Controlling Bulk Optical Properties of Emissive Polymersomes through Intramembranous Polymer-Fluorophore Interactions
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- 作者：P. Peter Ghoroghchian ; Paul R. Frail ; Guizhi Li ; John A. Zupancich ; Frank S. Bates ; Daniel A. Hammer ; Michael J. Therien
- 刊名：Chemistry of Materials
- 出版年：2007
- 出版时间：March 20, 2007
- 年：2007
- 卷：19
- 期：6
- 页码：1309 - 1318
- 全文大小：414K
- 年卷期：v.19,no.6(March 20, 2007)
- ISSN：1520-5002
文摘
Interdisciplinary investigation at the interface of chemistry, engineering, and medicine has enabled thedevelopment of self-assembled nanomaterials with novel biochemical and electro-optical properties. Wehave recently shown that emissive polymersomes, polymer vesicles incorporating porphyrin-basedfluorophores, feature large integrated-emission oscillator strengths and narrow emission bands; thesenanoscale assemblies can be further engineered to fluoresce at discrete wavelengths throughout the visibleand near-infrared (NIR) spectral domains. As such, emissive polymersomes effectively define an organic-based family of soft-matter quantum-dot analogs that possess not only impressive optical properties, butalso tunable physical and biomaterial characteristics relative to inorganic fluorescent nanoparticles. Here,we expand upon our initial studies on poly(ethyleneoxide)-block-poly(butadiene)-based vesicles to examinefluorophore membrane-loading in other polymersome systems. Through modulation of fluorophoreancilliary group substituents and choice of polymer chain chemistries, we are able to predictably controlintramembranous polymer-fluorophore interactions; these phenomena, in turn, influence the nature offluorophore solvation, local dielectric environment, and emission quantum yield within emissivepolymersome assemblies. By utilizing different classes of vesicle-generating diblock copolymers, includingbioresorbable poly(ethyleneoxide)-block-poly(
-caprolactone) (PEO-b-PCL) and poly(ethyleneoxide)-block-poly(
-methyl--caprolactone) (PEO-b-PMCL), we ascertain general principles important forengineering nanoscale optical vesicles. Further, this work heralds the first generation of fully biodegradablefluorescent nanoparticles suitable for deep-tissue in vivo imaging.
-caprolactone) (PEO-b-PCL) and poly(ethyleneoxide)-block-poly(-methyl--caprolactone) (PEO-b-PMCL), we ascertain general principles important forengineering nanoscale optical vesicles. Further, this work heralds the first generation of fully biodegradablefluorescent nanoparticles suitable for deep-tissue in vivo imaging.