Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
J Am Chem Soc. 2013 Feb 27;135(8):3011-6. doi: 10.1021/ja3078472. Epub 2013 Feb 12.
The placement of fluorophores in close proximity to metal nanoparticle surfaces is proposed to enhance several photophysical properties of the dyes, potentially leading to improved quantum yields and decreased photobleaching. It is difficult in practice, however, to establish and maintain the nanoscale distances that are required to maximize these effects. The type of metal, size, and shape of the nanoparticle, the physical distance separating the metal nanoparticle from the organic dye, and the spectral properties of the fluorophore itself are all proposed to influence the quantum yield and lifetime. This results in a complex behavior that can lead to either enhanced or quenched fluorescence in different contexts. In this report, we describe a well-defined system that can be used to explore these effects, while physically preventing the fluorophores from contacting the nanoparticle surfaces. The basis of this system is the spherical protein capsid of bacteriophage MS2, which was used to house gold particles within its interior volume. The exterior surface of each capsid was then modified with Alexa Fluor 488 (AF 488) labeled DNA strands. By placing AF 488 dyes at distances of 3, 12, and 24 bp from the surface of capsids containing 10 nm gold nanoparticles, fluorescence intensity enhancements of 2.2, 1.2, and 1.0 were observed, respectively. A corresponding decrease in fluorescence lifetime was observed for each distance. Because of its well-defined and modular nature, this architecture allows the rapid exploration of the many variables involved in metal-controlled fluorescence, leading to a better understanding of this phenomenon.
将荧光团放置在靠近金属纳米粒子表面的位置,据推测可以增强染料的几种光物理性质,从而潜在地提高量子产率并减少光漂白。然而,在实践中,很难建立和维持纳米尺度的距离,而这些距离是最大限度发挥这些效果所必需的。金属的类型、纳米粒子的尺寸和形状、金属纳米粒子与有机染料之间的物理距离以及荧光团本身的光谱性质都被认为会影响量子产率和寿命。这导致了一种复杂的行为,在不同的情况下可能会导致荧光增强或猝灭。在本报告中,我们描述了一个可以用来探索这些效应的明确定义的系统,同时物理上防止荧光团与纳米粒子表面接触。该系统的基础是噬菌体 MS2 的球形蛋白衣壳,它被用来将金颗粒容纳在其内部体积中。然后,每个衣壳的外表面都用 Alexa Fluor 488(AF 488)标记的 DNA 链进行修饰。通过将 AF 488 染料放置在距离包含 10nm 金纳米粒子的衣壳表面 3、12 和 24bp 的位置,观察到荧光强度分别增强了 2.2、1.2 和 1.0。对于每个距离,还观察到荧光寿命的相应降低。由于其明确的和模块化的性质,这种架构允许快速探索金属控制荧光中涉及的许多变量,从而更好地理解这种现象。