Photochemistry in Confined Environments for Single-Chain Nanoparticle Design
Photochemistry in Confined Environments for Single-Chain Nanoparticle Design
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DOI：
10.1021/jacs.8b04531
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发表时间：
2018-08-01
影响因子：
15
通讯作者：
Barner-Kowollik, Christopher
中科院分区：
文献类型：
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作者：
Frisch, Hendrik;Menzel, Jan P.;Barner-Kowollik, Christopher
模仿自然界的蛋白质范例，单链纳米颗粒（SCNP）是一类新兴的纳米材料。SCNP的合成途径受到超低浓度、苛刻的反应条件和单链崩溃后复杂的分离程序的限制。在此，我们利用苯乙烯基芘单元的可见光光二聚作为链折叠机制。重要的是，它们沿聚合物链沿着的位置产生了一个封闭的环境，显著增加了光环加成量子产率，使得能够在无与伦比的高浓度下进行单链折叠而无需后续纯化。重要的是，增强的光反应性允许在λ = 445 nm LED照射下在几分钟内以及通过环境光进行单链折叠，从而实现前所未有的折叠系统。本文证明的通过空间限制的量子产率的增强用作所有光化学连接系统的蓝图。
Emulating nature's protein paradigm, single-chain nanoparticles (SCNP) are an emerging class of nanomaterials. Synthetic access to SCNPs is limited by ultralow concentrations, demanding reaction conditions, and complex isolation procedures after single-chain collapse. Herein, we exploit the visible light photodimerization of styrylpyrene units as chain folding mechanism. Critically, their positioning along the polymer chain creates a confined environment, increasing the photocycloaddition quantum yields dramatically, enabling single-chain folding at unrivaled high concentrations without subsequent purification. Importantly, the enhanced photoreactivity allows for single-chain folding at lambda = 445 nm LED-irradiation within minutes as well as via ambient light, enabling an unprecedented folding system. The herein demonstrated enhancement of quantum yields by steric confinement serves as a blueprint for all photochemical ligation systems.