and Janet Cusido and Salvatore Sortino and Francisco Raymo",
year = "2011",
month = "10",
day = "4",
doi = "10.1021/la201062h",
language = "English",
volume = "27",
pages = "11773--11783",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "19",

}

TY - JOUR

T1 - Fast and stable photochromic oxazines for fluorescence switching

AU - Deniz, Erhan

AU - Tomasulo, Massimiliano

AU - Cusido, Janet

AU - Sortino, Salvatore

AU - Raymo, Francisco

PY - 2011/10/4

Y1 - 2011/10/4

N2 - The stringent limitations imposed by diffraction on the spatial resolution of fluorescence microscopes demand the identification of viable strategies to switch fluorescence under optical control. In this context, the photoinduced and reversible transformations of photochromic compounds are particularly valuable. In fact, these molecules can be engineered to regulate the emission intensities of complementary fluorophores in response to optical stimulations. On the basis of this general design logic, we assembled a functional molecular construct consisting of a borondipyrromethene fluorophore and a nitrospiropyran photochrome and demonstrated that the emission of the former can be modulated with the interconversion of the latter. This fluorophore-photochrome dyad, however, has a slow switching speed and poor fatigue resistance. To improve both parameters, we developed a new family of photochromic switches based on the photoinduced opening and thermal closing of an oxazine ring. These compounds switch back and forth between ring-closed and -open isomers on nanosecond-microsecond timescales and tolerate thousands of switching cycles with no sign of degradation. In addition, the attachment of appropriate chromophoric fragments to their switchable oxazine ring can be exploited to either deactivate or activate fluorescence reversibly in response to illumination with a pair of exciting beams. Specifically, we assembled three dyads, each based on either a borondipyrromethene or a coumarin fluorophore and an oxazine photochrome, and modulated their fluorescence in a few microseconds with outstanding fatigue resistance. The unique photochemical and photophysical properties of our fluorophore-photochrome dyads can facilitate the development of switchable fluorophores for superresolution imaging and, ultimately, provide valuable molecular probes for the visualization of biological samples on the nanometer level.

AB - The stringent limitations imposed by diffraction on the spatial resolution of fluorescence microscopes demand the identification of viable strategies to switch fluorescence under optical control. In this context, the photoinduced and reversible transformations of photochromic compounds are particularly valuable. In fact, these molecules can be engineered to regulate the emission intensities of complementary fluorophores in response to optical stimulations. On the basis of this general design logic, we assembled a functional molecular construct consisting of a borondipyrromethene fluorophore and a nitrospiropyran photochrome and demonstrated that the emission of the former can be modulated with the interconversion of the latter. This fluorophore-photochrome dyad, however, has a slow switching speed and poor fatigue resistance. To improve both parameters, we developed a new family of photochromic switches based on the photoinduced opening and thermal closing of an oxazine ring. These compounds switch back and forth between ring-closed and -open isomers on nanosecond-microsecond timescales and tolerate thousands of switching cycles with no sign of degradation. In addition, the attachment of appropriate chromophoric fragments to their switchable oxazine ring can be exploited to either deactivate or activate fluorescence reversibly in response to illumination with a pair of exciting beams. Specifically, we assembled three dyads, each based on either a borondipyrromethene or a coumarin fluorophore and an oxazine photochrome, and modulated their fluorescence in a few microseconds with outstanding fatigue resistance. The unique photochemical and photophysical properties of our fluorophore-photochrome dyads can facilitate the development of switchable fluorophores for superresolution imaging and, ultimately, provide valuable molecular probes for the visualization of biological samples on the nanometer level.

UR - http://www.scopus.com/inward/record.url?scp=80053312300&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80053312300&partnerID=8YFLogxK

U2 - 10.1021/la201062h

DO - 10.1021/la201062h

M3 - Article

C2 - 21591642

AN - SCOPUS:80053312300

VL - 27

SP - 11773

EP - 11783

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 19

ER -