Capping Ligand Size-Dependent LSPR Property Based on DNA Nanostructure-Mediated Morphological Evolution of Gold Nanorods for Ultrasensitive Visualization of Target DNA
Mengqi He, Shuai Chen, Jie Meng, Wei Shi, Kun Wang, Yong‐Liang Yu, Jianhua Wang
Abstract
Systematically tuning the structures and properties of noble-metal nanoparticles through biomolecule-mediated overgrowth is of significant importance for their applications in biosensing and imaging. Herein thiolated biomolecules with different concentrations and sizes (molecular weight and spatial structure) were used as a class of capping ligands to control the longitudinal surface plasmon resonance (LSPR) property of gold nanorods (GNRs). The LSPR peaks were red-shifted by increasing the capping agent concentration. The size effect could be divided to two aspects: (1) When the ligands are small molecules, the LSPR peak is blue-shifted as the size of the capping ligand increases. (2) When the ligands are macromolecular proteins, the LSPR property is similar to that of the overgrown nanoparticle (Au@gap@GNR) without thiolated biomolecules as capping agents. Interestingly, thiol-free and nonhomooligomeric DNA strands as capping agents present a similar influence in shaping the overgrowth of GNRs by varying their concentrations and sizes. In addition, the size effect of a DNA nanostructure was used to construct a ΔλLSPR-based catalytic nucleic acid biosensor using a DNA dendritic nanostructure as a capping agent combined with LSPR signals generated from the Au@gap@GNRs with morphological evolution. More importantly, the ΔλLSPR-based biosensor possesses three advantages in nucleic acid biosensing: (1) It is completely label- and wash-free, (2) it has an ultrahigh sensitivity and signal-to-noise ratio, and (3) it can be visualized without any instrumental aid, indicating a significant potential for ultrasensitive biosensing.