Controlling bulk optical properties of emissive polymersomes through intramembranous polymer-fluorophore interactions
Controlling bulk optical properties of emissive polymersomes through intramembranous polymer-fluorophore interactions
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DOI：
10.1021/cm062427w
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发表时间：
2007-03-20
影响因子：
8.6
通讯作者：
Therien, Michael J.
中科院分区：
文献类型：
--
作者：
Ghoroghchian, P. Peter;Frail, Paul R.;Therien, Michael J.
化学、工程和医学之间的交叉学科研究使自组装纳米材料具有新的生物化学和光电性能成为可能。我们最近已经证明，发射型聚合体，即含有基于卟啉的荧光团的聚合物囊泡，具有较大的集成发射振荡器强度和较窄的发射频带；这些纳米级组件可以进一步设计成在可见光和近红外(NIR)光谱域的离散波长下发光。因此，发射多聚体有效地定义了一类基于有机的软物质量子点类似物，这些类似物不仅具有令人印象深刻的光学性质，而且相对于无机荧光纳米粒子，还具有可调的物理和生物材料特性。在这里，我们扩展了我们对poly(ethyleneoxide)-block-poly(butadiene)-based囊泡的初步研究，以检查在其他聚合物系统中的荧光载体膜负载。通过调节荧光团辅助基团取代基和选择高分子链化学，我们能够预测地控制膜内聚合物-荧光团的相互作用；这些现象反过来影响到荧光团溶剂化的性质、局部介电环境和发射聚合物组装体中的发射量子产率。通过利用不同类型的产生囊泡的两嵌段共聚物，包括可生物可吸收的poly(ethyleneoxide)-block-poly(epsilon-caprolactone)(PEO-b-PCL)和poly(ethyleneoxide)-block-poly(gamma-methyl-epsilon-caprolactone)(PEO-b-PMCL)，我们确定了对工程纳米级光泡具有重要意义的一般原理。此外，这项工作预示着第一代完全可生物降解的荧光纳米颗粒适用于深部组织活体成像。
Interdisciplinary investigation at the interface of chemistry, engineering, and medicine has enabled the development of self-assembled nanomaterials with novel biochemical and electro-optical properties. We have recently shown that emissive polymersomes, polymer vesicles incorporating porphyrin-based fluorophores, feature large integrated-emission oscillator strengths and narrow emission bands; these nanoscale assemblies can be further engineered to fluoresce at discrete wavelengths throughout the visible and 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, but also 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 examine fluorophore membrane-loading in other polymersome systems. Through modulation of fluorophore ancilliary group substituents and choice of polymer chain chemistries, we are able to predictably control intramembranous polymer-fluorophore interactions; these phenomena, in turn, influence the nature of fluorophore solvation, local dielectric environment, and emission quantum yield within emissive polymersome assemblies. By utilizing different classes of vesicle-generating diblock copolymers, including bioresorbable poly(ethyleneoxide)-block-poly(epsilon-caprolactone) (PEO-b-PCL) and poly(ethyleneoxide)-block-poly(gamma-methyl-epsilon-caprolactone) (PEO-b-PMCL), we ascertain general principles important for engineering nanoscale optical vesicles. Further, this work heralds the first generation of fully biodegradable fluorescent nanoparticles suitable for deep-tissue in vivo imaging.