Wavelength-Selective Coupling and Decoupling of Polymer Chains via Reversible [2 + 2] Photocycloaddition of Styrylpyrene for Construction of Cytocompatible Photodynamic Hydrogels

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Abstract

Reversible photocycloaddition reactions have previously been employed in chemical cross-linking for the preparation of biomaterial scaffolds. However, the processes require activation by high-energy UV light, rendering them unsuitable for modification in biological environments. Here we demonstrate that the [2 + 2] photocycloaddition of styrylpyrene can be activated by visible light at λ = 400-500 nm, enabling rapid and effective conjugation and cross-linking of poly(ethylene glycol) (PEG) in water and under mild irradiation conditions (I = 20 mW cm-2). Notably, the reversion of the cycloaddition can be triggered by low-energy UV light at λ = 340 nm, which allows for efficient cleavage of the dimer adduct. Using this wavelength-gated reversible photochemical reaction we are able to prepare PEG hydrogels and modulate their mechanical properties in a bidirectional manner. We also demonstrate healing of the fractured hydrogel by external light triggers. Furthermore, we show that human mesenchymal stem cells can be encapsulated within the gels with high viability post encapsulation. This photochemical approach is therefore anticipated to be highly useful in studies of cell mechanotransduction, with relevance to disease progression and tissue regeneration.

Original languageEnglish
Pages (from-to)464-469
Number of pages6
JournalACS Macro Letters
Volume7
Issue number4
DOIs
Publication statusPublished - 17 Apr 2018

Cite this

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title = "Wavelength-Selective Coupling and Decoupling of Polymer Chains via Reversible [2 + 2] Photocycloaddition of Styrylpyrene for Construction of Cytocompatible Photodynamic Hydrogels",
abstract = "Reversible photocycloaddition reactions have previously been employed in chemical cross-linking for the preparation of biomaterial scaffolds. However, the processes require activation by high-energy UV light, rendering them unsuitable for modification in biological environments. Here we demonstrate that the [2 + 2] photocycloaddition of styrylpyrene can be activated by visible light at λ = 400-500 nm, enabling rapid and effective conjugation and cross-linking of poly(ethylene glycol) (PEG) in water and under mild irradiation conditions (I = 20 mW cm-2). Notably, the reversion of the cycloaddition can be triggered by low-energy UV light at λ = 340 nm, which allows for efficient cleavage of the dimer adduct. Using this wavelength-gated reversible photochemical reaction we are able to prepare PEG hydrogels and modulate their mechanical properties in a bidirectional manner. We also demonstrate healing of the fractured hydrogel by external light triggers. Furthermore, we show that human mesenchymal stem cells can be encapsulated within the gels with high viability post encapsulation. This photochemical approach is therefore anticipated to be highly useful in studies of cell mechanotransduction, with relevance to disease progression and tissue regeneration.",
author = "Truong, {Vinh X.} and Fanyi Li and Francesca Ercole and Forsythe, {John S.}",
year = "2018",
month = "4",
day = "17",
doi = "10.1021/acsmacrolett.8b00099",
language = "English",
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pages = "464--469",
journal = "ACS Macro Letters",
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publisher = "American Chemical Society",
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T1 - Wavelength-Selective Coupling and Decoupling of Polymer Chains via Reversible [2 + 2] Photocycloaddition of Styrylpyrene for Construction of Cytocompatible Photodynamic Hydrogels

AU - Truong, Vinh X.

AU - Li, Fanyi

AU - Ercole, Francesca

AU - Forsythe, John S.

PY - 2018/4/17

Y1 - 2018/4/17

N2 - Reversible photocycloaddition reactions have previously been employed in chemical cross-linking for the preparation of biomaterial scaffolds. However, the processes require activation by high-energy UV light, rendering them unsuitable for modification in biological environments. Here we demonstrate that the [2 + 2] photocycloaddition of styrylpyrene can be activated by visible light at λ = 400-500 nm, enabling rapid and effective conjugation and cross-linking of poly(ethylene glycol) (PEG) in water and under mild irradiation conditions (I = 20 mW cm-2). Notably, the reversion of the cycloaddition can be triggered by low-energy UV light at λ = 340 nm, which allows for efficient cleavage of the dimer adduct. Using this wavelength-gated reversible photochemical reaction we are able to prepare PEG hydrogels and modulate their mechanical properties in a bidirectional manner. We also demonstrate healing of the fractured hydrogel by external light triggers. Furthermore, we show that human mesenchymal stem cells can be encapsulated within the gels with high viability post encapsulation. This photochemical approach is therefore anticipated to be highly useful in studies of cell mechanotransduction, with relevance to disease progression and tissue regeneration.

AB - Reversible photocycloaddition reactions have previously been employed in chemical cross-linking for the preparation of biomaterial scaffolds. However, the processes require activation by high-energy UV light, rendering them unsuitable for modification in biological environments. Here we demonstrate that the [2 + 2] photocycloaddition of styrylpyrene can be activated by visible light at λ = 400-500 nm, enabling rapid and effective conjugation and cross-linking of poly(ethylene glycol) (PEG) in water and under mild irradiation conditions (I = 20 mW cm-2). Notably, the reversion of the cycloaddition can be triggered by low-energy UV light at λ = 340 nm, which allows for efficient cleavage of the dimer adduct. Using this wavelength-gated reversible photochemical reaction we are able to prepare PEG hydrogels and modulate their mechanical properties in a bidirectional manner. We also demonstrate healing of the fractured hydrogel by external light triggers. Furthermore, we show that human mesenchymal stem cells can be encapsulated within the gels with high viability post encapsulation. This photochemical approach is therefore anticipated to be highly useful in studies of cell mechanotransduction, with relevance to disease progression and tissue regeneration.

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U2 - 10.1021/acsmacrolett.8b00099

DO - 10.1021/acsmacrolett.8b00099

M3 - Article

VL - 7

SP - 464

EP - 469

JO - ACS Macro Letters

JF - ACS Macro Letters

SN - 2161-1653

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