Supramolecular Strategies To Construct Biocompatible andPhotoswitchable Fluorescent Assemblies

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

Research output: Contribution to journalArticle

Abstract

We designed and synthesized an amphiphiliccopolymer with pendant hydrophobic decyl and hydrophilicpoly(ethylene glycol) chains along a common poly(methacrylate)backbone. This macromolecular construct captures hydrophobicboron dipyrromethene fluorophores and hydrophobicspiropyran photochromes and transfers mixtures of bothcomponents in aqueous environments. Within the resultinghydrophilic supramolecular assemblies, the spiropyran componentsretain their photochemical properties and switchreversibly to the corresponding merocyanine isomers upon ultraviolet illumination. Their photoinduced transformations activateintermolecular 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 opticalcontrol. Furthermore, the macromolecular envelope around the fluorescent and photochromic components can cross themembrane of Chinese hamster ovarian cells and transport its cargo unaffected into the cytosol. Indeed, the fluorescence of thesesupramolecular constructs can be modulated also intracellularly by operating the photochromic component with optical inputs. Inaddition, cytotoxicity tests demonstrate that these supramolecular assemblies and the illumination conditions required for theiroperation have essentially no influence on cell viability. Thus, supramolecular events can be invoked to construct fluorescent andphotoswitchable systems from separate components, while imposing aqueous solubility and biocompatibility on the resultingassemblies. In principle, this simple protocol can evolve into a general strategy to deliver and operate intracellularly functionalmolecular components under optical control.
LanguageEnglish
Pages871-879
JournalJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume133
DOIs
Publication statusPublished - 20 Aug 2010

Fingerprint

Lighting
Fluorescence
Boron
Ethylene Glycol
Methacrylates
Fluorophores
Cytotoxicity
Biocompatibility
Isomers
Energy transfer
Quenching
Solubility
Cells
Electrons
dipyrromethene
merocyanine
spiropyran

Cite this

Yildiz, Ibrahim ; Impellizzeri, Stefania ; Deniz, Erhan ; McCaughan, Bridgeen ; Callan, John ; Raymo, Francisco. / Supramolecular Strategies To Construct Biocompatible andPhotoswitchable Fluorescent Assemblies. In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 2010 ; Vol. 133. pp. 871-879.
@article{f79442f2201a4c8a8f1c7b62921ecde0,
title = "Supramolecular Strategies To Construct Biocompatible andPhotoswitchable Fluorescent Assemblies",
abstract = "We designed and synthesized an amphiphiliccopolymer with pendant hydrophobic decyl and hydrophilicpoly(ethylene glycol) chains along a common poly(methacrylate)backbone. This macromolecular construct captures hydrophobicboron dipyrromethene fluorophores and hydrophobicspiropyran photochromes and transfers mixtures of bothcomponents in aqueous environments. Within the resultinghydrophilic supramolecular assemblies, the spiropyran componentsretain their photochemical properties and switchreversibly to the corresponding merocyanine isomers upon ultraviolet illumination. Their photoinduced transformations activateintermolecular 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 opticalcontrol. Furthermore, the macromolecular envelope around the fluorescent and photochromic components can cross themembrane of Chinese hamster ovarian cells and transport its cargo unaffected into the cytosol. Indeed, the fluorescence of thesesupramolecular constructs can be modulated also intracellularly by operating the photochromic component with optical inputs. Inaddition, cytotoxicity tests demonstrate that these supramolecular assemblies and the illumination conditions required for theiroperation have essentially no influence on cell viability. Thus, supramolecular events can be invoked to construct fluorescent andphotoswitchable systems from separate components, while imposing aqueous solubility and biocompatibility on the resultingassemblies. In principle, this simple protocol can evolve into a general strategy to deliver and operate intracellularly functionalmolecular components under optical control.",
author = "Ibrahim Yildiz and Stefania Impellizzeri and Erhan Deniz and Bridgeen McCaughan and John Callan and Francisco Raymo",
year = "2010",
month = "8",
day = "20",
doi = "10.1021/ja107341f",
language = "English",
volume = "133",
pages = "871--879",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",

}

Supramolecular Strategies To Construct Biocompatible andPhotoswitchable Fluorescent Assemblies. / Yildiz, Ibrahim; Impellizzeri, Stefania; Deniz, Erhan; McCaughan, Bridgeen; Callan, John; Raymo, Francisco.

In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 133, 20.08.2010, p. 871-879.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Supramolecular Strategies To Construct Biocompatible andPhotoswitchable Fluorescent Assemblies

AU - Yildiz, Ibrahim

AU - Impellizzeri, Stefania

AU - Deniz, Erhan

AU - McCaughan, Bridgeen

AU - Callan, John

AU - Raymo, Francisco

PY - 2010/8/20

Y1 - 2010/8/20

N2 - We designed and synthesized an amphiphiliccopolymer with pendant hydrophobic decyl and hydrophilicpoly(ethylene glycol) chains along a common poly(methacrylate)backbone. This macromolecular construct captures hydrophobicboron dipyrromethene fluorophores and hydrophobicspiropyran photochromes and transfers mixtures of bothcomponents in aqueous environments. Within the resultinghydrophilic supramolecular assemblies, the spiropyran componentsretain their photochemical properties and switchreversibly to the corresponding merocyanine isomers upon ultraviolet illumination. Their photoinduced transformations activateintermolecular 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 opticalcontrol. Furthermore, the macromolecular envelope around the fluorescent and photochromic components can cross themembrane of Chinese hamster ovarian cells and transport its cargo unaffected into the cytosol. Indeed, the fluorescence of thesesupramolecular constructs can be modulated also intracellularly by operating the photochromic component with optical inputs. Inaddition, cytotoxicity tests demonstrate that these supramolecular assemblies and the illumination conditions required for theiroperation have essentially no influence on cell viability. Thus, supramolecular events can be invoked to construct fluorescent andphotoswitchable systems from separate components, while imposing aqueous solubility and biocompatibility on the resultingassemblies. In principle, this simple protocol can evolve into a general strategy to deliver and operate intracellularly functionalmolecular components under optical control.

AB - We designed and synthesized an amphiphiliccopolymer with pendant hydrophobic decyl and hydrophilicpoly(ethylene glycol) chains along a common poly(methacrylate)backbone. This macromolecular construct captures hydrophobicboron dipyrromethene fluorophores and hydrophobicspiropyran photochromes and transfers mixtures of bothcomponents in aqueous environments. Within the resultinghydrophilic supramolecular assemblies, the spiropyran componentsretain their photochemical properties and switchreversibly to the corresponding merocyanine isomers upon ultraviolet illumination. Their photoinduced transformations activateintermolecular 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 opticalcontrol. Furthermore, the macromolecular envelope around the fluorescent and photochromic components can cross themembrane of Chinese hamster ovarian cells and transport its cargo unaffected into the cytosol. Indeed, the fluorescence of thesesupramolecular constructs can be modulated also intracellularly by operating the photochromic component with optical inputs. Inaddition, cytotoxicity tests demonstrate that these supramolecular assemblies and the illumination conditions required for theiroperation have essentially no influence on cell viability. Thus, supramolecular events can be invoked to construct fluorescent andphotoswitchable systems from separate components, while imposing aqueous solubility and biocompatibility on the resultingassemblies. In principle, this simple protocol can evolve into a general strategy to deliver and operate intracellularly functionalmolecular components under optical control.

U2 - 10.1021/ja107341f

DO - 10.1021/ja107341f

M3 - Article

VL - 133

SP - 871

EP - 879

JO - Journal of the American Chemical Society

T2 - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -