Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers

Self‐assembling filomicelles (FMs) are of great interest to nanomedicine due to their structural flexibility, extensive systemic circulation time, and amenability to unique “cylinder‐to‐sphere” morphological transitions. However, current fabrication techniques for preparing FMs are highly variable a...

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Autores principales:	Sophia Li, Sharan Bobbala, Michael P. Vincent, Mallika Modak, Yugang Liu, Evan A. Scott
Formato:	article
Lenguaje:	EN
Publicado:	Wiley-VCH 2021
Materias:	circulation time filaments flash nanoprecipitation flexibilities pi-stacking nanomaterials Biotechnology TP248.13-248.65 Medical technology R855-855.5
Acceso en línea:	https://doaj.org/article/bbefe2efe0ec45d4a38159a6dfc54171
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id	oai:doaj.org-article:bbefe2efe0ec45d4a38159a6dfc54171
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spelling	oai:doaj.org-article:bbefe2efe0ec45d4a38159a6dfc541712021-11-06T04:12:26ZPi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers2699-930710.1002/anbr.202100063https://doaj.org/article/bbefe2efe0ec45d4a38159a6dfc541712021-11-01T00:00:00Zhttps://doi.org/10.1002/anbr.202100063https://doaj.org/toc/2699-9307Self‐assembling filomicelles (FMs) are of great interest to nanomedicine due to their structural flexibility, extensive systemic circulation time, and amenability to unique “cylinder‐to‐sphere” morphological transitions. However, current fabrication techniques for preparing FMs are highly variable and difficult to scale. Herein, it is demonstrated that tetrablock copolymers composed of poly(ethylene glycol)‐b‐poly(propylene sulfide) (PEG‐b‐PPS) diblocks linked by a pi‐stacking perylene bisimide (PBI) moiety permit rapid, scalable, and facile assembly of FMs via the flash nanoprecipitation (FNP) method. Coassembling the tetrablocks and PEG‐b‐PPS diblocks at different molar ratios resulted in mixed PBI‐containing FMs (mPBI‐FM) with tunable length and flexibility. The flexibility of mPBI‐FM can be optimized to decrease uptake by macrophages in vivo, leading to increased circulation time versus (−)PBI‐FM without PBI tetrablocks after intravenous administration in mice. While PEG‐b‐PPS diblocks form FM within a narrow range of hydrophilic weight fractions, incorporation of pi‐stacking PBI groups expanded this range to increase favorability of FM assembly. Furthermore, the aggregation‐dependent fluorescence of PBI shifted during oxidation‐induced “cylinder‐to‐sphere” transitions of mPBI‐FM into micelles, resulting in a distinct emission wavelength for filamentous versus spherical nanostructures. Thus, incorporation of pi‐stacking allows for rapid, scalable assembly of FMs with tunable flexibility and stability for theranostic and nanomedicine applications.Sophia LiSharan BobbalaMichael P. VincentMallika ModakYugang LiuEvan A. ScottWiley-VCHarticlecirculation timefilamentsflash nanoprecipitationflexibilitiespi-stackingnanomaterialsBiotechnologyTP248.13-248.65Medical technologyR855-855.5ENAdvanced NanoBiomed Research, Vol 1, Iss 11, Pp n/a-n/a (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	circulation time filaments flash nanoprecipitation flexibilities pi-stacking nanomaterials Biotechnology TP248.13-248.65 Medical technology R855-855.5
spellingShingle	circulation time filaments flash nanoprecipitation flexibilities pi-stacking nanomaterials Biotechnology TP248.13-248.65 Medical technology R855-855.5 Sophia Li Sharan Bobbala Michael P. Vincent Mallika Modak Yugang Liu Evan A. Scott Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers
description	Self‐assembling filomicelles (FMs) are of great interest to nanomedicine due to their structural flexibility, extensive systemic circulation time, and amenability to unique “cylinder‐to‐sphere” morphological transitions. However, current fabrication techniques for preparing FMs are highly variable and difficult to scale. Herein, it is demonstrated that tetrablock copolymers composed of poly(ethylene glycol)‐b‐poly(propylene sulfide) (PEG‐b‐PPS) diblocks linked by a pi‐stacking perylene bisimide (PBI) moiety permit rapid, scalable, and facile assembly of FMs via the flash nanoprecipitation (FNP) method. Coassembling the tetrablocks and PEG‐b‐PPS diblocks at different molar ratios resulted in mixed PBI‐containing FMs (mPBI‐FM) with tunable length and flexibility. The flexibility of mPBI‐FM can be optimized to decrease uptake by macrophages in vivo, leading to increased circulation time versus (−)PBI‐FM without PBI tetrablocks after intravenous administration in mice. While PEG‐b‐PPS diblocks form FM within a narrow range of hydrophilic weight fractions, incorporation of pi‐stacking PBI groups expanded this range to increase favorability of FM assembly. Furthermore, the aggregation‐dependent fluorescence of PBI shifted during oxidation‐induced “cylinder‐to‐sphere” transitions of mPBI‐FM into micelles, resulting in a distinct emission wavelength for filamentous versus spherical nanostructures. Thus, incorporation of pi‐stacking allows for rapid, scalable assembly of FMs with tunable flexibility and stability for theranostic and nanomedicine applications.
format	article
author	Sophia Li Sharan Bobbala Michael P. Vincent Mallika Modak Yugang Liu Evan A. Scott
author_facet	Sophia Li Sharan Bobbala Michael P. Vincent Mallika Modak Yugang Liu Evan A. Scott
author_sort	Sophia Li
title	Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers
title_short	Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers
title_full	Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers
title_fullStr	Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers
title_full_unstemmed	Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers
title_sort	pi‐stacking enhances stability, scalability of formation, control over flexibility, and circulation time of polymeric filamentous nanocarriers
publisher	Wiley-VCH
publishDate	2021
url	https://doaj.org/article/bbefe2efe0ec45d4a38159a6dfc54171
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_version_	1718443939908812800

Pi‐Stacking Enhances Stability, Scalability of Formation, Control over Flexibility, and Circulation Time of Polymeric Filamentous Nanocarriers

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