Engineering single-molecule fluorescence with asymmetric nano-antennas

Single-molecule fluorescence detection (SMFD) is able to probe, one molecule at a time, dynamical processes that are crucial for understanding functional mechanisms in biosystems. Fluorescence in the near-infrared (NIR) offers improved signal to noise ratio (SNR) by reducing the scattering, absorption and autofluorescence from biological cellular or , and therefore, provides high imaging resolution with increased tissue penetration depths that are important for . However, most NIR-emitters suffer from low quantum yield and the weak NIR fluorescence signal makes the detection extremely difficult.

Plasmonic nanostructures are capable of converting localized electromagnetic energy into free radiation and vice versa. This capability makes them efficient nano-antennas for modulating molecular fluorescence. The plasmonic nano-antenna generally enhances the fluorescence of a nearby molecule by enhancing the excitation rate and the quantum yield of the molecule. In order to optimally enhance the fluorescence, the plasmonic mode of the nano-antenna has to 1) couple strongly to the molecule and 2) radiate strongly to free space. Simultaneously satisfying the two requirements poses a challenge that is impossible to overcome in conventional, symmetric plasmonic nanostructures.

(a) Schematic of double-bar nano-antenna coated with AIEE1000 molecules (black double ended arrows) in PMMA (light blue) on glass substrate (light grey). Inset shows the chemical structure of AIEE1000. (b-g) SEM images of fabricated nano-antennas with different bar-lengths. Credit: Wenqi Zhao, Xiaochaoran Tian, Zhening Fang, Shiyi Xiao, Meng Qiu, Qiong He, Wei Feng, Fuyou Li, Yuanbo Zhang, Lei Zhou, and Yan-Wen Tan

(a) Histogram of fluorescence enhancement with asymmetric double-bar antennas. Each histogram shows the distribution of fluorescence enhancement coming from molecules near asymmetric double-bar antennas with different bar-lengths. Maximums of simulated enhancement are indicated with blue dash-dotted lines (b) Fluorescence image of AIEE1000 in PMMA without antennas. (c) Fluorescence image of asymmetric antenna (left-half) and symmetric antenna (right-half) array coated with AIEE1000 in PMMA. Credit: Wenqi Zhao, Xiaochaoran Tian, Zhening Fang, Shiyi Xiao, Meng Qiu, Qiong He, Wei Feng, Fuyou Li, Yuanbo Zhang, Lei Zhou, and Yan-Wen Tan

Measurement of bleaching time on glass as a function of excitation power density displays an inverse proportional relationship (grey squares and grey line). While bleaching time of molecules on antenna-array are all longer than corresponding ones on glass (color symbols represent bleaching times on corresponding structure). Credit: Wenqi Zhao, Xiaochaoran Tian, Zhening Fang, Shiyi Xiao, Meng Qiu, Qiong He, Wei Feng, Fuyou Li, Yuanbo Zhang, Lei Zhou, and Yan-Wen Tan