Supramolecular Strategies To Construct Biocompatible and Photoswitchable Fluorescent Assemblies

Ibrahim Yildiz, Stefania Impellizzeri, Erhan Deniz, Bridgeen Callan, John Callan, Francisco M. Raymo

Research output: Contribution to journalArticle

113 Citations (Scopus)

Abstract

We designed and synthesized an amphiphilic copolymer with pendant hydrophobic decyl and hydrophilic poly(ethylene glycol) chains along a common poly(methacrylate) backbone. This macromolecular construct captures hydrophobic boron dipyrromethene fluorophores and hydrophobic spiropyran photochromes and transfers mixtures of both components in aqueous environments. Within the resulting hydrophilic supramolecular assemblies, the spiropyran components retain their photochemical properties and switch reversibly to the corresponding merocyanine isomers upon ultraviolet illumination. Their photoinduced transformations activate intermolecular electron and energy transfer pathways, which culminate in the quenching of the boron dipyrromethene fluorescence. As a result, the emission intensity of these supramolecular constructs can be modulated in aqueous environments under optical control. Furthermore, the macromolecular envelope around the fluorescent and photochromic components can cross the membrane of Chinese hamster ovarian cells and transport its cargo unaffected into the cytosol. Indeed, the fluorescence of these supramolecular constructs can be modulated also intracellularly by operating the photochromic component with optical inputs. In addition, cytotoxicity tests demonstrate that these supramolecular assemblies and the illumination conditions required for their operation have essentially no influence on cell viability. Thus, supramolecular events can be invoked to construct fluorescent and photoswitchable systems from separate components, while imposing aqueous solubility and biocompatibility on the resulting assemblies. In principle, this simple protocol can evolve into a general strategy to deliver and operate intracellularly functional molecular components under optical control.
LanguageEnglish
Pages871-879
JournalJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume133
Issue number4
DOIs
Publication statusPublished - Feb 2011

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Boron
Lighting
Fluorescence
Methacrylates
Fluorophores
Cytotoxicity
Biocompatibility
Isomers
Energy transfer
Polyethylene glycols
Quenching
Copolymers
Solubility
Cells
Switches
Membranes
Electrons
dipyrromethene
spiropyran
merocyanine

Cite this

Yildiz, Ibrahim ; Impellizzeri, Stefania ; Deniz, Erhan ; Callan, Bridgeen ; Callan, John ; Raymo, Francisco M. / Supramolecular Strategies To Construct Biocompatible and Photoswitchable Fluorescent Assemblies. In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 2011 ; Vol. 133, No. 4. pp. 871-879.
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Supramolecular Strategies To Construct Biocompatible and Photoswitchable Fluorescent Assemblies. / Yildiz, Ibrahim; Impellizzeri, Stefania; Deniz, Erhan; Callan, Bridgeen; Callan, John; Raymo, Francisco M.

In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 133, No. 4, 02.2011, p. 871-879.

Research output: Contribution to journalArticle

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AB - We designed and synthesized an amphiphilic copolymer with pendant hydrophobic decyl and hydrophilic poly(ethylene glycol) chains along a common poly(methacrylate) backbone. This macromolecular construct captures hydrophobic boron dipyrromethene fluorophores and hydrophobic spiropyran photochromes and transfers mixtures of both components in aqueous environments. Within the resulting hydrophilic supramolecular assemblies, the spiropyran components retain their photochemical properties and switch reversibly to the corresponding merocyanine isomers upon ultraviolet illumination. Their photoinduced transformations activate intermolecular electron and energy transfer pathways, which culminate in the quenching of the boron dipyrromethene fluorescence. As a result, the emission intensity of these supramolecular constructs can be modulated in aqueous environments under optical control. Furthermore, the macromolecular envelope around the fluorescent and photochromic components can cross the membrane of Chinese hamster ovarian cells and transport its cargo unaffected into the cytosol. Indeed, the fluorescence of these supramolecular constructs can be modulated also intracellularly by operating the photochromic component with optical inputs. In addition, cytotoxicity tests demonstrate that these supramolecular assemblies and the illumination conditions required for their operation have essentially no influence on cell viability. Thus, supramolecular events can be invoked to construct fluorescent and photoswitchable systems from separate components, while imposing aqueous solubility and biocompatibility on the resulting assemblies. In principle, this simple protocol can evolve into a general strategy to deliver and operate intracellularly functional molecular components under optical control.

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