Effects of Amine Linkers with Different Carbon Chain Lengths at Guanine-Rich Polynucleotides on Chemical Interface Damping in Single Gold Nanorods

Abstract

DNA-functionalized gold nanoparticles (AuNPs) are used for various bioapplications, such as biosensor development and drug delivery. Nevertheless, no study has reported the effect of polynucleotide chains on chemical interface damping (CID), the most recently proposed plasmon damping pathway in single AuNPs. In this study, we conducted total internal reflection scattering measurements of gold nanorods (AuNRs) to reveal the CID effect induced by amine (NH2)-linked polynucleotides (or DNA) with guanine-rich sequences through the interaction between nitrogen and Au surfaces. Additionally, we elucidated the effect of a linear hydrocarbon chain length between NH2 and DNA (NH2–Cn–DNA, n = 6, 12, 18, 24) on spectral changes in single AuNRs. The localized surface plasmon resonance (LSPR) linewidth increased with an increasing number of linear carbon, from 6 to 24, due to the increase in van der Waals forces. Second, the effect of the direction (5′ or 3′ ends) of DNA attachment to the AuNR surfaces on LSPR spectral changes was investigated, and there was no significant difference in LSPR wavelength and full linewidth at half-maximum shifts caused by the DNA attachment directions (5′ or 3′ ends). Third, guanine-rich DNA can fold into four-stranded secondary structures called G-quadruplexes (GQs). We demonstrated the effect of linear carbon chain length, between NH2 and GQs, on CID in single AuNRs. Lastly, a label-free detection of DNA hybridization events on single AuNRs was demonstrated for sensing applications. Thus, we provide an insight into the effect of amine-functionalized guanine-rich DNA with different carbon chains on LSPR spectral changes, including CID in single AuNRs.